JP2024003008A - Photosensitive transfer material, method for producing resin pattern, method for producing conductive pattern, and touch sensor - Google Patents

Abstract

To provide a photosensitive transfer material that forms a resin pattern with reduced occurrence of pinholes, and an application thereof.SOLUTION: Provided are a photosensitive transfer material and an application thereof. The photosensitive transfer material comprises a temporary support and a photosensitive resin layer in that order. The temporary support is a polyester film consisting of two or more layers, where at least one of the surface layers does not contain filler.SELECTED DRAWING: Figure 1

Description

The present disclosure relates to a photosensitive transfer material, a method for manufacturing a resin pattern, a method for manufacturing a conductive pattern, and a touch sensor.

In display devices (eg, organic electroluminescent (EL) display devices and liquid crystal display devices) including a touch panel such as a capacitive input device, the touch panel includes a conductive pattern. The conductive pattern is used, for example, as a sensor in a visual recognition section, peripheral wiring, or lead-out wiring. In the manufacturing method of patterns such as conductive patterns and resin patterns, for example, a step of providing a photosensitive resin layer and a temporary support on a substrate using a photosensitive transfer material, a pattern exposure of the photosensitive resin layer through the temporary support, etc. A method including a step of developing the exposed photosensitive resin layer is widely adopted.

In order to avoid a decrease in resolution due to foreign substances contained in the temporary support, JP 2019-101405A discloses a photosensitive resin laminate roll in which the number of fine particles with a diameter of 2 μm or more is limited. .

As the definition of conductive patterns increases, or in other words, the required resolution improves, failures (especially pinholes) of conductive patterns due to foreign matter (e.g. coarse particles) contained in the temporary support are becoming more common. It's becoming obvious. Foreign matter contained in the temporary support inhibits exposure of the photosensitive resin layer and causes failures (for example, pinholes) in the resin pattern. For example, in etching for forming a conductive pattern, if a resin pattern containing pinholes is used as a protective film, pinholes will occur in the conductive pattern. Therefore, there is a need to reduce pinholes that occur in resin patterns.

An embodiment of the present disclosure aims to provide a photosensitive transfer material that forms a resin pattern in which the generation of pinholes is suppressed.
Another embodiment of the present disclosure aims to provide a method for manufacturing a resin pattern in which the generation of pinholes is suppressed.
Another embodiment of the present disclosure aims to provide a method for manufacturing a conductive pattern in which the generation of pinholes is suppressed.
Another embodiment of the present disclosure aims to provide a touch sensor including a conductive pattern in which the generation of pinholes is suppressed.

The present disclosure includes the following aspects.
<1> A temporary support and a photosensitive resin layer are included in this order, the critical resolution of the photosensitive resin layer is defined as X μm, and the reference diameter of the particles is expressed by the formula (1): Y=0.75× A photosensitive transfer material, wherein the number of particles having a diameter of Yμm or more in the temporary support is 15 particles/cm ² or less when defined as Yμm represented by X.
<2> The photosensitive transfer material according to <1>, wherein the number of particles having a diameter of 10.5 μm or more in the temporary support is 1.0 pieces/cm ² or less.
<3> The photosensitive transfer material according to <1> or <2>, wherein the temporary support has a thickness of 16 μm or less.
<4> The photosensitive transfer material according to any one of <1> to <3>, wherein the photosensitive resin layer has a thickness of 5 μm or less.

<5> A photosensitive material comprising a temporary support and a photosensitive resin layer in this order, wherein the temporary support is a polyester film consisting of two or more layers, and at least one surface layer does not contain a filler. Sex transfer material.
<6> The photosensitive transfer material according to <5>, wherein the surface layer on the photosensitive resin layer side of the temporary support does not contain a filler.
<7> If the critical resolution of the photosensitive resin layer is defined as X μm and the reference diameter of the particles is defined as Y μm expressed by formula (1): Y=0.75×X, Y μm in the temporary support The photosensitive transfer material according to <5> or <6>, wherein the number of particles having the above diameter is 15 particles/cm ² or less.
<8> The photosensitive transfer material according to any one of <5> to <7>, wherein the surface of the temporary support opposite to the photosensitive resin layer has an arithmetic mean roughness Ra of 1 nm to 50 nm. .
<9> The photosensitive transfer material according to any one of <5> to <8>, wherein the surface layer has a phase-separated structure.
<10> The photosensitive transfer material according to any one of <5> to <9>, wherein the surface layer contains a polyester resin having an alicyclic structure.
<11> The photosensitive transfer material according to <10>, wherein the alicyclic structure is a cyclohexane ring.
<12> The photosensitive transfer material according to <10> or <11>, wherein the surface layer contains copolymerized polyethylene terephthalate containing isophthalic acid as a copolymerization component.

<13> A method for manufacturing a resin pattern using the photosensitive transfer material according to any one of <1> to <12>, comprising the steps of preparing a substrate and contacting the photosensitive transfer material to the substrate. a step of arranging a photosensitive resin layer and a temporary support on the substrate in this order, a step of exposing the photosensitive resin layer in a pattern, and developing the exposed photosensitive resin layer, A method for manufacturing a resin pattern, comprising: forming a resin pattern.
<14> The method for manufacturing a resin pattern according to <13>, wherein the resin pattern has a line width of 10 μm or less.
<15> A method for manufacturing a conductive pattern using the photosensitive transfer material according to any one of <1> to <12>, comprising: preparing a substrate including a conductive layer; and applying the photosensitive layer to the substrate. A step of placing a photosensitive resin layer and a temporary support on the substrate in this order by bringing a transfer material into contact with the substrate, a step of exposing the photosensitive resin layer to pattern light, and a step of exposing the exposed photosensitive resin layer to light. A method for producing a conductive pattern, comprising the steps of developing to form a resin pattern, and etching the conductive layer not covered by the resin pattern to form a conductive pattern.
<16> A touch sensor including a conductive pattern obtained by the method for manufacturing a conductive pattern described in <15>.

According to an embodiment of the present disclosure, a photosensitive transfer material is provided that forms a resin pattern in which the generation of pinholes is suppressed.
According to another embodiment of the present disclosure, a method for manufacturing a resin pattern in which the generation of pinholes is suppressed is provided.
According to another embodiment of the present disclosure, a method for manufacturing a conductive pattern in which the generation of pinholes is suppressed is provided.
According to another embodiment of the present disclosure, there is provided a touch sensor including a conductive pattern in which pinhole generation is suppressed.

FIG. 1 is a schematic side view showing a layer structure of a photosensitive transfer material according to the present disclosure. FIG. 3 is a schematic side view showing another layer structure of the photosensitive transfer material according to the present disclosure. FIG. 3 is a schematic side view showing another layer structure of the photosensitive transfer material according to the present disclosure.

Embodiments of the present disclosure will be described in detail below. The present disclosure is not limited to the following embodiments. The following embodiments may be modified as appropriate within the scope of the present disclosure.

When embodiments of the present disclosure are described with reference to the drawings, explanations of overlapping components and symbols in the drawings may be omitted. Components indicated using the same reference numerals in the drawings mean the same components. The proportions of dimensions in the drawings do not necessarily represent the proportions of actual dimensions.

In the present disclosure, a numerical range indicated using "-" indicates a range that includes the numerical values written before and after "-" as the lower limit and upper limit, respectively. In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit described in a certain numerical range may be replaced with the upper limit or lower limit of another numerical range described step by step. Furthermore, in the numerical ranges described in this disclosure, the upper limit or lower limit described in a certain numerical range may be replaced with the value shown in the Examples.

In this disclosure, the term "process" includes not only an independent process but also a process that is not clearly distinguishable from other processes, as long as the intended purpose of the process is achieved. .

In the present disclosure, "mass %" and "weight %" have the same meaning, and "mass parts" and "weight parts" have the same meaning.

In the present disclosure, if a plurality of substances corresponding to a certain component are present in the composition, the amount of the above component in the composition refers to the total amount of the plurality of substances present in the composition, unless otherwise specified. means.

In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.

In this disclosure, ordinal terms (e.g., "first" and "second") are terms used to distinguish between multiple components, and limit the number of components and the superiority of the components. isn't it.

In the present disclosure, groups (atomic groups) in which substitution and unsubstitution are not indicated include groups having a substituent and groups having no substituent. For example, the expression "alkyl group" includes an alkyl group having a substituent (substituted alkyl group) and an alkyl group having no substituent (unsubstituted alkyl group).

In the present disclosure, chemical structural formulas may be represented by simplified structural formulas that omit hydrogen atoms.

In the present disclosure, "(meth)acrylic acid" means acrylic acid or methacrylic acid.

In this disclosure, "(meth)acrylate" means acrylate or methacrylate.

In the present disclosure, "(meth)acryloyl group" means an acryloyl group or a methacryloyl group.

In the present disclosure, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of the light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet rays and extreme ultraviolet lithography (EUV (Extreme ultraviolet lithography) light) typified by excimer lasers, and active rays (active energy rays) such as X-rays. .

In this disclosure, unless otherwise specified, weight average molecular weight (Mw) and number average molecular weight (Mn) are those of TSKgel GMHxL (Tosoh Corporation), TSKgel G4000HxL (Tosoh Corporation), and TSKgel G2000HxL (Tosoh Corporation) columns. The compound in tetrahydrofuran (THF) was detected using a differential refractometer using a Gel Permeation Chromatography (GPC) analyzer using GPC, and the molecular weight was calculated using polystyrene as a standard substance.

In the present disclosure, unless otherwise specified, the refractive index is a value measured using an ellipsometer at a wavelength of 550 nm.

In the present disclosure, "solid content" refers to all components of the object excluding the solvent.

<Photosensitive transfer material>
The photosensitive transfer material according to the first embodiment of the present disclosure includes a temporary support and a photosensitive resin layer in this order, the limiting resolution of the photosensitive resin layer is defined as X μm, and the reference diameter of particles is When defined as Yμm expressed by the formula (1): Y=0.75×X, the number of particles having a diameter of Yμm or more in the temporary support is 15 particles/cm ² or less.
According to the first embodiment described above, a photosensitive transfer material is provided that forms a resin pattern in which the generation of pinholes is suppressed.

The presumed reason for the above-mentioned effects will be explained below. As described above, the coarse particles contained in the temporary support inhibit the exposure of the photosensitive resin layer and generate pinholes in the resin pattern. For example, in the technique disclosed in Japanese Patent Application Laid-Open No. 2019-101405, the number of fine particles with a diameter of 2 μm or more is limited to avoid a decrease in resolution due to foreign substances contained in the temporary support. However, the size of particles that cause exposure disturbances varies depending on the required resolution. As the required resolution becomes smaller, even the tiny particles that were tolerated in the prior art interfere with the exposure of the photosensitive resin layer. Therefore, the inventor of the present disclosure focused on the relationship between the size and number of particles contained in the temporary support with respect to the resolution of the photosensitive resin layer. Through verification of the relationship between the resolution of the photosensitive resin layer and the size of particles that cause exposure problems, the inventors of the present disclosure found that Y (Y = 0.75 x It was revealed that particles having a diameter of X) μm or more lead to an increased incidence of exposure damage. In the photosensitive transfer material according to the first embodiment of the present disclosure, the number of particles having a diameter of Y μm or more in the temporary support according to the standard diameter (Y) of particles derived from the critical resolution (X) of the photosensitive resin layer. By adjusting the number of particles to 15 pieces/cm ² or less, the incidence of exposure damage can be reduced. Therefore, the photosensitive transfer material according to the first embodiment of the present disclosure provides a photosensitive transfer material that forms a resin pattern in which the generation of pinholes is suppressed.

The photosensitive transfer material according to the second embodiment of the present disclosure includes a temporary support and a photosensitive resin layer in this order, and the temporary support is a polyester film consisting of two or more layers, and at least One surface layer (that is, at least one of the layer disposed as the outermost layer on the first surface side and the layer disposed as the outermost layer on the second surface side) does not contain filler.
Even in the second embodiment described above, a photosensitive transfer material that forms a resin pattern in which the generation of pinholes is suppressed is provided.

In addition, in the present disclosure, unless otherwise specified, when the term "photosensitive transfer material according to the present disclosure" or "photosensitive transfer material" is simply referred to, both the above-mentioned first embodiment and the above-mentioned second embodiment shall be described. .

<<Temporary support>>
The photosensitive transfer material according to the present disclosure includes a temporary support. In the photosensitive transfer material, the temporary support supports at least the photosensitive resin layer. In a photosensitive transfer material, the temporary support is a member that can be peeled off from an adjacent layer (for example, a photosensitive resin layer). Hereinafter, in the photosensitive transfer material, the main surface of the temporary support facing the photosensitive resin layer will be referred to as the second surface, and the main surface of the temporary support opposite to the second surface will be referred to as the first surface.

<Temporary support in photosensitive transfer material according to the first embodiment of the present disclosure>
The temporary support (hereinafter also referred to as temporary support (1)) in the photosensitive transfer material according to the first embodiment of the present disclosure will be described below.
In the photosensitive transfer material according to the first embodiment of the present disclosure, the critical resolution of the photosensitive resin layer is defined as X μm, and the standard diameter of the particles is Y μm expressed by the formula (1): Y=0.75×X. When defined as , the number of particles having a diameter of Yμm or more (hereinafter sometimes referred to as "number of specific particles (A)") in the temporary support is 15 particles/cm ² or less. When the number of specific particles (A) in the temporary support (1) is 15 particles/cm ² or less, the incidence of exposure failure is reduced and the occurrence of pinholes is suppressed. From the viewpoint of reducing pinholes, the number of specific particles (A) is preferably 14 particles/cm ² or less, more preferably 12 particles/cm ² or less, and 9 particles/cm ² or less. This is particularly preferred. Further, the number of specific particles (A) is preferably 7 particles/cm ² or less, more preferably 6 particles/cm ² or less, and particularly preferably 5 particles/cm ² or less. The lower limit of the number of specific particles (A) is not limited. The number of specific particles (A) may be determined, for example, in a range of 0 particles/cm ² or more. The number of specific particles (A) may be 0/cm ² or more than 0/cm ² . Examples of methods for reducing the number of specific particles (A) include reducing the amount of particles added to the temporary support (1), and reducing the precipitation or crystallization of additives during the production of the temporary support (1). One example is to suppress the In addition, from the perspective of reducing impurities (including particles regulated in this disclosure), the temporary support (1) may be manufactured using highly pure raw materials or used in the manufacture of the temporary support (1). It is preferable to reduce foreign matter such as particles adhering to the equipment being used. Further, from the viewpoint of reducing the number of foreign particles per unit area (including particles regulated in the present disclosure), it is preferable to reduce the thickness of the temporary support (1). For example, in a method for manufacturing the temporary support (1) using an extrusion method, by adjusting the pore size of the filter of a filter for filtering the melt and the number of times the melt is filtered, The number of specific particles (A) included can be adjusted.

The critical resolution (X) of the photosensitive resin layer will be explained below. In this disclosure, the critical resolution of the photosensitive resin layer is defined as X μm. The term "μm" as used in reference to Xμm is a unit of length, ie, micrometer. The critical resolution (X) of the photosensitive resin layer is preferably 15 μm or less, more preferably 10 μm or less, and particularly preferably 7 μm or less. The lower limit of the critical resolution (X) of the photosensitive resin layer is not limited. The lower limit of the critical resolution (X) of the photosensitive resin layer may be, for example, 0.5 μm, 1 μm, or 2 μm. The critical resolution (X) of the photosensitive resin layer is adjusted depending on, for example, the composition of the photosensitive resin layer, the thickness of the photosensitive resin layer, and the distance between the mask and the base material during exposure. The critical resolution (X) of the photosensitive resin layer is determined by the following method. (1) A photosensitive transfer material is brought into contact with a polyethylene terephthalate (PET) film having a thickness of 100 μm, and a photosensitive resin layer and a temporary support are placed on the PET film in this order. That is, by laminating the PET film and the photosensitive transfer material, a laminate containing at least the PET film, the photosensitive resin layer, and the temporary support in this order is obtained. In the laminate, the configuration of the layers disposed on the PET film varies depending on the layer configuration of the photosensitive transfer material. (2) The obtained laminate is degassed under pressure for 30 minutes at 0.6 MPa and 60° C. using an autoclave device. (3) Line and space pattern mask (Duty ratio is 1:1, line width changes stepwise at 1 μm intervals from 1 μm to 20 μm, without peeling off the temporary support) using an ultra-high pressure mercury lamp .) to expose the photosensitive resin layer to light. (4) After peeling off the temporary support, development is performed. Development is performed using a 1.0 mass % sodium carbonate aqueous solution at 25° C. for 30 seconds by shower development. A resin pattern is formed by developing the photosensitive resin layer. Repeat the above series while adjusting the exposure amount (unit: mJ/cm ² ) each time until a resin pattern with the minimum line width corresponding to the mask pattern (hereinafter referred to as the "reference pattern" in this paragraph) is obtained. Perform steps (1) to (4). If necessary, a mask having a line width of less than 1 μm may be used. The minimum line width of the reference pattern is adopted as the critical resolution (X) of the photosensitive resin layer.

The reference diameter (Y) of particles will be explained below. In this disclosure, the reference diameter of a particle is defined as Y μm, expressed by equation (1): Y=0.75×X. The term "X" used with respect to formula (1) is the critical resolution (X) of the photosensitive resin layer. The unit of X is micrometer. The term "μm" as used in reference to Yμm is a unit of length, ie, micrometer.

In the present disclosure, the number of specific particles (A) is measured by the following method. Ten arbitrary regions (size of each region: 10 mm x 10 mm, total area: 1000 mm ² ) on the surface of the temporary support are visually observed using an optical microscope. The number of particles having a diameter of Y μm or more contained in each region is measured. "Diameter" is the maximum value of a straight line connecting two points on the contour of a particle in plan view. Based on the total number of particles measured in 10 areas, the number of particles per 1 cm ² of the measurement area (particles/cm ² ) is calculated. The obtained value is employed as the number of specific particles (A).

From the viewpoint of reducing pinholes, the number of particles having a diameter of 10.5 μm or more in the temporary support (1) (hereinafter sometimes referred to as "the number of specific particles (B)") is 1.0. /cm ² or less, more preferably 0.5 pieces/cm ² or less, particularly preferably 0.2 pieces/cm ² or less. The lower limit of the number of specific particles (B) is not limited. The number of specific particles (B) may be determined, for example, in a range of 0 particles/cm ² or more. The number of specific particles (B) may be 0 pieces/cm ² or more than 0 pieces/cm ² . The number of specific particles (B) is measured by a method similar to the method for measuring the number of specific particles (A). The number of specific particles (B) is adjusted by a method similar to the method for adjusting the number of specific particles (A).

The particles in the temporary support (1) (including specific particles (A) and specific particles (B); the same applies hereinafter in this paragraph) are particulate compounds added during the preparation of the temporary support (1). It may be. The particles in the temporary support (1) may be particles generated by polycondensation of additives added during the preparation of the temporary support, precipitation during the stretching or cooling process, or crystallization.

Examples of particulate compounds include inorganic particles and organic particles. Examples of the inorganic particles include particles containing inorganic oxides. Examples of the inorganic oxide include silicon oxide (silica), titanium oxide (titania), zirconium oxide (zirconia), magnesium oxide (magnesia), and aluminum oxide (alumina). Examples of organic particles include particles containing polymers. Examples of the polymer include acrylic resin, polyester, polyurethane, polycarbonate, polyolefin, and polystyrene.

Examples of additives added during production of the temporary support (1) include a reaction catalyst for polycondensation, a coloring inhibitor, and a film-forming agent.

Examples of reaction catalysts for polycondensation include alkali metal compounds, alkaline earth metal compounds, zinc compounds, lead compounds, manganese compounds, cobalt compounds, aluminum compounds, antimony compounds, titanium compounds, and phosphorus compounds. Note that an antimony compound, germanium compound, or titanium compound is usually preferably used as a polymerization catalyst at any stage before the polyester manufacturing method is completed.

Examples of the coloring inhibitor include phosphoric acid ester compounds. Examples of phosphoric acid ester compounds include pentavalent phosphoric acid esters that do not have an aromatic ring as a substituent. As a pentavalent phosphoric acid ester having no aromatic ring as a substituent, for example, a phosphoric acid ester having a lower alkyl group having 2 or less carbon atoms as a substituent [(RO) ₃ -P=O, R=carbon number is 1 or 2 alkyl groups]. Examples of the compound represented by "(RO) ₃ -P=O" include trimethyl phosphate and triethyl phosphate.

Examples of the film-forming agent include alkali metal and alkaline earth metal compounds. In addition, in the production of the temporary support or the production of polyester used as a raw material for the temporary support, magnesium compounds are particularly preferably used. By including a magnesium compound in the polyester, the electrostatic application properties of the polyester are improved. In this case, coloring is likely to occur, but by using a coloring inhibitor in combination, coloring can be suppressed and excellent color tone and heat resistance can be obtained. Examples of the magnesium compound include magnesium salts. Examples of magnesium salts include magnesium oxide, magnesium hydroxide, magnesium alkoxide, magnesium acetate, and magnesium carbonate. Among them, magnesium acetate is most preferably used from the viewpoint of solubility in ethylene glycol.

The shape of the particles is not limited. Examples of the shape of the particles in a plan view include a circle, an ellipse, a polygon, and an amorphous shape.

The particles may be transparent particles, translucent particles, or colored particles such as black.

It is preferable that the temporary support (1) has light transmittance. In the present disclosure, "having light transmittance" means that the transmittance at the wavelength used for pattern exposure is 50% or more. From the viewpoint of improving the exposure sensitivity of the photosensitive resin layer, the transmittance of the temporary support (1) at the wavelength used for pattern exposure (more preferably a wavelength of 365 nm) is preferably 60% or more, and 70% or more. It is more preferable that Transmittance is the ratio of the intensity of light that has passed through the object (outgoing light) to the intensity of light that has entered the main surface of the object perpendicularly (incident light). Transmittance is measured using a known spectrometer (eg, "MCPD Series", Otsuka Electronics Co., Ltd.).

The thickness of the temporary support (1) is not limited. The thickness of the temporary support (1) is determined depending on the material from the viewpoints of strength as a support, flexibility required for bonding with the substrate, and light transparency required for exposure. Good too. From the viewpoint of ease of handling and versatility, the thickness of the temporary support (1) is preferably 100 μm or less, more preferably 50 μm or less, even more preferably 20 μm or less, and even more preferably 16 μm or less. It is particularly preferable that there be. From the viewpoint of ease of handling and versatility, the thickness of the temporary support (1) is preferably 5 μm or more, more preferably 10 μm or more. Furthermore, as the thickness of the temporary support (1) becomes thinner, the volume of the temporary support decreases, and the absolute amount of particles contained in the temporary support per unit area decreases.
The thickness of the temporary support is measured by the following method. A cross section along the thickness direction of the temporary support (perpendicular to the main surface of the temporary support) is observed using a scanning electron microscope (SEM) or a transmission electron microscope (TEM). The thickness of the temporary support is measured at 10 locations based on the observed image, and the measured values are arithmetic averaged. The obtained value is adopted as the thickness of the temporary support.

The layer structure of the temporary support (1) is not limited. The temporary support (1) may be a temporary support having a single layer structure or a temporary support having a multilayer structure. The layer structure of the temporary support (1) will be explained below. However, the layer structure of the temporary support (1) is not limited to the layer structure shown below.

Examples of the temporary support (1) having a single layer structure include a glass substrate, a resin film, and paper. A resin film is preferred from the viewpoints of strength, flexibility, and light transmittance. Examples of the resin film include polyethylene terephthalate (PET) film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among the above, PET film is preferred, and biaxially stretched PET film is more preferred. Examples of methods for producing resin films include extrusion molding.

Examples of the temporary support (1) having a multilayer structure include a temporary support including a base material and a particle-containing layer. The temporary support (1) having a multilayer structure may include a layer (for example, an adhesive layer) other than the above-described particle-containing layer.

From the viewpoint of transportability, the temporary support (1) has a particle-containing layer (hereinafter referred to as "first particle-containing layer") disposed as the outermost layer of the temporary support in the lamination direction from the temporary support to the photosensitive resin layer. It is preferable to include a base material and a base material in this order. In other words, the temporary support (1) includes, in this order, a base material and a particle-containing layer (first particle-containing layer) disposed as the outermost layer on the first surface side of the temporary support. is preferred. The surface of the first particle-containing layer includes the first surface of the temporary support (1).

From the viewpoint of ensuring transportability during the production of the temporary support, the temporary support (1) consists of a base material and particles arranged as the outermost layer of the temporary support in the lamination direction from the temporary support to the photosensitive resin layer. containing layer (hereinafter sometimes referred to as "second particle containing layer"), and may be included in this order. In other words, the temporary support (1) may include, in this order, the base material and the particle-containing layer (second particle-containing layer) disposed as the outermost layer on the second surface side of the temporary support. good. The surface of the second particle-containing layer includes the second surface of the temporary support (1).

The temporary support (1) may include a plurality of particle-containing layers. For example, the temporary support (1) may include a first particle-containing layer, a base material, and a second particle-containing layer in this order in the lamination direction from the temporary support toward the photosensitive resin layer. good.

Examples of the base material include glass substrates, resin films, and paper. The base material is preferably a resin film, more preferably a polyethylene terephthalate (PET) film, and particularly preferably a biaxially stretched PET film. Examples of the resin film include the resin films described above. Examples of methods for producing resin films include extrusion molding.

Examples of the particles in the particle-containing layer include inorganic particles and organic particles. Examples of the inorganic particles include particles containing inorganic oxides. Examples of the inorganic oxide include silicon oxide (silica), titanium oxide (titania), zirconium oxide (zirconia), magnesium oxide (magnesia), and aluminum oxide (alumina). Examples of organic particles include particles containing polymers. Examples of the polymer include acrylic resin, polyester, polyurethane, polycarbonate, polyolefin, and polystyrene. From the viewpoint of the wear resistance of the particles, the particles are preferably inorganic particles, more preferably particles containing an inorganic oxide, and include particles of the group consisting of silicon oxide, titanium oxide, zirconium oxide, magnesium oxide, and aluminum oxide. It is more preferable that the particles contain at least one kind selected from the above, and it is particularly preferable that the particles contain silicon oxide.

From the viewpoint of reducing pinholes, the average particle diameter of the particles in the particle-containing layer is preferably 2 μm or less, more preferably 1 μm or less. Further, from the viewpoint of transparency (haze), the average particle diameter of the particles in the particle-containing layer is preferably 300 nm or less, more preferably 100 nm or less, and particularly preferably 80 nm or less. From the viewpoint of transportability, the average particle diameter of the particles in the particle-containing layer is preferably 5 nm or more, more preferably 20 nm or more, and particularly preferably 40 nm or more. In the present disclosure, the average particle diameter of particles in the particle-containing layer is measured by the following method. The particle diameters of 10 particles are measured using a transmission electron microscope (TEM). Here, the "particle diameter" is the maximum value of a straight line connecting two points on the contour of a particle. The arithmetic mean of the measured values is taken as the average particle diameter of the particles.

The shape of the particles in the particle-containing layer is not limited. Examples of the shape of the particles in a plan view include a circle, an ellipse, a polygon, and an amorphous shape.

The particle-containing layer may include a binder. Examples of the binder include polymers. Examples of the polymer include acrylic resin, polyurethane, polyolefin, styrene-butadiene polymer, polyester, polyvinyl chloride, and polyvinylidene chloride.

The thickness of the particle-containing layer is not limited. From the viewpoint of ease of forming protrusions by the added particles, the thickness of the particle-containing layer (excluding particles exposed on the surface of the particle-containing layer; hereinafter the same in this paragraph) is preferably 3 μm or less, More preferably, it is 2 μm or less. Further, from the viewpoint of uniformly distributing particles, the thickness of the particle-containing layer is preferably 5 nm or more, more preferably 20 nm or more. The thickness of the particle-containing layer is measured by a method similar to the method for measuring the thickness of the temporary support.

The method of manufacturing the particle-containing layer is not limited. The particle-containing layer is formed, for example, by applying a particle-containing layer-forming composition onto a base material and, if necessary, drying the applied particle-containing layer-forming composition. The composition for forming a particle-containing layer is a raw material for forming a particle-containing layer. In the above method, the particle-containing layer-forming composition may be applied onto an unstretched film, a uniaxially stretched film, or a biaxially stretched film. The unstretched film or uniaxially stretched film coated with the particle-containing layer-forming composition may be further stretched. The particle-containing layer may be formed with the base material, for example, by coextrusion.

The film used as temporary support (1) is preferably free from deformations (eg wrinkles), scratches and defects.

From the viewpoint of pattern formation during pattern exposure through the temporary support and transparency of the temporary support, it is preferable that the number of fine particles, foreign matter, defects and precipitates contained in the temporary support (1) is small. The number of fine particles, foreign matter, and defects with a diameter of 2 μm or more is preferably 50 pieces/10 mm ² or less, more preferably 10 pieces/10 mm ² or less, and still more preferably 3 pieces/10 mm ² or less. Preferably, 0 pieces/10 mm ² is particularly preferable.

Preferred embodiments of the temporary support (1) are, for example, paragraphs 0017 to 0018 of JP2014-85643A, paragraphs 0019 to 0026 of JP2016-27363A, and paragraphs of International Publication No. 2012/081680. It is described in paragraphs 0041 to 0057, paragraphs 0029 to 0040 of International Publication No. 2018/179370, and paragraphs 0012 to 0032 of JP 2019-101405. The contents of these publications are incorporated herein by reference.

Examples of the temporary support (1) include a biaxially stretched polyethylene terephthalate film with a thickness of 16 μm, a biaxially stretched polyethylene terephthalate film with a thickness of 12 μm, and a biaxially stretched polyethylene terephthalate film with a thickness of 9 μm.

<Temporary support in photosensitive transfer material according to second embodiment of the present disclosure>
The temporary support (hereinafter also referred to as temporary support (2)) in the photosensitive transfer material according to the second embodiment of the present disclosure will be described below.
In the photosensitive transfer material according to the second embodiment of the present disclosure, the temporary support is a polyester film consisting of two or more layers, and at least one surface layer does not contain filler.
Here, the "filler" in the present disclosure refers to an inorganic material added to fill the gaps between polyester resins in the surface layer, and refers to a material having a particle size of 2.0 μm or more.
Examples of the inorganic material that is the filler include the previously described inorganic materials (preferably inorganic oxides).
The presence or absence of fillers and their number are confirmed by the method described below, but in the method for measuring particles described above, they may be measured as part of the particles.
"The surface layer does not contain filler" means that when the surface layer is observed with a scanning electron microscope (SEM) and a transmission electron microscope (TEM) and 10 fields of view are confirmed at 5,000x magnification, the number of fillers present is This means that the average number is 0.5 pieces/mm ² or less. That is, when confirmed by the above method, if the average number of fillers present is 0.5 pieces/mm ² or less, it is considered that "the surface layer does not contain filler".

The above observation method will be explained in more detail.
The polyester resin is removed from the polyester film, which is the surface layer of the temporary support, by a plasma low-temperature ashing process, and the filler, which is an inorganic material, is left and exposed. The processing conditions are selected so that the polyester resin is ashed but the filler is not damaged as much as possible. The treated sample was observed using a scanning electron microscope (SEM, e.g. Hitachi Co., Ltd. S-4000 model) at a magnification of 5000 times, and the particle image was taken into an image analyzer (Nireco LUZEX_AP Co., Ltd.), and the filler Check the presence or absence of particles and the number of particles.
If the filler is significantly damaged by the plasma low-temperature ashing method, the cross section of the temporary support should be examined at 5000x magnification using a transmission electron microscope (TEM, e.g. H-600 model manufactured by Hitachi, Ltd.). Observe and check the presence or absence of fillers and the number of fillers.
When observed with SEM and TEM, if the average number of fillers present is 0.5 pieces/mm2 ^or less when checking 10 fields of view at 5,000x magnification, the surface layer to be observed does not contain particles. I judge that.

If the temporary support (2) is a polyester film consisting of two layers, one of the two layers is the surface layer on the first surface side (i.e., the layer disposed as the outermost layer on the first surface side). The other layer is the surface layer on the second surface side (that is, the layer disposed as the outermost layer on the second surface side). If the temporary support (2) is a polyester film consisting of three or more layers, the surface layer on the first surface side (that is, the layer disposed as the outermost layer on the first surface side) and the surface layer on the second surface side. (that is, the layer disposed as the outermost layer on the second surface side), and one or more intermediate layers sandwiched between these two surface layers.
The temporary support (2) has two surface layers, at least one of which does not contain filler.

Further, from the viewpoint of reducing pinholes, it is preferable that the surface layer of the temporary support (2) on the photosensitive resin layer side (ie, the surface layer on the second surface side) does not contain a filler.

From the viewpoint of reducing pinholes, if the critical resolution of the photosensitive resin layer is defined as Xμm and the reference diameter of the particle is defined as Yμm expressed by formula (1): Y=0.75×X, temporary support The number of particles having a diameter of Y μm or more in the body (2) is preferably 15 particles/cm ² or less, more preferably 12 particles/cm ² or less, and 9 particles/cm ² or less. is more preferable, and particularly preferably 7 pieces/cm ² or less. The lower limit of the number of particles having a diameter of Y μm or more in the temporary support (2) is not limited, and may be 0 particles/cm ² or more than 0 particles/cm ² .

From the viewpoint of transportability, the arithmetic mean roughness Ra of the surface of the temporary support (2) opposite to the photosensitive resin layer (i.e., the first surface) is preferably 1 nm to 50 nm, and preferably 1 nm to 40 nm. It is more preferable that
The arithmetic mean roughness Ra of the surface of the temporary support (2) opposite to the photosensitive resin layer (ie, the first surface) is measured by a method based on JIS B 0601:1994. Specifically, it can be measured in the same manner as the arithmetic mean roughness Ra of the surface of the protective film, which will be described later.

The polyester film consisting of two or more layers constituting the temporary support (2) may be any resin as long as the resin constituting the film has a polyester resin as its main component. In addition, "the resin constituting the film has a polyester resin as a main component" means that at least 70 mol% or more of the resin constituting the film is polyester resin.

The polyester resin constituting the polyester film is obtained by polymerization of monomers containing dicarboxylic acids, diols, and ester-forming derivatives thereof. Specific examples of the polyester resin constituting the film include polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, polybutylene naphthalate, polyhexamethylene terephthalate, polyhexamethylene naphthalate, copolymers thereof, etc. is particularly preferred.

As the dicarboxylic acid component (including dicarboxylic acid and its ester-forming derivative) which is a monomer for obtaining a polyester resin, it is preferable to use an aromatic dicarboxylic acid.
Examples of the aromatic dicarboxylic acid include terephthalic acid, 2,6-naphthalene dicarboxylic acid, and isophthalic acid, with terephthalic acid being particularly preferred.
One type of dicarboxylic acid component may be used, or two or more types may be used in combination. For example, two or more aromatic dicarboxylic acids may be used in combination, or an aromatic dicarboxylic acid and an aliphatic dicarboxylic acid may be used in combination.

Examples of the diol component (including diol and its ester-forming derivative) which is a monomer for obtaining polyester include ethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, etc. Among them, ethylene glycol is particularly preferred.
One type of diol component may be used, or two or more types may be used in combination.

The polyester resin constituting the polyester film can be produced by a conventionally known method. For example, a method in which a dicarboxylic acid component is directly esterified with a diol component, and then the product of this reaction is heated under reduced pressure to polycondense while removing the excess diol component; Examples include a method in which a dialkyl ester of a dicarboxylic acid is used, a transesterification reaction is performed between the dialkyl ester and a diol component, and then polycondensation is performed in the same manner as described above. At this time, conventionally known alkali metals, alkaline earth metals, manganese, cobalt, zinc, antimony, germanium, titanium compounds, and the like can also be used as reaction catalysts, if necessary.

The intrinsic viscosity of the polyester resin constituting the polyester film is preferably 0.5 dl/g to 0.8 dl/g, more preferably 0.55 dl/g to 0.70 dl/g.

The surface layer of the temporary support (2) that does not contain particles preferably has a phase-separated structure. That is, it is preferable that the surface layer does not contain particles and has a phase separation structure (specifically, it may have a sea-island structure). Although the surface layer does not contain particles, it has a phase separation structure (for example, a sea-island structure), so that surface irregularities resulting from the phase separation structure are formed. Specifically, when a film having a surface layer having a phase-separated structure is biaxially stretched, regions that are easily stretched and regions that are difficult to stretch arise due to the phase-separated structure, and this stretching unevenness causes , it is possible to form minute surface irregularities.
In order to form a phase-separated structure in the surface layer as described above, the surface layer preferably contains a polyester resin having an alicyclic structure. In other words, the surface layer contains a main polyester resin (e.g., a polyester resin with an aromatic ring structure) and a polyester resin with an alicyclic structure that is different in compatibility with the main polyester resin, resulting in a phase-separated structure (e.g., , sea-island structures) are formed.

Preferred examples of the alicyclic structure in the polyester resin having an alicyclic structure include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, and a cyclohexane ring, with a cyclohexane ring being particularly preferred. The polyester resin having an alicyclic structure includes, for example, dimethyl terephthalate as the dicarboxylic acid component and 1,3-cyclopropanediol, 1,3-cyclobutanediol, 1,3-cyclopentanediol, 1,4- as the diol component. It is obtained by performing a polycondensation reaction using cyclohexanedimethanol or the like in the presence of 200 ppm of butyltin tris(2-ethylhexanoate).

The content of the polyester resin having an alicyclic structure is 3% by mass to 10% by mass based on the total mass of the surface layer, from the viewpoint of forming surface irregularities and the occurrence of coating defects of the composition for forming a photosensitive resin layer. Mass % is preferred.

The temporary support (2) preferably contains, in its surface layer, copolymerized polyethylene terephthalate containing isophthalic acid as a copolymerization component together with a polyester resin having an alicyclic structure.
Here, copolymerized polyethylene terephthalate containing isophthalic acid as a copolymerization component is a polyester resin in which the diol component that is most abundant in the polyester resin is ethylene glycol, and the dicarboxylic acid component that is the most common is terephthalic acid. A polyester resin containing isophthalic acid. The copolymerization rate of isophthalic acid is preferably in the range of 0.1 mol% to 49 mol%, more preferably 0.5 mol% to 40 mol%, based on the entire dicarboxylic acid component. Containing copolymerized polyethylene terephthalate containing isophthalic acid component as a copolymerization component in the surface layer is preferable from the viewpoint of film forming properties, and it is easier to form surface irregularities due to the difference in stretchability from polyester resin having an alicyclic structure. It is preferable.

The content of copolymerized polyethylene terephthalate containing isophthalic acid as a copolymerization component is not particularly limited, but is preferably 10% by mass to 20% by mass with respect to the total mass constituting the surface layer.

From the viewpoint of reducing pinholes, the thickness of the surface layer is preferably 0.5 μm to 2.5 μm, more preferably 0.6 μm to 2.0 μm.

From the viewpoint of reducing pinholes, the thickness of the temporary support (2) is preferably 50 μm or less, more preferably 40 μm or less. The lower limit of the thickness of the temporary support is, for example, 5 μm or more.

(Layer structure)
In the temporary support (2), the layer structure of the polyester film consisting of two layers includes layer A (surface layer)/layer B (surface layer), and the layer structure of the polyester film consisting of three layers includes: Examples include layer A/layer B (intermediate layer)/layer A, and layer A/layer B (intermediate layer)/layer C (surface layer). Examples of polyester films having four or more layers include those in which the intermediate layer has a laminated structure.
In addition, when the above-mentioned A layer is a surface layer that does not contain particles, the B layer (surface layer), the B layer (intermediate layer), and the C layer (surface layer) may each be a polyester film, and the present disclosure The layer may contain particles as long as it does not impair the purpose of the layer A, but it can also be a layer (polyester film) that does not contain particles, similar to layer A. When the above B layer (surface layer), B layer (intermediate layer), or C layer (surface layer) is a layer containing particles, the contained particles may be organic particles. , may be inorganic particles. Examples of organic particles include particles of polyimide resin, olefin or modified olefin resin, crosslinked polystyrene resin, silicone resin, and the like. Examples of inorganic particles include particles such as silicon oxide, calcium carbonate, agglomerated alumina, aluminum silicate, mica, clay, talc, and barium sulfate.

The above-mentioned particles are preferably particles whose surfaces have been surface-modified with a surfactant or the like to improve affinity with the polyester resin. Further, particles whose particle shape is close to spherical and further have a small difference in refractive index from polyester resin are preferable, such as colloidal silica and organic particles, and silicone resin particles and crosslinked polystyrene resin particles are particularly preferable. . Among them, crosslinked polystyrene resin particles made of styrene-divinylbenzene copolymer prepared by emulsion polymerization have a particle shape close to a true sphere and a uniform particle size distribution, making it possible to form uniform protrusions. It is preferable.

A preferred embodiment of the temporary support (2) is a polyester film consisting of three or more layers, both surface layers containing no particles, containing a polyester resin having an alicyclic structure, and having a thickness of The roughness is 0.5 μm to 2.5 μm, and the arithmetic mean roughness Ra of the first surface is 1 nm to 50 nm.

The method for manufacturing the temporary support (2) will be described below.
The polyester film consisting of two or more layers, which is the temporary support (2), may be produced by melt film forming by coextrusion. When obtaining a layer containing particles (polyester film), for example, the particles are dispersed in ethylene glycol, which is a diol component, to form a slurry, and after high-precision filtration of coarse particles is performed, this ethylene glycol slurry is There is a method of adding it at any stage before the completion of polyester polymerization. Here, when adding the particles, for example, the aqueous sol or alcohol sol obtained during particle synthesis may be added as is without drying. Alternatively, a method may be used in which an aqueous slurry of particles is mixed with polyester pellets and then supplied to a vent-type twin-screw kneading extruder to incorporate the particles into a polyester film.

Using the pellets containing particles and the pellets not containing particles prepared for each layer, if necessary, after mixing the pellets containing particles and the pellets not containing particles, the well-known extrusion for melt lamination is carried out. feed the machine. As the extruder, a single-screw or twin-screw extruder can be used. Furthermore, in order to omit the step of drying the pellets, a vent-type extruder may be used, in which the extruder is equipped with a vacuum line. Furthermore, to form layer B, which has the highest extrusion amount, a so-called tandem extruder may be used, in which each extruder has the function of melting the pellets and the function of maintaining the melted pellets at a constant temperature.

The melted material melted and extruded by the extruder is filtered through a filter. For example, a filter with high precision that captures 95% or more of foreign matter with a diameter of 5 μm or more can be used. Subsequently, it is extruded into a sheet through a slit die and cooled and solidified on a casting roll to produce an unstretched film. That is, the sheets are laminated using a plurality of extruders, a plurality of manifolds or a merging block (for example, a merging block having a rectangular merging section), extruded from a die, and cooled with a casting roll to produce an unstretched film. In this case, it is preferable to install a static mixer and a gear pump in the flow path of the melt.

The temporary support (2) is preferably a biaxially stretched film.
The stretching method may be simultaneous biaxial stretching or sequential biaxial stretching. In the case of sequential stretching, the stretching temperature in the first longitudinal stretching should be 90°C to 130°C, more preferably 100°C to 125°C, from the viewpoint of suppressing film breakage and thermal damage. is desirable. Further, from the viewpoint of preventing stretching unevenness and scratches, it is preferable to carry out the stretching in two or more stages.

From the viewpoint of suppressing stretching unevenness and film breakage, the stretching ratio is 3 to 4.5 times (preferably 3.5 to 4.3 times) in the longitudinal direction, and It is desirable that the width be 3.2 times to 5 times (preferably 4.0 times to 4.6 times) in the width direction. After stretching, heat treatment is performed at 200° C. to 230° C. (preferably 210° C. to 230° C.) for 0.5 seconds to 20 seconds (preferably 1 second to 15 seconds) in order to obtain the desired heat shrinkage rate. It is desirable to perform fixation. Further, after heat solidification, it is preferable to perform a relaxation treatment of 0.1% to 7.0% in the longitudinal and/or width directions.

Hereinafter, unless otherwise specified, the term "temporary support" refers to both the temporary support (1) and the temporary support (2).

<<Photosensitive resin layer>>
The photosensitive transfer material according to the present disclosure includes a photosensitive resin layer. The photosensitive resin layer is preferably a negative photosensitive resin layer in which the solubility of exposed areas in a developer decreases upon exposure, and the non-exposed areas are removed through development. However, the photosensitive resin layer is not limited to a negative photosensitive resin layer. The photosensitive resin layer may be a positive photosensitive resin layer in which the solubility of exposed areas in a developer is improved by exposure, and the exposed areas are removed by development.

It is preferable that the photosensitive resin layer contains a polymer A, a polymerizable compound B, and a photopolymerization initiator. The photosensitive resin layer contains 10% to 90% by mass of polymer A, 5% to 70% by mass of polymerizable compound B, and 0.01% by mass based on the total solid mass of the photosensitive resin layer. % to 20% by mass of a photopolymerization initiator. The components of the photosensitive resin layer will be explained below.

(Polymer A)
Examples of the polymer A include acrylic resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide, polyester, polyamide resin, epoxy resin, polyacetal, polyhydroxystyrene, polyimide resin, polybenzoxazole, Mention may be made of polysiloxanes, polyethyleneimines, polyallylamines and polyalkylene glycols. It is preferable that the polymer A is an alkali-soluble polymer compound. The alkali-soluble polymer compound includes a polymer compound that is easily soluble in an alkali substance. In the present disclosure, "alkali-soluble" means a property in which the solubility in an aqueous solution (100 g) containing 1% by mass of sodium carbonate at 22° C. is 0.1 g or more.

The acid value of the polymer A is preferably 220 mgKOH/g or less, and preferably less than 200 mgKOH/g, since the resolution is better by suppressing the swelling of the photosensitive resin layer caused by the developer. More preferably, it is less than 190 mgKOH/g. The lower limit of the acid value of polymer A is not limited. In terms of better developability, the acid value of polymer A is preferably 60 mgKOH/g or more, more preferably 120 mgKOH/g or more, even more preferably 150 mgKOH/g or more, and 170 mgKOH/g. It is particularly preferable that it is at least g. The acid value of the polymer A may be adjusted by the types of structural units constituting the polymer A and the content of the structural units containing acid groups.

In the present disclosure, "acid value" is the mass (mg) of potassium hydroxide required to neutralize 1 g of sample. The unit of acid value is expressed in mgKOH/g. The acid value can be calculated, for example, from the average content of acid groups in the compound.

The weight average molecular weight of Polymer A is preferably 5,000 to 500,000. It is preferable to adjust the weight average molecular weight to 500,000 or less from the viewpoint of improving resolution and developability. The weight average molecular weight of the polymer A is more preferably 100,000 or less, even more preferably 80,000 or less, and particularly preferably 70,000 or less. On the other hand, it is preferable to adjust the weight average molecular weight to 5,000 or more from the viewpoint of controlling the properties of the developed aggregate and the properties of the unexposed film (for example, edge fusing properties and cut chip properties). The weight average molecular weight of the polymer A is more preferably 10,000 or more, even more preferably 20,000 or more, and particularly preferably 30,000 or more. Edge fusing property refers to the degree of ease with which a photosensitive resin layer protrudes from the end surface of a roll of a photosensitive transfer material wound into a roll. The cut chip property refers to the degree of ease with which chips fly when an unexposed film is cut with a cutter. For example, if the generated chips are transferred to a mask used for exposure, it may cause defective products. The degree of dispersion of the polymer A is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, even more preferably 1.0 to 4.0, and 1. It is particularly preferable that it is between .0 and 3.0. In this disclosure, dispersity is the ratio of weight average molecular weight to number average molecular weight (weight average molecular weight/number average molecular weight). In the present disclosure, weight average molecular weight and number average molecular weight are values measured using gel permeation chromatography.

The glass transition temperature (Tg) of polymer A is preferably 30°C or higher and 135°C or lower. By setting the Tg of the polymer A to 135° C. or lower, it is possible to suppress line width thickening or deterioration of resolution when the focal position during exposure shifts. The Tg of the polymer A is more preferably 130°C or lower, even more preferably 120°C or lower, and particularly preferably 110°C or lower. When the Tg of Polymer A is 30° C. or higher, edge fuse resistance can be improved. The Tg of the polymer A is more preferably 40°C or higher, even more preferably 50°C or higher, particularly preferably 60°C or higher, and most preferably 70°C or higher.

From the viewpoint of suppressing thickening of the line width or deterioration of resolution when the focal position shifts during exposure, it is preferable that the polymer A contains a structural unit having an aromatic hydrocarbon group. Polymer A may include a structural unit having one or more aromatic hydrocarbon groups. Examples of the aromatic hydrocarbon group include a substituted or unsubstituted phenyl group and a substituted or unsubstituted aralkyl group. The content of structural units having an aromatic hydrocarbon group in polymer A is preferably 20% by mass or more, more preferably 30% by mass or more, and 40% by mass or more, based on the total mass of polymer A. It is more preferably at least 45% by mass, particularly preferably at least 45% by mass, and most preferably at least 50% by mass. The upper limit of the content of the structural unit having an aromatic hydrocarbon group in the polymer A is not limited. The content of structural units having an aromatic hydrocarbon group in polymer A is preferably 95% by mass or less, more preferably 85% by mass or less. In addition, when the photosensitive resin layer contains a plurality of types of polymers A, the content rate of the structural unit having an aromatic hydrocarbon group is determined as a weight average value.

The structural unit having an aromatic hydrocarbon group is introduced using a monomer having an aromatic hydrocarbon group. Examples of the monomer having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene and polymerizable styrene derivatives (for example, methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinyl benzoic acid, styrene dimer, styrene trimer). Among the above, monomers having an aralkyl group or styrene are preferred. When the structural unit having an aromatic hydrocarbon group in polymer A is a structural unit derived from styrene, the content of the structural unit derived from styrene is 20% by mass to 80% by mass based on the total mass of polymer A. It is preferably 25% to 70% by weight, particularly preferably 30% to 60% by weight.

Examples of the aralkyl group include substituted or unsubstituted phenylalkyl groups (excluding benzyl groups) and substituted or unsubstituted benzyl groups, with substituted or unsubstituted benzyl groups being preferred.

Examples of the monomer having a phenylalkyl group include phenylethyl (meth)acrylate.

Examples of monomers having a benzyl group include (meth)acrylates having a benzyl group (e.g., benzyl (meth)acrylate and chlorobenzyl (meth)acrylate) and vinyl monomers having a benzyl group (e.g., vinylbenzyl chloride and vinylbenzyl alcohol). Among the above, benzyl (meth)acrylate is preferred. When the structural unit having an aromatic hydrocarbon group in Polymer A is a structural unit derived from benzyl (meth)acrylate, the content of the structural unit derived from benzyl (meth)acrylate is based on the total mass of Polymer A. In contrast, it is preferably 50% to 95% by mass, more preferably 60% to 90% by mass, even more preferably 70% to 90% by mass, and even more preferably 75% to 90% by mass. % is particularly preferred.

Polymer A containing a structural unit having an aromatic hydrocarbon group includes a structural unit having an aromatic hydrocarbon group, a structural unit derived from a first monomer, and a structural unit derived from a second monomer. It is preferable to include at least one selected from the group consisting of:

The polymer A that does not contain a structural unit having an aromatic hydrocarbon group preferably contains a structural unit derived from a first monomer, and a structural unit derived from a first monomer and a second monomer. It is more preferable to include a structural unit derived from a polymer.

The first monomer is a monomer having a carboxyl group in its molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among the above, (meth)acrylic acid is preferred. Polymer A may contain one or more structural units derived from the first monomer. The content of the first monomer in polymer A is preferably 5% to 50% by mass, more preferably 10% to 45% by mass, based on the total mass of polymer A. It is preferably 15% by weight to 35% by weight, particularly preferably.

The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in its molecule. Examples of the second monomer include (meth)acrylates (for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, ) acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate and 2-ethylhexyl (meth)acrylate), Examples include esters of vinyl alcohol (eg, vinyl acetate) and (meth)acrylonitrile. Among the above, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and n-butyl (meth)acrylate are preferred, and methyl (meth)acrylate is particularly preferred. The content of the second monomer in polymer A is preferably 5% to 60% by mass, more preferably 15% to 50% by mass, based on the total mass of polymer A. It is preferably 20% by weight to 45% by weight, particularly preferably.

From the viewpoint of suppressing thickening of line width or deterioration of resolution when the focal position shifts during exposure, polymer A is a group consisting of constitutional units derived from a monomer having an aralkyl group and constitutional units derived from styrene. It is preferable to include at least one selected from the following. Preferred specific examples of the above polymer A include a copolymer of methacrylic acid, benzyl methacrylate, and styrene, and a copolymer of methacrylic acid, methyl methacrylate, benzyl methacrylate, and styrene.

In one embodiment, the polymer A contains 25% to 40% by mass of structural units having aromatic hydrocarbon groups, 20% to 35% by mass of structural units derived from the first monomer, and 25% to 40% by mass of structural units having an aromatic hydrocarbon group, and 20% to 35% by mass of structural units derived from the first monomer. It is preferable that the polymer contains 30% by mass to 45% by mass of structural units derived from the monomer. In another embodiment, the polymer A contains 70% by mass to 90% by mass of structural units derived from a monomer having an aromatic hydrocarbon group and 70% by mass to 90% by mass of structural units derived from a first monomer. A polymer containing 10% by mass to 25% by mass is preferable.

Polymer A may have a branched structure or an alicyclic structure in its side chain. For example, by using a monomer containing a group having a branched structure in the side chain or a monomer containing a group having an alicyclic structure in the side chain, the side chain of the polymer (A) may have a branched structure or an alicyclic structure. structure can be introduced. The alicyclic structure in the side chain of polymer A may be monocyclic or polycyclic.
Moreover, the polymer A may have a linear structure in the side chain.

Examples of monomers containing a group having a branched structure in the side chain include isopropyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, ( Isoamyl meth)acrylate, tert-amyl (meth)acrylate, sec-amyl (meth)acrylate, 2-octyl (meth)acrylate, 3-octyl (meth)acrylate and tert-octyl (meth)acrylate can be mentioned. Among the above, isopropyl (meth)acrylate, isobutyl (meth)acrylate, and tert-butyl methacrylate are preferred, and isopropyl methacrylate or tert-butyl methacrylate is more preferred.

Specific examples of the monomer containing a group having an alicyclic structure in its side chain include monomers having a monocyclic aliphatic hydrocarbon group and monomers having a polycyclic aliphatic hydrocarbon group. Specific examples of the monomer containing a group having an alicyclic structure in the side chain include (meth)acrylates having an alicyclic hydrocarbon group having 5 to 20 carbon atoms. Examples of monomers containing a group having an alicyclic structure in the side chain include (meth)acrylic acid (bicyclo[2.2.1]heptyl-2), (meth)acrylic acid-1-adamantyl, and (meth)acrylic acid (bicyclo[2.2.1]heptyl-2). ) 2-adamantyl acrylate, 3-methyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-1-adamantyl (meth)acrylate, 3-ethyladamantyl (meth)acrylate, ( 3-methyl-5-ethyl-1-adamantyl (meth)acrylate, 3,5,8-triethyl-1-adamantyl (meth)acrylate, 3,5-dimethyl-8-ethyl (meth)acrylate -1-adamantyl, 2-methyl-2-adamantyl (meth)acrylate, 2-ethyl-2-adamantyl (meth)acrylate, 3-hydroxy-1-adamantyl (meth)acrylate, octahydro (meth)acrylate -4,7-menthanoinden-5-yl, octahydro-4,7-menthanoinden-1-ylmethyl (meth)acrylate, -1-menthyl (meth)acrylate, tricyclodecane (meth)acrylate , (meth)acrylic acid-3-hydroxy-2,6,6-trimethyl-bicyclo[3.1.1]heptyl, (meth)acrylic acid-3,7,7-trimethyl-4-hydroxy-bicyclo[4 .1.0] Heptyl, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, fentyl (meth)acrylate, -2,2,5-trimethylcyclohexyl (meth)acrylate and (meth)acrylate Examples include cyclohexyl acid. Among the above, cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, 2-adamantyl (meth)acrylate, (meth)acrylate, ) Fenthyl acrylate, 1-menthyl (meth)acrylate and tricyclodecane (meth)acrylate are preferred, and cyclohexyl (meth)acrylate, (nor)bornyl (meth)acrylate, isobornyl (meth)acrylate, ( More preferred are 2-adamantyl meth)acrylate and tricyclodecane (meth)acrylate.

The photosensitive resin layer may contain one or more types of polymer A. When using two or more types of polymer A, two types of polymer A containing a structural unit having an aromatic hydrocarbon group are used, or a polymer A containing a structural unit having an aromatic hydrocarbon group, It is preferable to use a mixture of the polymer A and the polymer A which does not contain a structural unit having an aromatic hydrocarbon group. In the latter case, the proportion of polymer A containing a structural unit having an aromatic hydrocarbon group is preferably 50% by mass or more, and preferably 70% by mass or more, based on the total mass of polymer A. is more preferable, still more preferably 80% by mass or more, and particularly preferably 90% by mass or more.

The content of polymer A in the photosensitive resin layer is preferably 10% by mass to 90% by mass, more preferably 30% by mass to 70% by mass, based on the total mass of the photosensitive resin layer. , 40% by mass to 60% by mass is particularly preferred. It is preferable to keep the content of polymer A at 90% by mass or less from the viewpoint of controlling the development time. It is preferable to make the content of polymer A 10% by mass or more from the viewpoint of improving edge fuse resistance.

Polymer A is synthesized by adding an appropriate amount of a radical polymerization initiator (e.g., benzoyl peroxide and azoisobutyronitrile) to a solution in which the monomer is diluted with a solvent (e.g., acetone, methyl ethyl ketone, and isopropanol). , is preferably carried out by heating and stirring. In some cases, synthesis may be carried out while dropping a portion of the mixture into the reaction solution. After the reaction is completed, a solvent may be further added to adjust the concentration to a desired level. As the synthesis means, in addition to solution polymerization, bulk polymerization, suspension polymerization, or emulsion polymerization may be used.

(Polymerizable compound B)
Polymerizable compound B is a compound having a polymerizable group. In the present disclosure, the term "polymerizable compound" refers to a compound that polymerizes under the action of a polymerization initiator and is different from the above-mentioned polymer A.

The polymerizable group is not limited as long as it participates in the polymerization reaction, and includes, for example, ethylenically unsaturated groups (e.g., vinyl group, acryloyl group, methacryloyl group, styryl group, and maleimide group) and cationic polymerizable groups. (For example, epoxy groups and oxetane groups). The polymerizable group is preferably an ethylenically unsaturated group, more preferably an acryloyl group or a methacryloyl group.

In order to improve the photosensitivity of the photosensitive resin layer, the polymerizable compound B is preferably a compound having at least one ethylenically unsaturated group (i.e., an ethylenically unsaturated compound), with 2 More preferably, it is a compound having three or more ethylenically unsaturated groups (ie, a polyfunctional ethylenically unsaturated compound). In addition, in terms of better resolution and releasability, the number of ethylenically unsaturated groups contained in one molecule of the ethylenically unsaturated compound is preferably 6 or less, more preferably 3 or less. Preferably, the number is particularly preferably 2 or less. The ethylenically unsaturated compound is preferably a (meth)acrylate compound having a (meth)acryloyl group.

The photosensitive resin layer is made of a compound having two or three ethylenically unsaturated groups in one molecule (i.e., 2 The compound preferably contains a functional or trifunctional ethylenically unsaturated compound), and more preferably a compound having two ethylenically unsaturated groups in one molecule (ie, a difunctional ethylenically unsaturated compound). From the viewpoint of excellent releasability, the content of the bifunctional ethylenically unsaturated compound in the photosensitive resin layer is preferably 60% by mass or more, and more than 70% by mass, based on the total mass of the polymerizable compound B. It is more preferable that the amount is 90% by mass or more, and particularly preferably 90% by mass or more. There is no upper limit to the content of the difunctional ethylenically unsaturated compound. The content of the bifunctional ethylenically unsaturated compound in the photosensitive resin layer may be 100% by mass based on the total mass of the polymerizable compound B. That is, all of the polymerizable compound B contained in the photosensitive resin layer may be a difunctional ethylenically unsaturated compound.

The photosensitive resin layer preferably contains a polymerizable compound B1 having an aromatic ring and two ethylenically unsaturated groups. Polymerizable compound B1 is a compound included in the compounds having two ethylenically unsaturated groups in one molecule (ie, bifunctional ethylenically unsaturated compounds) among the polymerizable compounds B mentioned above.

Examples of aromatic rings include aromatic hydrocarbon rings (e.g., benzene ring, naphthalene ring, and anthracene ring), aromatic heterocycles (e.g., thiophene ring, furan ring, pyrrole ring, imidazole ring, triazole ring, and pyridine ring). and fused rings thereof. The aromatic ring is preferably an aromatic hydrocarbon ring, more preferably a benzene ring. The aromatic ring may have a substituent. Polymerizable compound B1 may have two or more aromatic rings.

The polymerizable compound B1 preferably has a bisphenol structure, since resolution is improved by suppressing swelling of the photosensitive resin layer caused by the developer. Examples of bisphenol structures include bisphenol A structure derived from bisphenol A (2,2-bis(4-hydroxyphenyl)propane) and bisphenol A structure derived from bisphenol F (2,2-bis(4-hydroxyphenyl)methane). F structure and bisphenol B structure derived from bisphenol B (2,2-bis(4-hydroxyphenyl)butane). The bisphenol structure is preferably a bisphenol A structure. Examples of the polymerizable compound B1 having a bisphenol structure include a compound having a bisphenol structure and two ethylenically unsaturated groups (preferably (meth)acryloyl groups) bonded to both ends of the bisphenol structure. . Each ethylenically unsaturated group may be bonded directly to the terminal end of the bisphenol structure, or may be bonded via one or more alkyleneoxy groups. The alkyleneoxy group is preferably an ethyleneoxy group or a propyleneoxy group, more preferably an ethyleneoxy group. The number of alkyleneoxy groups added to the bisphenol structure is not limited. The number of alkyleneoxy groups added to the bisphenol structure is preferably 4 to 16, more preferably 6 to 14 per molecule. The polymerizable compound B1 having a bisphenol structure is described in paragraphs 0072 to 0080 of JP-A No. 2016-224162. The contents of the above publications are incorporated herein by reference.

The polymerizable compound B1 is preferably a bifunctional ethylenically unsaturated compound having a bisphenol A structure, and more preferably 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane. . As the 2,2-bis(4-((meth)acryloxypolyalkoxy)phenyl)propane, for example, 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (FA-324M, Hitachi Chemical Co., Ltd. Company), 2,2-bis(4-(methacryloxyethoxypropoxy)phenyl)propane, 2,2-bis(4-(methacryloxypentaethoxy)phenyl)propane (BPE-500, Shin Nakamura Chemical Co., Ltd.) , 2,2-bis(4-(methacryloxydecaethoxytetrapropoxy)phenyl)propane (FA-3200MY, Hitachi Chemical Co., Ltd.), 2,2-bis(4-(methacryloxypentadecaethoxy)phenyl)propane ( BPE-1300, Shin Nakamura Chemical Co., Ltd.), 2,2-bis(4-(methacryloxydiethoxy)phenyl)propane (BPE-200, Shin Nakamura Chemical Co., Ltd.) and ethoxylated (10) bisphenol A di Examples include acrylate (NK Ester A-BPE-10, Shin Nakamura Chemical Industries, Ltd.).

Examples of the polymerizable compound B1 include a compound represented by the following formula (I).

In formula (I), R ₁ and R ₂ each independently represent a hydrogen atom or a methyl group, A represents C ₂ H ₄ , B represents C ₃ H ₆ , and n ₁ and n ₃ each independently represents an integer from 1 to 39, n ₁ + n ₃ represents an integer from 2 to 40, n ₂ and n ₄ each independently represent an integer from 0 to 29, n ₂ + n ₄ is an integer from 0 to 30, and the arrangement of repeating units of -(AO)- and -(BO)- may be random or block. In the case of a block, -(AO)- may be on the bisphenyl group side, and -(BO)- may be on the bisphenyl group side. n ₁ +n ₂ +n ₃ +n ₄ is preferably an integer of 2 to 20, more preferably an integer of 2 to 16, and particularly preferably an integer of 4 to 12. n ₂ +n ₄ is preferably an integer of 0 to 10, more preferably an integer of 0 to 4, even more preferably an integer of 0 to 2, and particularly preferably 0.

The photosensitive resin layer may contain one or more kinds of polymerizable compounds B1.

The content of the polymerizable compound B1 in the photosensitive resin layer is preferably 10% by mass or more, more preferably 20% by mass or more, based on the total mass of the photosensitive resin layer, from the viewpoint of better resolution. The upper limit is not particularly limited, but from the viewpoint of transferability and edge fuse resistance, it is preferably 70% by mass or less, more preferably 60% by mass or less.

From the viewpoint of better resolution, the ratio of the content of polymerizable compound B1 to the content of polymerizable compound B in the photosensitive resin layer is preferably 40% or more, and 50% by mass or more, based on mass. The content is more preferably 55% by mass or more, even more preferably 60% by mass or more. The upper limit of the ratio of the content of polymerizable compound B1 to the content of polymerizable compound B in the photosensitive resin layer is not limited. From the viewpoint of removability, the ratio of the content of polymerizable compound B1 to the content of polymerizable compound B in the photosensitive resin layer is preferably 99% by mass or less, and 95% by mass or less, based on mass. The content is more preferably 90% by mass or less, even more preferably 85% by mass or less.

The photosensitive resin layer may contain a polymerizable compound B other than the above-mentioned polymerizable compound B1. Examples of polymerizable compounds B other than polymerizable compound B1 include monofunctional ethylenically unsaturated compounds (that is, compounds having one ethylenically unsaturated group in one molecule), and difunctional ethylenes having no aromatic ring. (i.e., compounds that have no aromatic ring and have two ethylenically unsaturated groups in one molecule) and trifunctional or higher-functional ethylenically unsaturated compounds (i.e., compounds that have two ethylenically unsaturated groups in one molecule) compounds having three or more ethylenically unsaturated groups).

Examples of monofunctional ethylenically unsaturated compounds include ethyl (meth)acrylate, ethylhexyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate, polyethylene glycol mono(meth)acrylate, and polypropylene glycol mono(meth)acrylate. Acrylates and phenoxyethyl (meth)acrylates may be mentioned.

Examples of the bifunctional ethylenically unsaturated compound having no aromatic ring include alkylene glycol di(meth)acrylate, polyalkylene glycol di(meth)acrylate, urethane di(meth)acrylate, and trimethylolpropane diacrylate.

Examples of the alkylene glycol di(meth)acrylate include tricyclodecane dimethanol diacrylate (A-DCP, Shin Nakamura Chemical Co., Ltd.), tricyclodecane dimethanol dimethacrylate (DCP, Shin Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (A-NOD-N, Shin Nakamura Chemical Co., Ltd.), 1,6-hexanediol diacrylate (A-HD-N, Shin Nakamura Chemical Co., Ltd.), ethylene glycol dimethacrylate , 1,10-decanediol diacrylate and neopentyl glycol di(meth)acrylate.

Examples of the polyalkylene glycol di(meth)acrylate include polyethylene glycol di(meth)acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, and polypropylene glycol di(meth)acrylate.

Examples of urethane di(meth)acrylates include propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide- and propylene oxide-modified urethane di(meth)acrylates. Commercially available urethane di(meth)acrylates include, for example, 8UX-015A (Taisei Fine Chemical Co., Ltd.), UA-32P (Shin Nakamura Chemical Co., Ltd.), and UA-1100H (Shin Nakamura Chemical Co., Ltd.).

Examples of trifunctional or more ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth)acrylate, pentaerythritol (tri/tetra)(meth)acrylate, trimethylolpropane tri(meth) Examples include acrylate, ditrimethylolpropane tetra(meth)acrylate, trimethylolethane tri(meth)acrylate, isocyanuric acid tri(meth)acrylate, glycerin tri(meth)acrylate, and alkylene oxide modified products thereof. Here, "(tri/tetra/penta/hexa)(meth)acrylate" is a concept that includes tri(meth)acrylate, tetra(meth)acrylate, penta(meth)acrylate, and hexa(meth)acrylate. , and "(tri/tetra)(meth)acrylate" is a concept that includes tri(meth)acrylate and tetra(meth)acrylate.

Examples of alkylene oxide-modified compounds of trifunctional or higher-functional ethylenically unsaturated compounds include caprolactone-modified (meth)acrylate compounds (for example, KAYARAD DPCA-20 (Nippon Kayaku Co., Ltd.) and A-9300-1CL (Shin Nakamura Chemical Co., Ltd.) Kogyo Co., Ltd.)), alkylene oxide modified (meth)acrylate compounds (KAYARAD RP-1040 (Nippon Kayaku Co., Ltd.), ATM-35E (Shin Nakamura Chemical Co., Ltd.), A-9300 (Shin Nakamura Chemical Co., Ltd.) and EBECRYL 135 (Daicel Allnex)), ethoxylated glycerin triacrylate (e.g. A-GLY-9E (Shin-Nakamura Chemical Co., Ltd.)), Aronix TO-2349 (Toagosei Co., Ltd.), Aronix M-520 ( Toagosei Co., Ltd.) and Aronix M-510 (Toagosei Co., Ltd.).

From the viewpoint of resistance to processing liquids such as development, the photosensitive resin layer preferably contains the polymerizable compound B1 and a trifunctional or higher functional ethylenic unsaturated compound, and the photosensitive resin layer contains the polymerizable compound B1 and two or more trifunctional or higher functional ethylene unsaturated compounds. More preferably, it contains a sexually unsaturated compound. The mass ratio of the polymerizable compound B1 and the trifunctional or higher functional ethylenically unsaturated compound (total mass of the polymerizable compound B1: total mass of the trifunctional or higher functional ethylenically unsaturated compound) is 1:1 to 5:1. The ratio is preferably 1.2:1 to 4:1, more preferably 1.5:1 to 3:1.

As the polymerizable compound B other than the polymerizable compound B1, the polymerizable compounds having acid groups described in paragraphs 0025 to 0030 of JP-A No. 2004-239942 may be used.

The photosensitive resin layer may contain one or more kinds of polymerizable compounds B.

The content of polymerizable compound B in the photosensitive resin layer is preferably 10% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, based on the total mass of the photosensitive resin layer. It is preferably 20% by weight to 50% by weight, particularly preferably.

The molecular weight of the polymerizable compound B is preferably 200 to 3,000, more preferably 280 to 2,200, particularly preferably 300 to 2,200. The molecular weight of the polymerizable compound B having a molecular weight distribution is represented by the weight average molecular weight (Mw).

From the viewpoint of resolution and linearity, the value of the ratio Mm/Mb between the content Mm of ethylenically unsaturated compounds and the content Mb of polymer A in the photosensitive resin layer is preferably 1.0 or less. It is preferably 0.9 or less, more preferably 0.5 or more and 0.9 or less. From the viewpoint of curability and resolution, the ethylenically unsaturated compound in the photosensitive resin layer preferably contains a (meth)acrylic compound, and more preferably contains a (meth)acrylate compound. From the viewpoint of curability, resolution, and linearity, the ethylenically unsaturated compound in the photosensitive resin layer contains a (meth)acrylic compound, and the total mass of the (meth)acrylic compound contained in the photosensitive resin layer It is more preferable that the content of the acrylic compound is 60% by mass or less.

(Photopolymerization initiator)
A photopolymerization initiator is a compound that initiates polymerization of a polymerizable compound upon receiving actinic rays (eg, ultraviolet rays, visible rays, and X-rays).

The type of photopolymerization initiator is not limited. The photopolymerization initiator according to the present disclosure includes known photopolymerization initiators. Examples of the photopolymerization initiator include radical photopolymerization initiators and cationic photopolymerization initiators, with radical photopolymerization initiators being preferred.

Examples of the radical photopolymerization initiator include a photopolymerization initiator having an oxime ester structure, a photopolymerization initiator having an α-aminoalkylphenone structure, a photopolymerization initiator having an α-hydroxyalkylphenone structure, and acylphosphine oxide. Examples include a photopolymerization initiator having a structure and a photopolymerization initiator having an N-phenylglycine structure.

From the viewpoint of photosensitivity, visibility of exposed areas, visibility of unexposed areas, and resolution, the photosensitive resin layer contains 2,4,5-triarylimidazole dimer and its like as a photoradical polymerization initiator. It is preferable that at least one selected from the group consisting of derivatives is included. The two 2,4,5-triarylimidazole structures in the 2,4,5-triarylimidazole dimer and its derivatives may be the same or different. Examples of derivatives of 2,4,5-triarylimidazole dimer include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer and 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer. (methoxyphenyl)imidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer and 2-( p-methoxyphenyl)-4,5-diphenylimidazole dimer.

As the photoradical polymerization initiator, for example, the polymerization initiators described in paragraphs 0031 to 0042 of JP-A No. 2011-95716 and paragraphs 0064 to 0081 of JP-A No. 2015-14783 may be used.

Examples of the photoradical polymerization initiator include ethyl dimethylaminobenzoate (DBE, CAS No. 10287-53-3), benzoin methyl ether, and anisyl (p,p'-dimethoxybenzyl).

Commercially available photoradical polymerization initiators include, for example, TAZ-110 (trade name: Midori Kagaku Co., Ltd.), benzophenone, TAZ-111 (trade name: Midori Kagaku Co., Ltd.), 1-[4-(phenylthio)phenyl ]-1,2-octanedione-2-(O-benzoyloxime) (trade name: IRGACURE OXE01, BASF), 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3- IRGACURE OXE03 (BASF), IRGACURE OXE04 (BASF), 2-(dimethylamino)-2-[(4- methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (trade name: Omnirad 379EG, IGM Resins B.V.), 2-methyl-1-(4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: Omnirad 907, IGM Resins B.V.), 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl] phenyl}-2-methylpropan-1-one (product name: Omnirad 127, IGM Resins B.V.), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone-1 (product name) Name: Omnirad 369, IGM Resins B.V.), 2-Hydroxy-2-methyl-1-phenylpropan-1-one (Product name: Omnirad 1173, IGM Resins B.V.), 1-hydroxycyclohexyl Phenylketone (trade name: Omnirad 184, IGM Resins B.V.), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Omnirad 651, IGM Resins B.V.), 2,4,6-trimethylbenzolyl-diphenylphosphine oxide (trade name: Omnirad TPO H, IGM Resins B.V.), bis(2,4,6-trimethylbenzolyl) phenylphosphine oxide (trade name) : Omnirad 819, IGM Resins B.V.), oxime ester photopolymerization initiator (product name: Lunar 6, DKSH Japan Co., Ltd.), 2,2'-bis(2-chlorophenyl)-4,4' , 5,5'-tetraphenylbisimidazole (alias: 2-(2-chlorophenyl)-4,5-diphenylimidazole dimer, trade name: B-CIM, Hampford), 2-(o-chlorophenyl)- 4,5-diphenylimidazole dimer (trade name: BCTB, Tokyo Chemical Industry Co., Ltd.), 1-[4-(phenylthio)phenyl]-3-cyclopentylpropane-1,2-dione-2-(O-benzoyl) oxime) (trade name: TR-PBG-305, Changzhou Strong Electronics New Materials Co., Ltd.), 1,2-propanedione, 3-cyclohexyl-1-[9-ethyl-6-(2-furanylcarbonyl)-9H- carbazol-3-yl]-,2-(O-acetyloxime) (trade name: TR-PBG-326, Changzhou Strong Electronics New Materials Co., Ltd.) and 3-cyclohexyl-1-(6-(2-(benzoyloxyimino) )Hexanoyl)-9-ethyl-9H-carbazol-3-yl)-propane-1,2-dione-2-(O-benzoyloxime) (Product name: TR-PBG-391, Changzhou Powerful Electronic New Materials Co., Ltd.) can be mentioned.

A photocationic polymerization initiator (photoacid generator) is a compound that generates acid upon receiving actinic rays. The photocationic polymerization initiator is preferably a compound that is sensitive to actinic light having a wavelength of 300 nm or more (preferably a wavelength of 300 nm to 450 nm) and generates an acid. In addition, the photocationic polymerization initiator that is not directly sensitive to actinic rays having a wavelength of 300 nm or more may be a compound that generates an acid in response to actinic rays having a wavelength of 300 nm or more when used in combination with a sensitizer. It can be preferably used in combination with a sensitizer.

The photocationic polymerization initiator is preferably a photocationic polymerization initiator that generates an acid with a pKa of 4 or less, and more preferably a photocationic polymerization initiator that generates an acid with a pKa of 3 or less. A photocationic polymerization initiator that generates 2 or less acids is particularly preferred. The lower limit of pKa is not restricted. The pKa of the acid generated by the photocationic polymerization initiator is preferably -10.0 or more.

Examples of the cationic photopolymerization initiator include ionic cationic photopolymerization initiators and nonionic cationic photopolymerization initiators. Examples of ionic photocationic polymerization initiators include onium salt compounds (eg, diaryliodonium salts and triarylsulfonium salts) and quaternary ammonium salts. As the ionic photocationic polymerization initiator, the ionic photocationic polymerization initiator described in paragraphs 0114 to 0133 of JP 2014-85643A may be used. Examples of the nonionic photocationic polymerization initiator include trichloromethyl-s-triazines, diazomethane compounds, imidosulfonate compounds, and oxime sulfonate compounds. As the trichloromethyl-s-triazines, diazomethane compounds and imidosulfonate compounds, for example, compounds described in paragraphs 0083 to 0088 of JP-A No. 2011-221494 may be used. Further, as the oxime sulfonate compound, compounds described in paragraphs 0084 to 0088 of International Publication No. 2018/179640 may be used.

The photosensitive resin layer preferably contains a photoradical polymerization initiator, and more preferably contains at least one selected from the group consisting of 2,4,5-triarylimidazole dimers and derivatives thereof.

The photosensitive resin layer may contain one or more photopolymerization initiators.

The content of the photopolymerization initiator in the photosensitive resin layer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on the total mass of the photosensitive resin layer. It is particularly preferable that the content is 1.0% by mass or more. There is no upper limit to the content of the photopolymerization initiator. The content of the photopolymerization initiator in the photosensitive resin layer is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive resin layer.

(dye)
From the viewpoint of visibility of exposed areas, visibility of non-exposed areas, pattern visibility after development, and resolution, the photosensitive resin layer should have a maximum absorption wavelength of 450 nm or more in the wavelength range of 400 nm to 780 nm during color development. It is preferable that the dye contains a dye (hereinafter sometimes referred to as "dye N") whose maximum absorption wavelength changes depending on an acid, a base, or a radical. When the photosensitive resin layer contains the dye N, the adhesion between the photosensitive resin layer and an adjacent layer (for example, a temporary support) is improved, and resolution is improved.

In the present disclosure, the term "maximum absorption wavelength is changed by an acid, base, or radical" used in relation to a dye refers to (1) an aspect in which a dye in a coloring state is decolored by an acid, a base, or a radical; (2) (3) A mode in which a dye in a decolored state develops color by an acid, a base, or a radical, and (3) a mode in which a dye in a colored state changes to a colored state of another hue. For example, the dye N may be a compound that changes from a decolorized state and develops color upon exposure to light, or a compound that changes from a color developed state and decolorizes upon exposure. The dye N may be a dye whose coloring or decoloring state changes due to the action of acids, bases, or radicals generated in the photosensitive resin layer upon exposure to light. The dye N may be a dye whose coloring or decoloring state changes when the state (for example, pH) in the photosensitive resin layer changes with an acid, a base, or a radical. Further, the dye N may be a dye that changes its coloring or decoloring state by directly receiving the action of an acid, a base, or a radical without being exposed to light.

From the viewpoint of visibility of exposed areas and visibility of unexposed areas, it is preferable that the dye N is a dye that develops color with an acid, a base, or a radical.

From the viewpoint of visibility of exposed areas, visibility of non-exposed areas, and resolution, the dye N is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and a dye whose maximum absorption wavelength changes with radicals. It is more preferable that From the viewpoint of visibility in exposed areas, visibility in non-exposed areas, and resolution, the photosensitive resin layer should include a dye N whose maximum absorption wavelength changes with radicals, and a photoradical polymerization initiator. is preferred.

From the viewpoint of visibility of exposed areas, visibility of non-exposed areas, pattern visibility after development, and resolution, the dye N is preferably a dye whose maximum absorption wavelength changes with radicals, and which develops color with radicals. More preferably, it is a dye.

The coloring mechanism of the dye N in the present disclosure includes, for example, radicals, acids, or Examples include embodiments in which radical-reactive dyes, acid-reactive dyes, or base-reactive dyes (for example, leuco dyes) develop color depending on the base.

From the viewpoint of visibility of exposed areas and visibility of non-exposed areas, the maximum absorption wavelength of dye N in the wavelength range of 400 nm to 780 nm during color development is preferably 550 nm or more, and preferably 550 to 700 nm. The wavelength is more preferably 550 to 650 nm. The number of maximum absorption wavelengths in the wavelength range of 400 to 780 nm during color development may be one or more. When there are two or more maximum absorption wavelengths in the wavelength range of 400 to 780 nm during color development, it is sufficient that the maximum absorption wavelength with the highest absorbance among the two or more maximum absorption wavelengths is 450 nm or more.

The maximum absorption wavelength of dye N is measured by the following method. Under atmospheric conditions, the transmission spectrum of a solution containing dye N (liquid temperature: 25°C) was measured in the wavelength range of 400 nm to 780 nm using a spectrophotometer (e.g. UV3100, Shimadzu Corporation), and the light Detects the wavelength where the intensity is minimum. The wavelength at which the light intensity is minimum is adopted as the maximum absorption wavelength.

Examples of dyes that develop or decolor when exposed to light include leuco dyes.

Examples of dyes that disappear upon exposure to light include leuco dyes, diarylmethane dyes, oxazine dyes, xanthene dyes, iminonaphthoquinone dyes, azomethine dyes, and anthraquinone dyes.

From the viewpoint of visibility of exposed areas and visibility of non-exposed areas, it is preferable that the dye N is a leuco dye.

Examples of leuco dyes include leuco dyes having a triarylmethane skeleton (triarylmethane dyes), leuco dyes having a spiropyran skeleton (spiropyran dyes), leuco dyes having a fluorane skeleton (fluoran dyes), and diarylmethane skeletons. Leuco dyes with a rhodamine lactam skeleton (rhodamine lactam dyes), leuco dyes with an indolylphthalide skeleton (indolylphthalide dyes), and leuco dyes with a leuco auramine skeleton Examples include pigments (leuco auramine pigments). Among the above, triarylmethane dyes or fluoran dyes are preferred, and leuco dyes having a triphenylmethane skeleton (triphenylmethane dyes) or fluoran dyes are more preferred.

From the viewpoint of visibility of exposed areas and unexposed areas, the leuco dye preferably has a lactone ring, a sultine ring, or a sultone ring. The lactone ring, sultine ring, or sultone ring in the leuco dye reacts with the radical generated from the photoradical polymerization initiator or the acid generated from the photocationic polymerization initiator, thereby changing the leuco dye to a ring-closed state and decolorizing it. Alternatively, color can be developed by changing the leuco dye to an open ring state. The leuco dye preferably has a lactone ring, a sultine ring, or a sultone ring, and is preferably a compound that develops color when the lactone ring, sultine ring, or sultone ring opens with a radical or acid. Or, it is more preferable that the compound is a compound that develops color when the lactone ring is opened by an acid.

Specific examples of leuco dyes include p, p', p''-hexamethyltriaminotriphenylmethane (leuco crystal violet), Pergascript Blue SRB (Ciba Geigy), crystal violet lactone, malachite green lactone, benzoyl leucomethylene blue, 2 -(N-phenyl-N-methylamino)-6-(N-p-tolyl-N-ethyl)aminofluorane, 2-anilino-3-methyl-6-(N-ethyl-p-toluidino)fluoran, 3,6-dimethoxyfluorane, 3-(N,N-diethylamino)-5-methyl-7-(N,N-dibenzylamino)fluorane, 3-(N-cyclohexyl-N-methylamino)-6- Methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-anilinofluorane, 3-(N,N-diethylamino)-6-methyl-7-xylidinofluorane , 3-(N,N-diethylamino)-6-methyl-7-chlorofluorane, 3-(N,N-diethylamino)-6-methoxy-7-aminofluorane, 3-(N,N-diethylamino) -7-(4-chloroanilino)fluorane, 3-(N,N-diethylamino)-7-chlorofluorane, 3-(N,N-diethylamino)-7-benzylaminofluorane, 3-(N,N- diethylamino)-7,8-benzofluorane, 3-(N,N-dibutylamino)-6-methyl-7-anilinofluorane, 3-(N,N-dibutylamino)-6-methyl-7- Xylidinofluorane, 3-piperidino-6-methyl-7-anilinofluorane, 3-pyrrolidino-6-methyl-7-anilinofluorane, 3,3-bis(1-ethyl-2-methylindole- 3-yl)phthalide, 3,3-bis(1-n-butyl-2-methylindol-3-yl)phthalide, 3,3-bis(p-dimethylaminophenyl)-6-dimethylaminophthalide, 3 -(4-diethylamino-2-ethoxyphenyl)-3-(1-ethyl-2-methylindol-3-yl)-4-zaphthalide, 3-(4-diethylaminophenyl)-3-(1-ethyl-2 -methylindol-3-yl)phthalide and 3',6'-bis(diphenylamino)spiroisobenzofuran-1(3H),9'-[9H]xanthene-3-one.

Examples of the dye N include dyes. Examples of dyes include brilliant green, ethyl violet, methyl green, crystal violet, basic fuchsin, methyl violet 2B, quinaldine red, rose bengal, methanyl yellow, thymol sulfophthalein, xylenol blue, methyl orange, and paramethyl red. , Congo Red, Benzopurpurin 4B, α-Naphthyl Red, Nile Blue 2B, Nile Blue A, Methyl Violet, Malachite Green, Parafuchsin, Victoria Pure Blue-Naphthalene Sulfonate, Victoria Pure Blue BOH (Hodogaya Chemical Industry Co., Ltd.) ), Oil Blue #603 (Orient Chemical Industry Co., Ltd.), Oil Pink #312 (Orient Chemical Industry Co., Ltd.), Oil Red 5B (Orient Chemical Industry Co., Ltd.), Oil Scarlet #308 (Orient Chemical Industry Co., Ltd.), Oil Red OG (Orient Chemical Industry Co., Ltd.), Oil Red RR (Orient Chemical Industry Co., Ltd.), Oil Green #502 (Orient Chemical Industry Co., Ltd.), Spiron Red BEH Special (Hodogaya Chemical Industry Co., Ltd.), m-cresol purple, Cresol red, rhodamine B, rhodamine 6G, sulforhodamine B, auramine, 4-p-diethylaminophenylimino naphthoquinone, 2-carboxyanilino-4-p-diethylaminophenylimino naphthoquinone, 2-carboxystearylamino-4-p-N , N-bis(hydroxyethyl)amino-phenylimino naphthoquinone, 1-phenyl-3-methyl-4-p-diethylaminophenylimino-5-pyrazolone and 1-β-naphthyl-4-p-diethylaminophenylimino-5- Examples include pyrazolone.

Preferably, the dye N is leuco crystal violet, crystal violet lactone, brilliant green or Victoria Pure Blue-naphthalene sulfonate.

The photosensitive resin layer may contain one or more types of dye N.

From the viewpoint of visibility of exposed areas, visibility of non-exposed areas, pattern visibility after development, and resolution, the content of dye N is 0.1% by mass based on the total mass of the photosensitive resin layer. It is preferably 0.1% by mass to 10% by mass, even more preferably 0.1% by mass to 5% by mass, and even more preferably 0.1% by mass to 1% by mass. It is particularly preferable. The content of dye N means the content of dye N when all of the dye N contained in the photosensitive resin layer is brought into a colored state. Hereinafter, a method for quantifying a dye will be explained using a dye that develops color due to radicals as an example. Prepare a solution of dye (0.001 g) in methyl ethyl ketone (100 mL) and a solution of 0.01 g in methyl ethyl ketone (100 mL). A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF) is added to each solution, and then 365 nm light is irradiated to generate radicals and bring all the dyes into a colored state. Using a spectrophotometer (UV3100, manufactured by Shimadzu Corporation) under atmospheric conditions, the absorbance of each solution at a liquid temperature of 25° C. is measured, and a calibration curve is created. Next, the absorbance of the solution in which all the dyes are colored is measured by the same method as described above except that the photosensitive resin layer (3 g) is dissolved in methyl ethyl ketone instead of the dye. Based on the calibration curve, the amount of dye contained in the photosensitive resin layer is calculated from the absorbance of the solution containing the photosensitive resin layer.

(surfactant)
From the viewpoint of thickness uniformity, the photosensitive resin layer preferably contains a surfactant. Examples of the surfactant include anionic surfactants, cationic surfactants, nonionic (nonionic) surfactants, and amphoteric surfactants. Preferably, the surfactant is a nonionic surfactant. The surfactant is preferably a fluorosurfactant or a silicone surfactant.

Commercially available fluorosurfactants include Megafac (for example, F-171, F-172, F-173, F-176, F-177, F-141, F-142, F-143, F-144, F-437, F-444, F-475, F-477, F-479, F-482, F-551-A, F-552, F-554, F-555-A, F- 556, F-557, F-558, F-559, F-560, F-561, F-565, F-563, F-568, F-575, F-780, EXP, MFS-330, MFS- 578, MFS-578-2, MFS-579, MFS-586, MFS-587, MFS-628, MFS-631, MFS-603, R-41, R-41-LM, R-01, R-40, R-40-LM, RS-43, TF-1956, RS-90, R-94, RS-72-K and DS-21, DIC Corporation), Florado (e.g. FC430, FC431 and FC171, Sumitomo 3M Stock) ), Surflon (e.g. S-382, SC-101, SC-103, SC-104, SC-105, SC-1068, SC-381, SC-383, S-393 and KH-40, AGC Corporation) ), PolyFox (e.g. PF636, PF656, PF6320, PF6520 and PF7002, OMNOVA) and Ftergent (e.g. 710FL, 710FM, 610FM, 601AD, 601ADH2, 602A, 215M, 245F, 251, 212M, 250, 209 F, 222F , 208G, 710LA, 710FS, 730LM, 650AC, 681 and 683 (Neos Co., Ltd.), and U-120E (Unichem Co., Ltd.).

As the fluorine-based surfactant, an acrylic compound may be used, which has a molecular structure containing a functional group containing a fluorine atom, and when heat is applied, the functional group containing the fluorine atom is severed and the fluorine atom volatizes. . Examples of the above-mentioned fluorine-based surfactants include Megafac DS series by DIC Corporation (Kagaku Kogyo Nippo (February 22, 2016), Nikkei Sangyo Shimbun (February 23, 2016), -21).

As the fluorine-based surfactant, a polymer of a fluorine atom-containing vinyl ether compound having a fluorinated alkyl group or a fluorinated alkylene ether group and a hydrophilic vinyl ether compound may be used.

A block polymer may be used as the fluorosurfactant.

The fluorine-based surfactant contains a structural unit derived from a (meth)acrylate compound containing a fluorine atom and two or more (preferably five or more) alkyleneoxy groups (preferably ethyleneoxy or propyleneoxy groups). A fluorine-containing polymer compound containing a structural unit derived from a (meth)acrylate compound may also be used.

As the fluorine-containing surfactant, a fluorine-containing polymer having a group containing an ethylenically unsaturated bond in its side chain may be used. Commercial products of the above-mentioned fluorine-based surfactants include, for example, Megafac (eg, RS-101, RS-102, RS-718K and RS-72-K, manufactured by DIC Corporation).

From the perspective of improving environmental suitability, fluorosurfactants include compounds having a linear perfluoroalkyl group with 7 or more carbon atoms, such as perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS). Surfactants derived from alternative materials are preferred.

Examples of nonionic surfactants include glycerol, trimethylolpropane, trimethylolethane, and their ethoxylates (eg, glycerol ethoxylate) and propoxylates (eg, glycerol propoxylate). Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, and polyethylene glycol. Distearate, sorbitan fatty acid ester, Pluronic (e.g. L10, L31, L61, L62, 10R5, 17R2 and 25R2, HYDROPALAT WE 3323, BASF), Tetronic (e.g. 304, 701, 704, 901, 904 and 150R1) , BASF), Solsperse 20000 (Japan Lubrizol Co., Ltd.), NCW-101 (Fujifilm Wako Pure Chemical Industries, Ltd.), NCW-1001 (Fujifilm Wako Pure Chemical Industries, Ltd.), NCW-1002 (Fujifilm Wako Pure Chemical Industries, Ltd.) Co., Ltd.), Pionin (e.g. D-1105, D-6112, D-6112-W and D-6315, Takemoto Yushi Co., Ltd.), Olfine E1010 (Nissin Chemical Industry Co., Ltd.) and Surfynol (e.g. 104, 400 and 440, Nissin Chemical Industry Co., Ltd.).

Examples of silicone surfactants include linear polymers comprising siloxane bonds and modified siloxane polymers in which organic groups are introduced into side chains or terminals.

Examples of the surfactant include DOWSIL8032 ADDITIVE, Tore Silicone DC3PA, Tore Silicone SH7PA, Tore Silicone DC11PA, Tore Silicone SH21PA, Tore Silicone SH28PA, Tore Silicone SH29PA, Tore Silicone SH30PA, and Tore Silicone SH8400 (Tore Silicone SH8400). Le Dow Corning Co., Ltd.) can be mentioned.

Examples of the surfactant include EXP. S-309-2, EXP. S-315, EXP. S-503-2, EXP. Examples include S-505-2 (manufactured by DIC Corporation).

Examples of the surfactant include X-22-4952, X-22-4272, 643, X-22-6191, X-22-4515, KF-6004, KP-341, KF-6001 and KF-6002 (Shin-Etsu Chemical Co., Ltd.).

Examples of the surfactant include F-4440, TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (Momentive Performance Materials).

Examples of the surfactant include BYK307, BYK323 and BYK330 (BYK Chemie).

Examples of the surfactant include BYK300, BYK306, BYK310, BYK320, BYK325, BYK313, BYK315N, BYK331, BYK333, BYK345, BYK347, BYK348, BYK349, BYK370, BYK377, BYK378, BY K323 (manufactured by BIC Chemie) etc. Can be mentioned.

The photosensitive resin layer may contain one or more surfactants.

The content of the surfactant is preferably 0.001% by mass to 10% by mass, more preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive resin layer.

(Additive)
In addition to the above-mentioned components, the photosensitive resin layer may contain known additives as necessary. Examples of additives include thermally crosslinkable compounds, radical polymerization inhibitors, benzotriazoles, carboxybenzotriazoles, sensitizers, plasticizers, heterocyclic compounds, and solvents. The photosensitive resin layer may contain one or more kinds of additives.

The photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film. In addition, in this specification, the thermally crosslinkable compound having an ethylenically unsaturated group, which will be described later, is not treated as an ethylenically unsaturated compound, but as a thermally crosslinkable compound.
Examples of thermally crosslinkable compounds include methylol compounds and blocked isocyanate compounds. Among these, blocked isocyanate compounds are preferred from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film.
Since blocked isocyanate compounds react with hydroxy groups and carboxy groups, for example, when the polymer A and/or the ethylenically unsaturated compound has at least one of a hydroxy group and a carboxy group, the resulting film is hydrophilic. There is a tendency for the properties of the photosensitive resin layer to decrease, and the functionality of the cured photosensitive resin layer to be enhanced when used as a protective film.
Note that the blocked isocyanate compound refers to "a compound having a structure in which the isocyanate group of isocyanate is protected (so-called masked) with a blocking agent."

The dissociation temperature of the blocked isocyanate compound is not particularly limited, but is preferably 100°C to 160°C, more preferably 130°C to 150°C.
The dissociation temperature of the blocked isocyanate means "the temperature of the endothermic peak associated with the deprotection reaction of the blocked isocyanate when measured by differential scanning calorimetry (DSC) analysis using a differential scanning calorimeter."
As the differential scanning calorimeter, for example, a differential scanning calorimeter (model: DSC6200) manufactured by Seiko Instruments Inc. can be suitably used. However, the differential scanning calorimeter is not limited to this.

Blocking agents with a dissociation temperature of 100°C to 160°C include active methylene compounds [malonic acid diesters (dimethyl malonate, diethyl malonate, di-n-butyl malonate, di-2-ethylhexyl malonate, etc.)], oxime compounds; (Compounds having a structure represented by -C(=N-OH)- in the molecule, such as formaldoxime, acetaldoxime, acetoxime, methyl ethyl ketoxime, and cyclohexanone oxime).
Among these, the blocking agent having a dissociation temperature of 100° C. to 160° C. preferably includes, for example, an oxime compound from the viewpoint of storage stability.

The blocked isocyanate compound preferably has an isocyanurate structure, for example, from the viewpoint of improving the brittleness of the film and improving the adhesion to the transfer target.
A blocked isocyanate compound having an isocyanurate structure can be obtained, for example, by converting hexamethylene diisocyanate into isocyanurate and protecting it.
Among the blocked isocyanate compounds having an isocyanurate structure, a compound having an oxime structure using an oxime compound as a blocking agent is easier to maintain the dissociation temperature in a preferable range than a compound not having an oxime structure, and produces less development residue. This is preferable from the viewpoint of ease of use.

The blocked isocyanate compound may have a polymerizable group.
The polymerizable group is not particularly limited, and any known polymerizable group can be used, with radically polymerizable groups being preferred.
Examples of the polymerizable group include ethylenically unsaturated groups such as a (meth)acryloxy group, (meth)acrylamide group, and styryl group, and groups having an epoxy group such as a glycidyl group.
Among these, the polymerizable group is preferably an ethylenically unsaturated group, more preferably a (meth)acryloxy group, and even more preferably an acryloxy group.

As the blocked isocyanate compound, commercially available products can be used.
Examples of commercially available block isocyanate compounds include Karenz (registered trademark) AOI-BM, Karenz (registered trademark) MOI-BM, Karenz (registered trademark) MOI-BP, etc. (manufactured by Showa Denko K.K.), block type Duranate series (eg, Duranate (registered trademark) TPA-B80E, Duranate (registered trademark) WT32-B75P, etc., manufactured by Asahi Kasei Chemicals Co., Ltd.).
Moreover, a compound having the following structure can also be used as the blocked isocyanate compound.

One type of thermally crosslinkable compound may be used alone, or two or more types may be used.
When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, and 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer. is more preferable.

Examples of the radical polymerization inhibitor include thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784. The radical polymerization inhibitor is preferably phenothiazine, phenoxazine or 4-methoxyphenol. Examples of radical polymerization inhibitors include naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, and diphenylnitrosamine. In order not to impair the sensitivity of the photosensitive resin layer, it is preferable to use nitrosophenylhydroxyamine aluminum salt as the radical polymerization inhibitor.

Examples of benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, Bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole are mentioned.

Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N-(N,N-di-2-ethylhexyl)aminomethylene. Mention may be made of carboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole. Commercially available carboxybenzotriazoles include, for example, CBT-1 (Johoku Kagaku Kogyo Co., Ltd.).

The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01% by mass to 3% by mass, based on the total mass of the photosensitive resin layer, and 0. More preferably, it is .05% by mass to 1% by mass. It is preferable that the total content of the above additives be 0.01% by mass or more from the viewpoint of imparting storage stability to the photosensitive resin layer. On the other hand, it is preferable to keep the total content of the above additives at 3% by mass or less from the viewpoint of maintaining sensitivity and suppressing decolorization of the dye.

The type of sensitizer is not limited. Examples of the sensitizer include dialkylaminobenzophenone compounds, pyrazoline compounds, anthracene compounds, coumarin compounds, xanthone compounds, thioxanthone compounds, acridone compounds, oxazole compounds, benzoxazole compounds, thiazole compounds, benzothiazole compounds, triazole compounds (for example, 1,2,4-triazole), stilbene compounds, triazine compounds, thiophene compounds, naphthalimide compounds, triarylamine compounds and aminoacridine compounds.

From the viewpoint of improving the sensitivity to the light source and improving the curing rate due to the balance between polymerization rate and chain transfer, when the photosensitive resin layer contains a sensitizer, the content of the sensitizer is determined by the total mass of the photosensitive resin layer. It is preferably 0.01% by mass to 5% by mass, more preferably 0.05% by mass to 1% by mass.

Examples of the plasticizer and heterocyclic compound include compounds described in paragraphs 0097 to 0103 and paragraphs 0111 to 0118 of International Publication No. 2018/179640.

Examples of the solvent include the solvents described in the section "Method for forming photosensitive resin layer" below. For example, when a photosensitive resin layer is formed using a composition for forming a photosensitive resin layer containing a solvent, the solvent may remain in the photosensitive resin layer.

The photosensitive resin layer contains metal oxide particles, antioxidant, dispersant, acid multiplying agent, development accelerator, conductive fiber, thermal radical polymerization initiator, thermal acid generator, ultraviolet absorber, thickener, and crosslinking agent. The composition may further contain at least one selected from the group consisting of additives, organic suspending agents, and inorganic suspending agents.

The additives contained in the photosensitive resin layer are described in paragraphs 0165 to 0184 of JP-A No. 2014-85643. The contents of the above publications are incorporated herein by reference.

(impurities)
The photosensitive resin layer may contain impurities. Examples of impurities include sodium, potassium, magnesium, calcium, iron, manganese, copper, aluminum, titanium, chromium, cobalt, nickel, zinc, tin, halogen, and ions thereof. Since halide ions, sodium ions, and potassium ions are likely to be mixed in as impurities, the contents of halide ions, sodium ions, and potassium ions are preferably within the following ranges.

The content of impurities in the photosensitive resin layer is preferably 80 ppm or less, more preferably 10 ppm or less, particularly preferably 2 ppm or less, based on the total mass of the photosensitive resin layer. The content of impurities in the photosensitive resin layer may be 1 ppb or more or 0.1 ppm or more based on the total mass of the photosensitive resin layer. Methods for keeping the content of impurities within the above range include selecting raw materials with a low content of impurities, preventing contamination of impurities during formation of the photosensitive resin layer, and removing them by washing. Impurities are quantified by known methods such as ICP (Inductively Coupled Plasma) emission spectroscopy, atomic absorption spectroscopy, and ion chromatography.

The content of compounds such as benzene, formaldehyde, trichloroethylene, 1,3-butadiene, carbon tetrachloride, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide and hexane in the photosensitive resin layer is preferably small. . The content of the above compound in the photosensitive resin layer is preferably 100 ppm or less, more preferably 20 ppm or less, particularly preferably 4 ppm or less, based on the total mass of the photosensitive resin layer. The content of the above compound in the photosensitive resin layer may be 10 ppb or more or 100 ppb or more based on the total mass of the photosensitive resin layer. The content of the above compound is adjusted by the same method as the method of adjusting the content of the impurities. Moreover, the above-mentioned compound is quantified by a known measuring method.

In order to improve reliability and lamination properties, the water content in the photosensitive resin layer is preferably 0.01% by mass to 1.0% by mass based on the total mass of the photosensitive resin layer. More preferably, it is 0.05% by mass to 0.5% by mass.

(Residual monomer)
The photosensitive resin layer may contain residual monomers, for example, residual monomers corresponding to each structural unit of the polymer A described above.
In terms of patterning properties and reliability, the content of the residual monomer is preferably 5,000 mass ppm or less, more preferably 2,000 mass ppm or less, and 500 mass ppm or less, based on the total mass of polymer A. The following are more preferable. Although the lower limit of the content of the residual monomer is not particularly limited, it is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more, based on the total mass of the polymer A.
The content of the residual monomer corresponding to each structural unit of polymer A is preferably 3,000 mass ppm or less, and 600 mass ppm or less, based on the total mass of the photosensitive resin layer, from the viewpoint of patterning properties and reliability. It is more preferably at most ppm, and even more preferably at most 100 ppm by mass. The lower limit of the content of the residual monomer corresponding to each structural unit of the polymer A is not particularly limited, but is preferably 0.1 mass ppm or more, more preferably 1 mass ppm or more, based on the total mass of the photosensitive resin layer. .

It is also preferable that the amount of residual monomers in the synthesis of polymer A by polymer reaction is within the above range. For example, when polymer A is synthesized by reacting glycidyl acrylate with a carboxylic acid side chain, the content of glycidyl acrylate is preferably within the above range.
The amount of residual monomer can be measured by known methods such as liquid chromatography and gas chromatography.

(thickness)
The thickness of the photosensitive resin layer is not limited. The thickness of the photosensitive resin layer is determined, for example, in the range of 0.1 μm to 100 μm. From the viewpoint of developability and resolution, the thickness of the photosensitive resin layer is preferably 50 μm or less, more preferably 30 μm or less, and particularly preferably 20 μm or less. Furthermore, the thickness of the photosensitive resin layer is preferably 10 μm or less, more preferably 5 μm or less. From the viewpoint of resistance to processing liquids such as developing solutions, the thickness of the photosensitive resin layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, and particularly 0.5 μm or more. preferable. Furthermore, the thickness of the photosensitive resin layer is preferably 0.5 μm to 10 μm, more preferably 0.5 μm to 5 μm. Further, the thickness of the photosensitive resin layer is preferably 0.5 μm to 5 μm, particularly preferably 0.5 μm to 4 μm. The thickness of the photosensitive resin layer is measured by a method similar to the method for measuring the thickness of the temporary support.

(transmittance)
In terms of better adhesion, the transmittance of the photosensitive resin layer at a wavelength of 365 nm is preferably 10% or more, more preferably 30% or more, and particularly preferably 50% or more. The upper limit of the transmittance of the photosensitive resin layer at a wavelength of 365 nm is not limited. The transmittance of the photosensitive resin layer at a wavelength of 365 nm is preferably 99.9% or less.

(Method for forming photosensitive resin layer)
The method for forming the photosensitive resin layer is not limited as long as it can form a layer containing the above components. The photosensitive resin layer can be formed by, for example, preparing a composition for forming a photosensitive resin layer, applying the composition for forming a photosensitive resin layer onto a temporary support, and then applying the composition for forming a photosensitive resin layer to the temporary support. Formed by drying something.

Examples of the composition for forming a photosensitive resin layer include a composition containing a polymer A, a polymerizable compound B, and a photopolymerization initiator. In order to adjust the viscosity of the composition for forming a photosensitive resin layer and facilitate formation of the photosensitive resin layer, the composition for forming a photosensitive resin layer preferably contains a solvent.

The solvent is not limited as long as it can dissolve or disperse the components of the photosensitive resin layer. Solvents include, for example, alkylene glycol ether solvents, alkylene glycol ether acetate solvents, alcohol solvents (e.g. methanol and ethanol), ketone solvents (e.g. acetone and methyl ethyl ketone), aromatic hydrocarbon solvents (e.g. toluene), aprotic solvents. Examples include polar solvents (eg, N,N-dimethylformamide), cyclic ether solvents (eg, tetrahydrofuran), ester solvents, amide solvents, and lactone solvents.

Examples of the alkylene glycol ether solvent include ethylene glycol monoalkyl ether, ethylene glycol dialkyl ether, propylene glycol monoalkyl ether, propylene glycol dialkyl ether, diethylene glycol dialkyl ether, dipropylene glycol monoalkyl ether, and dipropylene glycol dialkyl ether. .

Examples of the alkylene glycol ether acetate solvent include ethylene glycol monoalkyl ether acetate, propylene glycol monoalkyl ether acetate, diethylene glycol monoalkyl ether acetate, and dipropylene glycol monoalkyl ether acetate.

Examples of the solvent include the solvents described in paragraphs 0092 to 0094 of International Publication No. 2018/179640 and the solvents described in paragraph 0014 of JP 2018-177889. The contents of these publications are incorporated herein by reference.

The composition for forming a photosensitive resin layer may contain one or more kinds of solvents. The composition for forming a photosensitive resin layer preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent, and preferably contains at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. It is more preferable to include at least one selected from the group consisting of a ketone solvent and a cyclic ether solvent, and at least one selected from the group consisting of an alkylene glycol ether solvent and an alkylene glycol ether acetate solvent. It is particularly preferable that the solvent contains at least one of a ketone solvent and a cyclic ether solvent.

The content of the solvent in the composition for forming a photosensitive resin layer is preferably 50 parts by mass to 1,900 parts by mass, based on 100 parts by mass of the total solid content in the composition for forming a photosensitive resin layer. More preferably, the amount is 100 parts by mass to 900 parts by mass.

The method for preparing the composition for forming a photosensitive resin layer is not limited. The composition for forming a photosensitive resin layer is prepared, for example, by preparing in advance a solution in which each component is dissolved in a solvent, and mixing the obtained solutions at a predetermined ratio. Before forming the photosensitive resin layer, it is preferable to filter the composition for forming the photosensitive resin layer using a filter having a pore size of 0.2 μm to 30 μm.

Examples of the coating method for the composition for forming a photosensitive resin layer include slit coating, spin coating, curtain coating, and inkjet coating.

<<Thermoplastic resin layer>>
The photosensitive transfer material according to the present disclosure may include a thermoplastic resin layer. Since the photosensitive transfer material includes a thermoplastic resin layer, the followability of the photosensitive transfer material to the substrate is improved when the photosensitive transfer material and the substrate are bonded together, and air bubbles are prevented between the photosensitive transfer material and the substrate. Prevents contamination. Furthermore, since the photosensitive transfer material includes a thermoplastic resin layer, the adhesion between the layers is improved. The photosensitive transfer material according to the present disclosure preferably includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer. The thermoplastic resin layer is described in, for example, paragraphs 0189 to 0193 of JP-A No. 2014-85643. The contents of the above publications are incorporated herein by reference.

(Alkali-soluble resin)
The thermoplastic resin layer preferably contains an alkali-soluble resin as the thermoplastic resin. Examples of the alkali-soluble resin include acrylic resin, polystyrene resin, styrene-acrylic copolymer, polyurethane resin, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyamide resin, epoxy resin, polyacetal resin, polyhydroxystyrene resin, Examples include polyimide resins, polybenzoxazole resins, polysiloxane resins, polyethyleneimines, polyallylamines and polyalkylene glycols.

From the viewpoint of developability and adhesion with adjacent layers, the alkali-soluble resin is preferably an acrylic resin. Here, the acrylic resin is at least one selected from the group consisting of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic acid esters, and structural units derived from (meth)acrylic acid amide. It means a resin containing one type. From the viewpoint of developability and adhesion with adjacent layers, the alkali-soluble resin is particularly preferably an acrylic resin having a structural unit derived from (meth)acrylic acid.

The total content of structural units derived from (meth)acrylic acid, structural units derived from (meth)acrylic esters, and structural units derived from (meth)acrylic acid amide is 50% of the total mass of the acrylic resin. It is preferable that it is at least % by mass. The total content of structural units derived from (meth)acrylic acid and structural units derived from (meth)acrylic acid ester is preferably 30% by mass to 100% by mass based on the total mass of the acrylic resin, More preferably, it is 50% by mass to 100% by mass.

It is preferable that the alkali-soluble resin contains an acid group. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group. Preferably, the acid group is a carboxy group.

From the viewpoint of developability, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH/g or more, and more preferably a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more. The acid value of the alkali-soluble resin is preferably 200 mgKOH/g or less, more preferably 150 mgKOH/g or less.

Examples of the carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more include carboxy group-containing acrylic resins having an acid value of 60 mgKOH/g or more among the polymers described in paragraph 0025 of JP-A No. 2011-95716, Carboxy group-containing acrylic resins having an acid value of 60 mgKOH/g or more among the polymers described in paragraphs 0033 to 0052 of JP 2010-237589 and paragraphs 0053 to 0068 of JP 2016-224162 Among the binder polymers, carboxy group-containing acrylic resins having an acid value of 60 mgKOH/g or more can be mentioned.

The content of the structural unit having a carboxyl group in the carboxy group-containing acrylic resin is preferably 5% by mass to 50% by mass, and preferably 10% by mass to 40% by mass, based on the total mass of the acrylic resin. The content is more preferably 12% by mass to 30% by mass.

The alkali-soluble resin may contain reactive groups. Examples of the reactive group include ethylenically unsaturated groups, polycondensable groups (eg, hydroxy groups and carboxy groups), and polyaddition-reactive groups (eg, epoxy groups and (block) isocyanate groups).

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 1,000 or more, more preferably 10,000 to 100,000, and particularly preferably 20,000 to 50,000.

The thermoplastic resin layer may contain one or more alkali-soluble resins.

From the viewpoint of developability and adhesion with adjacent layers, the content of the alkali-soluble resin is preferably 10% by mass to 99% by mass, and 20% by mass to 20% by mass, based on the total mass of the thermoplastic resin layer. It is more preferably 90% by weight, even more preferably 40% to 80% by weight, and particularly preferably 50% to 70% by weight.

(dye)
The thermoplastic resin layer contains a dye whose maximum absorption wavelength is 450 nm or more in the wavelength range of 400 to 780 nm during color development, and whose maximum absorption wavelength changes with acid, base, or radical (hereinafter referred to as "dye B"). ) is preferably included. Preferred embodiments of dye B are the same as those of dye N, except for the matters shown below.

From the viewpoint of visibility of exposed areas, visibility of unexposed areas, and resolution, dye B is preferably a dye whose maximum absorption wavelength changes with acid or radicals, and a dye whose maximum absorption wavelength changes with acid. It is more preferable that

The thermoplastic resin layer may contain one or more types of dye B.

From the viewpoint of visibility of exposed areas and visibility of non-exposed areas, the content of dye B is preferably 0.2% by mass or more, and 0.2% by mass based on the total mass of the thermoplastic resin layer. % to 6% by weight, even more preferably 0.2% to 5% by weight, particularly preferably 0.25% to 3.0% by weight. Here, the content of the dye B means the content of the dye when all of the dye B contained in the thermoplastic resin layer is brought into a colored state. Hereinafter, a method for quantifying a dye will be explained using a dye that develops color due to radicals as an example. Prepare a solution of dye B (0.001 g) in methyl ethyl ketone (100 mL) and a solution of dye B (0.01 g) in methyl ethyl ketone (100 mL). A photoradical polymerization initiator (Irgacure OXE01, manufactured by BASF) is added to each solution, and then 365 nm light is irradiated to generate radicals and bring all the dyes into a colored state. The absorbance of each solution at a liquid temperature of 25° C. is measured under atmospheric conditions using a spectrophotometer (UV3100, Shimadzu Corporation), and a calibration curve is created. Next, the absorbance of the solution in which all the dyes are colored is measured by the same method as described above except that the thermoplastic resin layer (0.1 g) is dissolved in methyl ethyl ketone instead of the dye. Based on the calibration curve, the amount of dye contained in the thermoplastic resin layer is calculated from the absorbance of the solution containing the thermoplastic resin layer.

From the viewpoint of visibility in exposed areas, visibility in non-exposed areas, and resolution, the thermoplastic resin layer contains, as dye B, a dye whose maximum absorption wavelength changes with acid, and a compound that generates acid when exposed to light. It is preferable to include. Compounds that generate acid when exposed to light will be described later.

(Compounds that generate acids, bases, or radicals when exposed to light)
The thermoplastic resin layer may contain a compound (hereinafter sometimes referred to as "compound C") that generates an acid, a base, or a radical when exposed to light. Compound C is preferably a compound that generates an acid, a base, or a radical upon receiving actinic rays (for example, ultraviolet rays and visible rays). Examples of the compound C include photoacid generators, photobase generators, and photoradical polymerization initiators (photoradical generators). Among the above, photoacid generators are preferred.

From the viewpoint of resolution, the thermoplastic resin layer preferably contains a photoacid generator. Examples of the photoacid generator include the photocationic polymerization initiators described in the section of "Photosensitive resin layer" above. Preferred embodiments of the photoacid generator are the same as the preferred embodiments of the photocationic polymerization initiator explained in the section of "Photosensitive resin layer" above, except for the matters shown below. From the viewpoint of sensitivity and resolution, the photoacid generator preferably contains at least one selected from the group consisting of onium salt compounds and oxime sulfonate compounds. From the viewpoints of sensitivity, resolution, and adhesion, the photoacid generator preferably contains an oxime sulfonate compound. Specific examples of preferred photoacid generators are shown below.

The thermoplastic resin layer may include a photobase generator. Examples of photobase generators include 2-nitrobenzylcyclohexylcarbamate, triphenylmethanol, O-carbamoylhydroxylamide, O-carbamoyloxime, [[(2,6-dinitrobenzyl)oxy]carbonyl]cyclohexylamine, bis[ [(2-nitrobenzyl)oxy]carbonyl]hexane 1,6-diamine, 4-(methylthiobenzoyl)-1-methyl-1-morpholinoethane, (4-morpholinobenzoyl)-1-benzyl-1-dimethylaminopropane , N-(2-nitrobenzyloxycarbonyl)pyrrolidine, hexaamminecobalt(III) tris(triphenylmethylborate), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone, 2,6 -dimethyl-3,5-diacetyl-4-(2-nitrophenyl)-1,4-dihydropyridine and 2,6-dimethyl-3,5-diacetyl-4-(2,4-dinitrophenyl)-1,4 -dihydropyridine.

The thermoplastic resin layer may contain a radical photopolymerization initiator (radical photopolymerization initiator). Examples of the radical photopolymerization initiator include the radical photopolymerization initiators described in the section of "Photosensitive resin layer" above. The preferred embodiments of the radical photopolymerization initiator are the same as the preferred embodiments of the radical photopolymerization initiator explained in the section of "Photosensitive resin layer" above.

The thermoplastic resin layer may contain one or more compounds C.

From the viewpoint of visibility in exposed areas, visibility in non-exposed areas, and resolution, the content of compound C in the thermoplastic resin layer is 0.1% by mass to 10% by mass based on the total mass of the thermoplastic resin layer. It is preferably 0.5% to 5% by weight, more preferably 0.5% to 5% by weight.

(Plasticizer)
From the viewpoints of resolution, adhesion with adjacent layers, and developability, the thermoplastic resin layer preferably contains a plasticizer.

The molecular weight of the plasticizer (in the case where the plasticizer has a molecular weight distribution, the weight average molecular weight (Mw)) is preferably smaller than the molecular weight of the alkali-soluble resin. The molecular weight of the plasticizer is preferably 200 to 2,000.

Examples of the plasticizer include compounds that are compatible with an alkali-soluble resin and exhibit plasticity. From the viewpoint of imparting plasticity, the plasticizer is preferably a compound containing an alkyleneoxy group in its molecule, and more preferably a polyalkylene glycol compound. It is more preferable that the alkyleneoxy group contained in the plasticizer has a polyethyleneoxy structure or a polypropyleneoxy structure.

From the viewpoint of resolution and storage stability, the plasticizer preferably contains a (meth)acrylate compound. From the viewpoint of compatibility, resolution, and adhesion with adjacent layers, it is more preferable that the alkali-soluble resin is an acrylic resin and that the plasticizer contains a (meth)acrylate compound. Examples of the (meth)acrylate compound used as a plasticizer include the (meth)acrylate compounds described in the section of "Polymerizable Compound B" above. When the thermoplastic resin layer is in contact with the photosensitive resin layer in the photosensitive transfer material, it is preferable that the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound. When the thermoplastic resin layer and the photosensitive resin layer contain the same (meth)acrylate compound, component diffusion between the layers is suppressed and storage stability is improved.

From the viewpoint of adhesion with adjacent layers, it is preferable that the (meth)acrylate compound used as a plasticizer does not polymerize even in the exposed area after exposure.

From the viewpoint of resolution, adhesion with adjacent layers, and developability, (meth)acrylate compounds used as plasticizers are (meth)acrylate compounds having two or more (meth)acryloyl groups in one molecule. is preferred.

The (meth)acrylate compound used as a plasticizer is also preferably a (meth)acrylate compound or a urethane (meth)acrylate compound having an acid group.

The thermoplastic resin layer may contain one or more types of plasticizer.

From the viewpoint of resolution, adhesion with adjacent layers, and developability, the content of the plasticizer in the thermoplastic resin layer is 1% by mass to 70% by mass based on the total mass of the thermoplastic resin layer. It is preferably 10% by mass to 60% by mass, and particularly preferably 20% by mass to 50% by mass.

(surfactant)
From the viewpoint of thickness uniformity, the thermoplastic resin layer preferably contains a surfactant. Examples of the surfactant include the surfactants described in the "Photosensitive resin layer" section above. Preferred embodiments of the surfactant are the same as the preferred embodiments of the surfactant explained in the section of "Photosensitive resin layer" above.

The thermoplastic resin layer may contain one or more surfactants.

The content of the surfactant in the thermoplastic resin layer is preferably 0.001% by mass to 10% by mass, and 0.01% by mass to 3% by mass, based on the total mass of the thermoplastic resin layer. It is more preferable.

(sensitizer)
The thermoplastic resin layer may contain a sensitizer. Examples of the sensitizer include the sensitizers described in the section of "Photosensitive resin layer" above.

The thermoplastic resin layer may contain one or more sensitizers.

From the viewpoint of improving sensitivity to the light source and visibility of exposed and unexposed areas, the content of the sensitizer is 0.01% by mass to 5% by mass based on the total mass of the thermoplastic resin layer. It is preferably 0.05% by mass to 1% by mass.

(Additive)
In addition to the above-mentioned components, the thermoplastic resin layer may contain known additives as necessary.

(thickness)
The thickness of the thermoplastic resin layer is not limited. From the viewpoint of adhesion with adjacent layers, the thickness of the thermoplastic resin layer is preferably 1 μm or more, more preferably 2 μm or more. From the viewpoint of developability and resolution, the thickness of the thermoplastic resin layer is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 5 μm or less. The thickness of the thermoplastic resin layer is measured by a method similar to the method for measuring the thickness of the temporary support.

(Method for forming thermoplastic resin layer)
The method of forming the thermoplastic resin layer is not limited as long as it can form a layer containing the above components. The thermoplastic resin layer can be formed by, for example, preparing a composition for forming a thermoplastic resin layer, applying the composition for forming a thermoplastic resin layer onto an object (for example, a photosensitive resin layer), and then applying the composition to the object (for example, a photosensitive resin layer). It is formed by drying the composition for forming a thermoplastic resin layer.

In order to adjust the viscosity of the composition for forming a thermoplastic resin layer and to facilitate formation of the thermoplastic resin layer, the composition for forming a thermoplastic resin layer preferably contains a solvent. The solvent is not limited as long as it can dissolve or disperse the components of the thermoplastic resin layer. Examples of the solvent include the solvents described in the section of "Photosensitive resin layer" above. The preferred embodiment of the solvent is the same as the preferred embodiment of the solvent explained in the section of "Photosensitive resin layer" above.

A composition for forming a thermoplastic resin layer. It may contain one or more kinds of solvents.

The content of the solvent in the composition for forming a thermoplastic resin layer is preferably 50 parts by mass to 1,900 parts by mass, based on 100 parts by mass of the total solid content in the composition for forming a thermoplastic resin layer. More preferably, the amount is 100 parts by mass to 900 parts by mass.

The composition for forming a thermoplastic resin layer is prepared, for example, by a method similar to the method for preparing the composition for forming a photosensitive resin layer. The composition for forming a thermoplastic resin layer is applied, for example, by a method similar to the method for applying the composition for forming a photosensitive resin layer.

＜＜Middle layer＞＞
The photosensitive transfer material according to the present disclosure preferably includes an intermediate layer between the photosensitive resin layer and the thermoplastic resin layer. By including the intermediate layer in the photosensitive transfer material, it is possible to suppress mixing of components between layers during formation of the photosensitive transfer material or storage of the photosensitive transfer material. The intermediate layer is preferably a water-soluble layer from the viewpoint of developability and suppression of mixing of components between layers during formation of the photosensitive transfer material or storage of the photosensitive transfer material. In the present disclosure, "water-soluble" means a property in which the solubility in water (100 g) with a pH of 7.0 and a liquid temperature of 22° C. is 0.1 g or more.

Examples of the intermediate layer include an oxygen barrier layer having an oxygen barrier function, which is described as a "separation layer" in JP-A-5-72724. The oxygen barrier layer is preferable because it improves the sensitivity during exposure, reduces the time load on the exposure machine, and improves productivity. The oxygen barrier layer is preferably an oxygen barrier layer that exhibits low oxygen permeability and is dispersed or dissolved in water or an alkaline aqueous solution (1% by mass aqueous sodium carbonate solution, liquid temperature: 22° C.).

Preferably, the intermediate layer contains resin. Examples of the resin include polyvinyl alcohol resin, polyvinylpyrrolidone resin, cellulose resin, acrylamide resin, polyethylene oxide resin, gelatin, vinyl ether resin, and polyamide resin. The resin may be a homopolymer or a copolymer. Preferably, the resin is a water-soluble resin.

From the viewpoint of oxygen barrier properties and suppression of mixing of components that occurs between layers during formation of a photosensitive transfer material or storage of a photosensitive transfer material, the intermediate layer preferably contains polyvinyl alcohol, polyvinyl alcohol, polyvinylpyrrolidone, It is more preferable to include.

From the viewpoint of suppressing mixing of components between layers, the resin contained in the intermediate layer is a resin different from the polymer A contained in the photosensitive resin layer, and the thermoplastic resin ( For example, it is preferable that the resin is different from the alkali-soluble resin.

The intermediate layer may contain one or more resins.

From the viewpoint of oxygen barrier properties and suppression of mixing of components between layers during formation of a photosensitive transfer material or storage of a photosensitive transfer material, the content of resin in the intermediate layer is 50% by mass based on the total mass of the intermediate layer. % to 100% by mass, more preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, and even more preferably 90% to 100% by mass. Particularly preferred.

The intermediate layer may contain additives such as surfactants, if necessary. Examples of the surfactant include the surfactants described in the "Photosensitive resin layer" section above. Preferred embodiments of the surfactant are the same as the preferred embodiments of the surfactant explained in the section of "Photosensitive resin layer" above.

The thickness of the intermediate layer is not limited. The thickness of the intermediate layer is preferably 0.1 μm to 5 μm, more preferably 0.5 μm to 3 μm. When the thickness of the intermediate layer is within the above range, oxygen barrier properties are not reduced, and mixing of components that occurs between layers during formation of a photosensitive transfer material or storage of a photosensitive transfer material can be suppressed, and It is possible to suppress an increase in the time required to remove the intermediate layer in the development process. The thickness of the intermediate layer is measured by a method similar to the method for measuring the thickness of the temporary support.

The method of forming the intermediate layer is not limited. For example, the intermediate layer can be formed by preparing an intermediate layer forming composition containing a resin and optional additives, applying the intermediate layer forming composition to the surface of a thermoplastic resin layer or a photosensitive resin layer, and applying the intermediate layer forming composition to the surface of a thermoplastic resin layer or a photosensitive resin layer. It is formed by drying the layer forming composition.

In order to adjust the viscosity of the intermediate layer forming composition and facilitate the formation of the intermediate layer, the intermediate layer forming composition preferably contains a solvent. The solvent is not limited as long as it can dissolve or disperse the resin. The solvent is preferably at least one selected from the group consisting of water and water-miscible organic solvents, and more preferably water or a mixed solvent of water and a water-miscible organic solvent. Examples of water-miscible organic solvents include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin. The water-miscible organic solvent is preferably an alcohol having 1 to 3 carbon atoms, more preferably methanol or ethanol.

<<Protective film>>
The photosensitive transfer material according to the present disclosure preferably includes a protective film. The photosensitive transfer material according to the present disclosure preferably includes a temporary support, a photosensitive resin layer, and a protective film in this order. Preferably, the protective film is the outermost layer of the photosensitive transfer material.

Examples of the protective film include resin films and paper. From the viewpoint of strength and flexibility, resin films are preferred. Examples of the resin film include polyethylene film, polypropylene film, polyethylene terephthalate film, cellulose triacetate film, polystyrene film, and polycarbonate film. Among the above, polyethylene film, polypropylene film, or polyethylene terephthalate film is preferred.

The thickness of the protective film is not limited. The thickness of the protective film is preferably 5 μm to 100 μm, more preferably 10 μm to 50 μm. The thickness of the protective film is measured by a method similar to the method for measuring the thickness of the temporary support.

For better resolution, the arithmetic mean roughness Ra of the surface of the protective film on the photosensitive resin layer side (hereinafter sometimes simply referred to as "the surface of the protective film") is preferably 0.3 μm or less. It is preferably 0.1 μm or less, more preferably 0.05 μm or less. It is thought that this is because when the arithmetic mean roughness Ra of the surface of the protective film is within the above range, the uniformity of the thickness of the photosensitive resin layer and the formed resin pattern is improved. The lower limit of the arithmetic mean roughness Ra of the protective film is preferably 0.001 μm or more.

The arithmetic mean roughness Ra of the surface of the protective film is measured by the following method. Using a three-dimensional optical profiler (New View 7300, Zygo), the surface profile of the protective film is obtained under the following conditions. Microscope Application of MetroPro ver. 8.3.2 is used as measurement and analysis software. Next, a Surface Map screen is displayed using the analysis software, and histogram data is obtained on the Surface Map screen. Arithmetic mean roughness Ra is calculated from the obtained histogram data. In measuring the arithmetic mean roughness Ra of the surface of the protective film included in the photosensitive transfer material, the arithmetic mean roughness Ra of the surface of the protective film that appears when the protective film is peeled off from the photosensitive transfer material is measured. good.

<<Relationship among temporary support, photosensitive resin layer, and protective film>>
In the photosensitive transfer material according to the present disclosure, the elongation at break of a cured film obtained by curing the photosensitive resin layer at 120°C is 15% or more, and the arithmetic mean roughness Ra of the surface of the temporary support on the photosensitive resin layer side is It is preferable that the arithmetic mean roughness Ra of the surface of the protective film on the photosensitive resin layer side is 150 nm or less.

Moreover, it is preferable that the photosensitive transfer material according to the present disclosure satisfies the following formula (R1).
X×Y<1,500: Formula (R1)
Here, in the above formula (R1), X represents the value (%) of elongation at break at 120°C of the cured film obtained by curing the photosensitive resin layer, and Y represents the surface of the temporary support on the photosensitive resin layer side. represents the value (nm) of the arithmetic mean roughness Ra.
More preferably, X×Y is 750 or less.

It is preferable that the elongation at break at 120°C is at least twice as large as the elongation at break at 23°C of the cured film obtained by curing the photosensitive resin layer.
The elongation at break was determined by exposing a 20 μm thick photosensitive resin layer to 120 mJ/cm ² using an ultra-high pressure mercury lamp and curing it, then additionally exposing it to 400 mJ/cm ² using a high pressure mercury lamp, and heating it at 145°C for 30 minutes. Measurement is performed using a tensile test using the cured film.

Moreover, it is preferable that the photosensitive transfer material according to the present disclosure satisfies the following formula (R2).
Y≦Z: Formula (R2)
Here, in the above formula (R2), Y represents the value (nm) of the arithmetic mean roughness Ra of the surface on the photosensitive resin layer side of the temporary support, and Z represents the value (nm) of the arithmetic mean roughness Ra of the surface on the photosensitive resin layer side of the protective film. It represents the value (nm) of the arithmetic mean roughness Ra of the surface.

＜＜Other layers＞＞
The photosensitive transfer material according to the present disclosure may include layers other than the above-mentioned layers (hereinafter referred to as "other layers" in this paragraph). Examples of other layers include a contrast enhancement layer (also referred to as a refractive index adjustment layer). The contrast enhancement layer is described in paragraph 0134 of International Publication No. 2018/179640. Further, other layers are described in paragraphs 0194 to 0196 of JP-A No. 2014-85643. The contents of these publications are incorporated herein by reference.

<<Production method of photosensitive transfer material>>
The method of manufacturing the photosensitive transfer material according to the present disclosure is not limited. The photosensitive transfer material is manufactured using, for example, the method for forming each layer described above. Hereinafter, a method for manufacturing a photosensitive transfer material will be described with reference to FIGS. 1 and 2. FIG. 1 is a schematic diagram showing the structure of a photosensitive transfer material according to the present disclosure. FIG. 2 is a schematic diagram showing the structure of a photosensitive transfer material according to another embodiment of the present disclosure. FIG. 3 is a schematic diagram showing the structure of a photosensitive transfer material according to another embodiment of the present disclosure.

The photosensitive transfer material 100 shown in FIG. 1 includes a temporary support 10, a photosensitive resin layer 20, and a protective film 30 in this order. The photosensitive transfer material 100 is manufactured, for example, by the following method. A temporary support 10 having a first surface 10a and a second surface 10b opposite to the first surface 10a is prepared. A photosensitive resin layer forming composition is applied onto the second surface 10b of the temporary support 10, and the applied photosensitive resin layer forming composition is dried to form the photosensitive resin layer 20. . A protective film 30 is placed on the photosensitive resin layer 20. A roll-shaped photosensitive transfer material 100 may be produced and stored by winding up the photosensitive transfer material 100 produced by the above method. The roll-shaped photosensitive transfer material 100 is used, for example, to bond to a substrate by a roll-to-roll method.

The photosensitive transfer material 110 shown in FIG. 2 includes a temporary support 11, a photosensitive resin layer 20, and a protective film 30 in this order. The temporary support 11 includes a particle-containing layer 11-1 and a base material 11-2 in this order in the lamination direction from the temporary support 11 toward the photosensitive resin layer 20. In the temporary support 11, the particle-containing layer 11-1 is arranged as the outermost layer on the first surface 11a side of the temporary support 11. In the temporary support 11, the base material 11-2 is arranged as the outermost layer on the second surface 11b side of the temporary support 11. The photosensitive transfer material 110 is manufactured, for example, by the same method as the method for manufacturing the photosensitive transfer material 100 described above, except that the temporary support 11 is prepared instead of the temporary support 10.

The photosensitive transfer material 120 shown in FIG. 3 includes a temporary support 10, a thermoplastic resin layer 40, an intermediate layer 50, a photosensitive resin layer 20, and a protective film 30 in this order. As a method for manufacturing the photosensitive transfer material 120, for example, the thermoplastic resin layer 40, the intermediate layer 50, the photosensitive resin layer 20, and the protective layer are placed on the second surface 10b of the temporary support according to the method described above. A method of forming the film 30 in this order can be mentioned.

The method for producing a photosensitive transfer material according to the present disclosure is not limited to the method described above. For example, a photosensitive transfer material may be manufactured by forming each layer on a protective film instead of the temporary support.

<<Applications of photosensitive transfer materials>>
The photosensitive transfer material according to the present disclosure is suitably used, for example, in various applications requiring precise microfabrication by photolithography. For example, after patterning the photosensitive resin layer, etching may be performed using the photosensitive resin layer or its cured product as a film, or electroforming, which mainly involves electroplating, may be performed. The cured product obtained by patterning may be used as a permanent film. The cured product obtained by patterning may be used, for example, as an interlayer insulating film, a wiring protective film, or a wiring protective film having an index matching layer. The photosensitive transfer material according to the present disclosure is suitably used, for example, in a method for forming wiring in a semiconductor package, a printed circuit board, or a sensor substrate. The photosensitive transfer material according to the present disclosure is suitably used, for example, in a method for forming conductive films such as touch panels, electromagnetic shielding materials, and film heaters. The photosensitive transfer material according to the present disclosure is suitably used, for example, in liquid crystal sealing materials, micromachines, and methods for forming structures in the microelectronics field.

The photosensitive transfer material according to the present disclosure may be used, for example, as a photosensitive transfer material for a wiring protective film. Examples of the layer structure of a photosensitive transfer material preferably used as a photosensitive transfer material for a wiring protective film include the following (1) and (2).
(1) Temporary support/photosensitive resin layer/refractive index adjustment layer/protective film (2) Temporary support/photosensitive resin layer/protective film

Hereinafter, constituent elements of a photosensitive transfer material preferably used as a photosensitive transfer material for a wiring protective film will be explained. However, the constituent elements of the photosensitive transfer material preferably used as the photosensitive transfer material for wiring protection film are not limited to the constituent elements shown below.

(temporary support)
Examples of the temporary support include the temporary support described in the section of "Temporary Support" above. Preferred embodiments of the temporary support are the same as the preferred embodiments of the temporary support explained in the section of "Temporary Support" above.

(Protective film)
Examples of the protective film include the protective films described in the "Protective Film" section above. Preferred embodiments of the protective film are the same as those described in the section of "Protective Film" above.

(Photosensitive resin layer)
-Alkali-soluble resin-
It is preferable that the photosensitive resin layer contains an alkali-soluble resin.
Examples of alkali-soluble resins include (meth)acrylic resins, styrene resins, epoxy resins, amide resins, amide epoxy resins, alkyd resins, phenol resins, ester resins, urethane resins, and reactions between epoxy resins and (meth)acrylic acid. and acid-modified epoxy acrylate resins obtained by reacting an epoxy acrylate resin with an acid anhydride.

One of the preferable embodiments of the alkali-soluble resin is (meth)acrylic resin, since it has excellent alkali developability and film-forming properties.
In addition, in this specification, a (meth)acrylic resin means resin which has a structural unit derived from a (meth)acrylic compound. The content of the structural units derived from the (meth)acrylic compound is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more, based on all the structural units of the (meth)acrylic resin. .
The (meth)acrylic resin may be composed only of structural units derived from a (meth)acrylic compound, or may have structural units derived from a polymerizable monomer other than the (meth)acrylic compound. . That is, the upper limit of the content of the structural units derived from the (meth)acrylic compound is 100% by mass or less based on all the structural units of the (meth)acrylic resin.

Examples of the (meth)acrylic compound include (meth)acrylic acid, (meth)acrylic acid ester, (meth)acrylamide, and (meth)acrylonitrile.
Examples of (meth)acrylic acid ester include (meth)acrylic acid alkyl ester, (meth)acrylic acid tetrahydrofurfuryl ester, (meth)acrylic acid dimethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, (meth)acrylic acid diethylaminoethyl ester, ) Acrylic acid glycidyl ester, (meth)acrylic acid benzyl ester, 2,2,2-trifluoroethyl (meth)acrylate, and 2,2,3,3-tetrafluoropropyl (meth)acrylate, ( Preferred are meth)acrylic acid alkyl esters.
Examples of (meth)acrylamide include acrylamide such as diacetone acrylamide.

Examples of (meth)acrylic acid alkyl esters include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, and (meth)acrylate. Hexyl acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, and Examples include (meth)acrylic acid alkyl esters having an alkyl group having 1 to 12 carbon atoms, such as dodecyl (meth)acrylate.
As the (meth)acrylic ester, a (meth)acrylic acid alkyl ester having an alkyl group having 1 to 4 carbon atoms is preferred, and methyl (meth)acrylate or ethyl (meth)acrylate is more preferred.

The (meth)acrylic resin may have structural units other than the structural units derived from the (meth)acrylic compound.
The polymerizable monomer forming the above structural unit is not particularly limited as long as it is a compound other than a (meth)acrylic compound that can be copolymerized with a (meth)acrylic compound, such as styrene, vinyltoluene, and α. - Styrene compounds that may have substituents at the α-position or aromatic ring such as methylstyrene, vinyl alcohol esters such as acrylonitrile and vinyl-n-butyl ether, maleic acid, maleic anhydride, monomethyl maleate, maleic acid Examples include maleic acid monoesters such as monoethyl and monoisopropyl maleate, fumaric acid, cinnamic acid, α-cyanocinnamic acid, itaconic acid, and crotonic acid.
These polymerizable monomers may be used alone or in combination of two or more.

Moreover, it is preferable that the (meth)acrylic resin has a structural unit having an acid group in order to improve the alkali developability. Examples of the acid group include a carboxy group, a sulfo group, a phosphoric acid group, and a phosphonic acid group.
Among these, the (meth)acrylic resin more preferably has a structural unit having a carboxy group, and even more preferably has a structural unit derived from the above-mentioned (meth)acrylic acid.

The content of the structural unit having an acid group (preferably a structural unit derived from (meth)acrylic acid) in the (meth)acrylic resin is determined based on the total mass of the (meth)acrylic resin in terms of excellent developability. It is preferably 10% by mass or more. Further, the upper limit is not particularly limited, but from the viewpoint of excellent alkali resistance, it is preferably 50% by mass or less, more preferably 40% by mass or less.

Moreover, it is more preferable that the (meth)acrylic resin has a structural unit derived from the above-mentioned (meth)acrylic acid alkyl ester.
The content of structural units derived from (meth)acrylic acid alkyl ester in the (meth)acrylic resin is preferably 50% to 90% by mass, and preferably 60% to 90% by mass, based on the total structural units of the (meth)acrylic resin. 90% by mass is more preferred, and even more preferably 65% by mass to 90% by mass.

As the (meth)acrylic resin, a resin having both a structural unit derived from (meth)acrylic acid and a structural unit derived from a (meth)acrylic acid alkyl ester is preferable. More preferred is a resin composed only of structural units derived from (meth)acrylic acid alkyl ester.
Moreover, as the (meth)acrylic resin, an acrylic resin having a structural unit derived from methacrylic acid, a structural unit derived from methyl methacrylate, and a structural unit derived from ethyl acrylate is also preferable.

Further, from the viewpoint of resolution, the (meth)acrylic resin preferably has at least one kind selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid alkyl ester. It is preferable to have both a structural unit derived from an acid and a structural unit derived from a methacrylic acid alkyl ester.
From the viewpoint of resolution, the total content of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl ester in (meth)acrylic resin is 40% of the total structural units of (meth)acrylic resin. It is preferably at least 60% by mass, more preferably at least 60% by mass. The upper limit is not particularly limited and may be 100% by mass or less, preferably 80% by mass or less.

In addition, from the viewpoint of resolution, the (meth)acrylic resin contains at least one kind selected from the group consisting of a structural unit derived from methacrylic acid and a structural unit derived from a methacrylic acid alkyl ester, and a structural unit derived from acrylic acid. It is also preferable to have at least one kind selected from the group consisting of structural units and structural units derived from acrylic acid alkyl esters.
From the viewpoint of resolution, the total content of structural units derived from methacrylic acid and structural units derived from methacrylic acid alkyl esters is the total content of structural units derived from acrylic acid and structural units derived from acrylic acid alkyl esters. The mass ratio to the amount is preferably 60/40 to 80/20.

The (meth)acrylic resin preferably has an ester group at the end, since the photosensitive resin layer after transfer has excellent developability.
Note that the terminal portion of the (meth)acrylic resin is composed of a site derived from the polymerization initiator used in the synthesis. A (meth)acrylic resin having an ester group at the end can be synthesized by using a polymerization initiator that generates a radical having an ester group.

Further, the alkali-soluble resin is preferably an alkali-soluble resin having an acid value of 60 mgKOH/g or more, for example, from the viewpoint of developability.
In addition, alkali-soluble resins are, for example, resins with carboxy groups with an acid value of 60 mgKOH/g or more (so-called carboxyl group-containing resins) because they are easily thermally crosslinked with crosslinking components when heated to form a strong film. More preferably, it is a (meth)acrylic resin having a carboxy group with an acid value of 60 mgKOH/g or more (so-called carboxy group-containing (meth)acrylic resin).
When the alkali-soluble resin is a resin having a carboxyl group, the three-dimensional crosslinking density can be increased by, for example, adding a thermally crosslinkable compound such as a blocked isocyanate compound and thermally crosslinking the resin. Moreover, when the carboxyl group of a resin having a carboxyl group is anhydrous and made hydrophobic, the resistance to wet heat can be improved.

The carboxy group-containing (meth)acrylic resin having an acid value of 60 mgKOH/g or more is not particularly limited as long as it satisfies the above acid value condition, and can be appropriately selected from known (meth)acrylic resins.
For example, among the polymers described in paragraph 0025 of JP-A-2011-095716, carboxy group-containing acrylic resins with an acid value of 60 mgKOH/g or more, among the polymers described in paragraphs 0033 to 0052 of JP-A-2010-237589. , a carboxyl group-containing acrylic resin having an acid value of 60 mgKOH/g or more can be preferably used.

Another preferred embodiment of the alkali-soluble resin includes styrene-acrylic copolymer. In addition, in this specification, the styrene-acrylic copolymer refers to a resin having a structural unit derived from a styrene compound and a structural unit derived from a (meth)acrylic compound, and the structural unit derived from the above-mentioned styrene compound. , and the total content of structural units derived from the (meth)acrylic compound is preferably 30% by mass or more, more preferably 50% by mass or more, based on all the structural units of the copolymer.
Further, the content of the structural units derived from the styrene compound is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 5% by mass to 80% by mass, based on all the structural units of the copolymer. preferable.
Further, the content of the structural units derived from the (meth)acrylic compound is preferably 5% by mass or more, more preferably 10% by mass or more, and 20% by mass to 95% by mass, based on the total constitutional units of the copolymer. Mass % is more preferred.

The alkali-soluble resin preferably has an aromatic ring structure, and more preferably has a structural unit having an aromatic ring structure, from the viewpoint of moisture permeability and strength of the resulting cured film.
Examples of the monomer forming the structural unit having an aromatic ring structure include styrene compounds such as styrene, tert-butoxystyrene, methylstyrene, and α-methylstyrene, and benzyl (meth)acrylate.
Among these, styrene compounds are preferred, and styrene is more preferred.
Further, from the viewpoint of moisture permeability and strength of the resulting cured film, the alkali-soluble resin more preferably has a structural unit represented by the following formula (S) (a structural unit derived from styrene).

When the alkali-soluble resin has a constituent unit having an aromatic ring structure, the content of the constituent unit having an aromatic ring structure is determined based on the total constituent units of the alkali-soluble resin from the viewpoint of moisture permeability and strength of the resulting cured film. , preferably 5% to 90% by weight, more preferably 10% to 70% by weight, and even more preferably 20% to 60% by weight.
In addition, the content of the structural unit having an aromatic ring structure in the alkali-soluble resin is 5 mol% to 70 mol% based on the total structural units of the alkali-soluble resin, from the viewpoint of moisture permeability and strength of the resulting cured film. It is preferably 10 mol% to 60 mol%, more preferably 20 mol% to 60 mol%.
Furthermore, the content of the structural unit represented by the above formula (S) in the alkali-soluble resin is 5 mol% to 5% by mole based on the total structural units of the alkali-soluble resin, from the viewpoint of moisture permeability and strength of the resulting cured film. It is preferably 70 mol%, more preferably 10 mol% to 60 mol%, even more preferably 20 mol% to 60 mol%, particularly preferably 20 mol% to 50 mol%.
In addition, in this specification, when the content of a "constituent unit" is defined by a molar ratio, the above-mentioned "constituent unit" shall have the same meaning as a "monomer unit." Moreover, in this specification, the above-mentioned "monomer unit" may be modified after polymerization by a polymer reaction or the like. The same applies to the following.

The alkali-soluble resin preferably has an aliphatic hydrocarbon ring structure from the viewpoints of development residue suppression, strength of the cured film obtained, and tackiness of the uncured film obtained. That is, it is preferable that the alkali-soluble resin has a structural unit having an aliphatic hydrocarbon ring structure. Among these, it is more preferable that the alkali-soluble resin has a ring structure in which two or more aliphatic hydrocarbon rings are condensed.

Examples of the rings constituting the aliphatic hydrocarbon ring structure in the structural unit having an aliphatic hydrocarbon ring structure include a tricyclodecane ring, a cyclohexane ring, a cyclopentane ring, a norbornane ring, and an isoborone ring.
Among these, from the viewpoint of suppressing development residue, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film, a ring in which two or more aliphatic hydrocarbon rings are condensed is preferable, and a tetrahydrodicyclopentadiene ring is preferable. (Tricyclo[5.2.1.0 ^2,6 ]decane ring) is more preferred.
Monomers forming the structural unit having an aliphatic hydrocarbon ring structure include dicyclopentanyl (meth)acrylate, cyclohexyl (meth)acrylate, and isobornyl (meth)acrylate.
In addition, from the viewpoints of development residue suppression, strength of the obtained cured film, and tackiness of the obtained uncured film, the alkali-soluble resin more preferably has a structural unit represented by the following formula (Cy). , a structural unit represented by the above formula (S), and a structural unit represented by the following formula (Cy).

In formula (Cy), R ^M represents a hydrogen atom or a methyl group, and R ^Cy represents a monovalent group having an aliphatic hydrocarbon ring structure.

R ^M in formula (Cy) is preferably a methyl group.
R ^Cy in formula (Cy) is a monomer having an aliphatic hydrocarbon ring structure having 5 to 20 carbon atoms, from the viewpoint of suppressing development residue, the strength of the obtained cured film, and the adhesiveness of the obtained uncured film. It is preferably a monovalent group having an aliphatic hydrocarbon ring structure having 6 to 16 carbon atoms, more preferably a monovalent group having an aliphatic hydrocarbon ring structure having 8 to 14 carbon atoms. More preferably, it is a group of
The aliphatic hydrocarbon ring structure in R ^Cy of formula (Cy) may be a monocyclic structure or a polycyclic structure.
In addition, the aliphatic hydrocarbon ring structure in R ^Cy of formula (Cy) is a cyclopentane ring structure, a cyclohexane ring structure, A ring structure, preferably a tetrahydrodicyclopentadiene ring structure, a norbornane ring structure, or an isoborone ring structure, more preferably a cyclohexane ring structure or a tetrahydrodicyclopentadiene ring structure, and a tetrahydrodicyclopentadiene ring structure It is more preferable that
Furthermore, the aliphatic hydrocarbon ring structure in R ^Cy of formula (Cy) is an aliphatic hydrocarbon ring structure of two or more rings, from the viewpoint of development residue suppression, strength of the obtained cured film, and adhesiveness of the obtained uncured film. A ring structure in which hydrocarbon rings are condensed is preferable, and a ring structure in which 2 to 4 aliphatic hydrocarbon rings are condensed is more preferable.
Furthermore, R ^Cy in the formula (Cy) is -C(=O)O- in the formula (Cy) from the viewpoint of development residue suppression properties, the strength of the obtained cured film, and the tackiness of the obtained uncured film. A group in which an oxygen atom and an aliphatic hydrocarbon ring structure are directly bonded, that is, an aliphatic hydrocarbon ring group is preferable, and a cyclohexyl group or a dicyclopentanyl group is more preferable, and a dicyclo More preferably, it is a pentanyl group.

The alkali-soluble resin may have one type of structural unit having an aliphatic hydrocarbon ring structure, or may have two or more types of structural units.
When the alkali-soluble resin has a structural unit having an aliphatic hydrocarbon ring structure, the content of the structural unit having an aliphatic hydrocarbon ring structure is determined based on the development residue suppressing property, the strength of the cured film obtained, and the obtained untreated film. From the viewpoint of adhesiveness of the cured film, it is preferably 5% by mass to 90% by mass, more preferably 10% by mass to 80% by mass, and further preferably 20% by mass to 70% by mass, based on the total constitutional units of the alkali-soluble resin. preferable.
In addition, the content of the structural unit having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is determined from the viewpoints of development residue suppression, strength of the obtained cured film, and tackiness of the obtained uncured film. It is preferably from 5 mol% to 70 mol%, more preferably from 10 mol% to 60 mol%, even more preferably from 20 mol% to 50 mol%, based on the total structural units.
Furthermore, the content of the structural unit represented by the above formula (Cy) in the alkali-soluble resin is determined based on the alkali-soluble resin, from the viewpoint of development residue suppression, the strength of the obtained cured film, and the tackiness of the obtained uncured film. The amount is preferably 5 mol% to 70 mol%, more preferably 10 mol% to 60 mol%, even more preferably 20 mol% to 50 mol%, based on the total constituent units of the resin.

When the alkali-soluble resin has a constituent unit having an aromatic ring structure and a constituent unit having an aliphatic hydrocarbon ring structure, the total content of the constituent units having an aromatic ring structure and the constituent units having an aliphatic hydrocarbon ring structure is: From the viewpoint of development residue suppression properties, the strength of the obtained cured film, and the tackiness of the obtained uncured film, it is preferably 10% by mass to 90% by mass, and 20% by mass, based on the total structural units of the alkali-soluble resin. It is more preferably 80% by mass, and even more preferably 40% by mass to 75% by mass.
In addition, the total content of the structural units having an aromatic ring structure and the structural units having an aliphatic hydrocarbon ring structure in the alkali-soluble resin is determined by the development residue suppressing property, the strength of the cured film obtained, and the strength of the uncured film obtained. From the viewpoint of tackiness, the amount is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, even more preferably 40 mol% to 60 mol%, based on the total constitutional units of the alkali-soluble resin.
Furthermore, the total content of the structural unit represented by the above formula (S) and the structural unit represented by the above formula (Cy) in the alkali-soluble resin is determined by the present development residue suppressing property, the strength of the cured film obtained, and From the viewpoint of the tackiness of the resulting uncured film, the amount is preferably 10 mol% to 80 mol%, more preferably 20 mol% to 70 mol%, and 40 mol% to 60 mol% based on the total constitutional units of the alkali-soluble resin. % is more preferable.
In addition, the molar amount nS of the structural unit represented by the above formula (S) in the alkali-soluble resin and the molar amount nCy of the structural unit represented by the above formula (Cy) are determined by the development residue suppression property and the strength of the resulting cured film. , and from the viewpoint of the tackiness of the resulting uncured film, it is preferable to satisfy the relationship shown in the following formula (SCy), more preferably to satisfy the following formula (SCy-1), and the following formula (SCy-2) It is more preferable to satisfy the following.
0.2≦nS/(nS+nCy)≦0.8: Formula (SCy)
0.30≦nS/(nS+nCy)≦0.75: Formula (SCy-1)
0.40≦nS/(nS+nCy)≦0.70: Formula (SCy-2)

The alkali-soluble resin preferably has a structural unit having an acid group from the viewpoint of developability and adhesion to the substrate.
Examples of the acid group include a carboxy group, a sulfo group, a phosphonic acid group, and a phosphoric acid group, with a carboxy group being preferred.
As the above-mentioned structural unit having an acid group, the following structural units derived from (meth)acrylic acid are preferable, and structural units derived from methacrylic acid are more preferable.

The alkali-soluble resin may have one type of structural unit having an acid group, or may have two or more types of structural units.
When the alkali-soluble resin has a structural unit having an acid group, the content of the structural unit having an acid group is determined based on the total structural units of the alkali-soluble resin from the viewpoint of developability and adhesion with the substrate. It is preferably 5% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, even more preferably 10% by mass to 30% by mass.
In addition, the content of the structural unit having an acid group in the alkali-soluble resin is preferably 5 mol% to 70 mol% based on the total structural units of the alkali-soluble resin from the viewpoint of developability and adhesion to the substrate. , more preferably 10 mol% to 50 mol%, and even more preferably 20 mol% to 40 mol%.
Furthermore, the content of structural units derived from (meth)acrylic acid in the alkali-soluble resin is 5 mol% to 70% by mole based on the total structural units of the alkali-soluble resin, from the viewpoint of developability and adhesion to the substrate. The amount is preferably mol%, more preferably 10 mol% to 50 mol%, even more preferably 20 mol% to 40 mol%.

From the viewpoint of curability and the strength of the resulting cured film, the alkali-soluble resin preferably has a reactive group, and more preferably has a structural unit having a reactive group.
As the reactive group, a radically polymerizable group is preferable, and an ethylenically unsaturated group is more preferable. Moreover, when the alkali-soluble resin has an ethylenically unsaturated group, it is preferable that the alkali-soluble resin has a structural unit having an ethylenically unsaturated group in a side chain.
In this specification, the "main chain" refers to the relatively longest bond chain in the molecules of the polymer compound that constitutes the resin, and the "side chain" refers to the atomic group branching from the main chain. represent.
As the ethylenically unsaturated group, an allyl group or a (meth)acryloxy group is more preferable.
Examples of the structural unit having a reactive group include, but are not limited to, those shown below.

The alkali-soluble resin may have one type of structural unit having a reactive group, or may have two or more types of structural units.
When the alkali-soluble resin has a constitutional unit having a reactive group, the content of the constitutional unit having a reactive group is determined based on the total constitutional unit of the alkali-soluble resin from the viewpoint of curability and the strength of the resulting cured film. On the other hand, it is preferably 5% by mass to 70% by mass, more preferably 10% by mass to 50% by mass, and even more preferably 20% by mass to 40% by mass.
In addition, from the viewpoint of curability and the strength of the resulting cured film, the content of structural units having reactive groups in the alkali-soluble resin is 5 mol % to 70 mol % based on the total structural units of the alkali-soluble resin. %, more preferably 10 mol% to 60 mol%, even more preferably 20 mol% to 50 mol%.

As a means of introducing a reactive group into an alkali-soluble resin, an epoxy compound, a block Examples include methods of reacting compounds such as isocyanate compounds, isocyanate compounds, vinyl sulfone compounds, aldehyde compounds, methylol compounds, and carboxylic acid anhydrides.
A preferred example of a means for introducing a reactive group into an alkali-soluble resin is to synthesize a polymer having a carboxyl group by a polymerization reaction, and then add glycidyl (meth) to some of the carboxyl groups of the resulting resin by a polymer reaction. Examples include a method of reacting acrylate to introduce a (meth)acryloxy group into the polymer. By this means, an alkali-soluble resin having a (meth)acryloxy group in the side chain can be obtained.
The above polymerization reaction is preferably carried out at a temperature of 70°C to 100°C, more preferably 80°C to 90°C. As the polymerization initiator used in the above polymerization reaction, an azo initiator is preferable, and for example, V-601 (trade name) or V-65 (trade name) manufactured by Fuji Film Wako Pure Chemical Industries, Ltd. is more preferable. The above polymer reaction is preferably carried out at a temperature of 80°C to 110°C. In the above polymer reaction, it is preferable to use a catalyst such as an ammonium salt.

As the alkali-soluble resin, the following resins are preferable from the viewpoint of more excellent effects in the present disclosure. Note that the content ratios (a to d) of each structural unit, weight average molecular weight Mw, etc. shown below can be changed as appropriate depending on the purpose.

In the above resin, it is preferable that a is 20% to 60% by mass, b is 10% to 50% by mass, c is 5.0% to 25% by mass, and d is 10% to 50% by mass. .

In the above resin, it is preferable that a is 20% to 60% by mass, b is 10% to 50% by mass, c is 5.0% to 25% by mass, and d is 10% to 50% by mass. .

In the above resin, a is 30% by mass to 65% by mass, b is 1.0% by mass to 20% by mass, c is 5.0% by mass to 25% by mass, and d is 10% by mass to 50% by mass. is preferred.

In the above resin, a is 1.0% by mass to 20% by mass, b is 20% by mass to 60% by mass, c is 5.0% by mass to 25% by mass, and d is 10% by mass to 50% by mass. is preferred.

Further, the alkali-soluble resin may include a polymer having a structural unit having a carboxylic acid anhydride structure (hereinafter also referred to as "polymer X").
The carboxylic anhydride structure may be either a chain carboxylic anhydride structure or a cyclic carboxylic anhydride structure, but is preferably a cyclic carboxylic anhydride structure.
The ring of the cyclic carboxylic acid anhydride structure is preferably a 5- to 7-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 5-membered ring.

The structural unit having a carboxylic acid anhydride structure is a structural unit containing a divalent group in the main chain obtained by removing two hydrogen atoms from the compound represented by the following formula P-1, or a structural unit having the following formula P-1. It is preferable to use a structural unit in which a monovalent group obtained by removing one hydrogen atom from the represented compound is bonded to the main chain directly or via a divalent linking group.

In formula P-1, R ^A1a represents a substituent, n ^1a R ^A1a 's may be the same or different, and Z ^1a is -C(=O)-O-C(=O)- represents a divalent group forming a ring containing n ^1a represents an integer of 0 or more.

Examples of the substituent represented by R ^A1a include an alkyl group.
Z ^1a is preferably an alkylene group having 2 to 4 carbon atoms, more preferably an alkylene group having 2 or 3 carbon atoms, and even more preferably an alkylene group having 2 carbon atoms.
n ^1a represents an integer of 0 or more. When Z ^1a represents an alkylene group having 2 to 4 carbon atoms, n ^1a is preferably an integer of 0 to 4, more preferably an integer of 0 to 2, and even more preferably 0.
When n ^1a represents an integer of 2 or more, multiple R ^A1a 's may be the same or different. Further, a plurality of R ^A1a may be bonded to each other to form a ring, but it is preferable that they are not bonded to each other to form a ring.

The structural unit having a carboxylic acid anhydride structure is preferably a structural unit derived from an unsaturated carboxylic anhydride, more preferably a structural unit derived from an unsaturated cyclic carboxylic acid anhydride, and a structural unit derived from an unsaturated aliphatic cyclic carboxylic acid anhydride is more preferable. Structural units derived from acid anhydrides are more preferred, structural units derived from maleic anhydride or itaconic anhydride are particularly preferred, and structural units derived from maleic anhydride are most preferred.

Specific examples of the structural unit having a carboxylic anhydride structure are listed below, but the structural unit having a carboxylic anhydride structure is not limited to these specific examples. In the following structural units, Rx represents a hydrogen atom, a methyl group, a CH ₂ OH group, or a CF ₃ group, and Me represents a methyl group.

The number of structural units having a carboxylic acid anhydride structure in the polymer X may be one type alone, or two or more types may be used.

The total content of the structural units having a carboxylic acid anhydride structure is preferably 0 mol% to 60 mol%, more preferably 5 mol% to 40 mol%, and 10 mol% based on all the structural units of the polymer X. More preferably 35 mol%.

The photosensitive resin layer may contain only one type of polymer X, or may contain two or more types of polymer X.
When the photosensitive resin layer contains polymer X, the content of polymer X is 0.1% by mass to 30% by mass based on the total mass of the photosensitive resin layer from the viewpoint of resolution and developability. is preferable, 0.2% by weight to 20% by weight is more preferable, still more preferably 0.5% to 20% by weight, even more preferably 1% to 20% by weight.

The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 or more, more preferably 10,000 or more, even more preferably 10,000 to 50,000, from the viewpoint of improving resolution and developability, and 20 ,000 to 30,000 is particularly preferred.

The acid value of the alkali-soluble resin is preferably 10 mgKOH/g to 200 mgKOH/g, more preferably 60 mgKOH/g to 200 mgKOH/g, even more preferably 60 mgKOH/g to 150 mgKOH/g, and particularly preferably 60 mgKOH/g to 110 mgKOH/g. .
Note that the acid value of the alkali-soluble resin is a value measured according to the method described in JIS K0070:1992.
The degree of dispersion (weight average molecular weight/number average molecular weight) of the alkali-soluble resin is preferably from 1.0 to 6.0, more preferably from 1.0 to 5.0, and from 1.0 to 4.0, from the viewpoint of developability. 0 is more preferable, and 1.0 to 3.0 is particularly preferable.

The photosensitive resin layer may contain only one kind of alkali-soluble resin, or may contain two or more kinds.
From the viewpoint of photosensitivity, resolution and developability, the content of the alkali-soluble resin is preferably 10% to 90% by mass, and 20% to 80% by mass, based on the total mass of the photosensitive resin layer. More preferably, 30% by mass to 70% by mass is even more preferred.

-Polymerizable compound-
The photosensitive resin layer may contain a polymerizable compound.
A polymerizable compound is a compound having a polymerizable group. Examples of the polymerizable group include a radically polymerizable group and a cationically polymerizable group, with the radically polymerizable group being preferred.

The polymerizable compound preferably includes a polymerizable compound having an ethylenically unsaturated group (hereinafter also simply referred to as an "ethylenic unsaturated compound").
As the ethylenically unsaturated group, a (meth)acryloxy group is preferred.
In addition, the ethylenically unsaturated compound in this specification is a compound other than the above-mentioned binder polymer, and preferably has a molecular weight of less than 5,000.
The preferred embodiments of the ethylenically unsaturated compound are the same as the preferred embodiments of the ethylenically unsaturated compound explained in the section of "Photosensitive resin layer" above.

One of the preferred embodiments of the ethylenically unsaturated compound is a compound represented by the following formula (M) (also simply referred to as "compound M").
Q ² -R ¹ -Q ¹ : Formula (M)
In formula (M), Q ¹ and Q ² each independently represent a (meth)acryloyloxy group, and R ¹ represents a divalent linking group having a chain structure.

Q ¹ and Q ² in formula ⁽ M ⁾ are preferably the same group from the viewpoint of ease of synthesis.
Further, Q ¹ and Q ² in formula (M) are preferably acryloyloxy groups from the viewpoint of reactivity.
R ¹ in formula (M) is an alkylene group, an alkyleneoxyalkylene group (-L ¹ -O-L ¹ -), or , a polyalkyleneoxyalkylene group (-(L ¹ -O) _p -L ¹ -) is preferable, a hydrocarbon group having 2 to 20 carbon atoms or a polyalkyleneoxyalkylene group is more preferable, and a polyalkyleneoxyalkylene group having 4 to 20 carbon atoms is preferable. Alkylene groups are more preferred, and linear alkylene groups having 6 to 18 carbon atoms are particularly preferred.
The above-mentioned hydrocarbon group only needs to have a chain structure at least in part, and the part other than the above-mentioned chain structure is not particularly limited. For example, it is branched, cyclic, or has 1 to 1 carbon atoms. It may be a linear alkylene group, an arylene group, an ether bond, or a combination thereof as shown in No. 5, and is preferably an alkylene group or a combination of two or more alkylene groups and one or more arylene group. , an alkylene group is more preferable, and a linear alkylene group is even more preferable.
Note that each of the above L ¹ independently represents an alkylene group, preferably an ethylene group, a propylene group, or a butylene group, and more preferably an ethylene group or a 1,2-propylene group.
p represents an integer of 2 or more, preferably an integer of 2 to 10.

In addition, the number of atoms in the shortest linking chain connecting Q ¹ and Q ² in Compound M is 3 to 50 from the viewpoint of development residue suppression, rust prevention, and bending resistance of the resulting cured film. is preferable, 4 to 40 pieces are more preferable, 6 to 20 pieces are still more preferable, and 8 to 12 pieces are particularly preferable.
In this specification, "the number of atoms in the shortest connecting chain connecting Q ¹ and Q ² " refers to the number of atoms in R ¹ connecting to Q ¹ to the atom in R ¹ connecting to Q ² . This is the shortest number of atoms.

Specific examples of compound M include 1,3-butanediol di(meth)acrylate, tetramethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,7-heptanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, hydrogenated Bisphenol A di(meth)acrylate, hydrogenated bisphenol F di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, poly(ethylene glycol/propylene glycol) di(meth)acrylate, and polybutylene glycol di(meth)acrylate. The above ester monomers can also be used as a mixture.
Among the above compounds, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1 , 10-decanediol di(meth)acrylate, and neopentylglycol di(meth)acrylate, and 1,6-hexanediol di(meth)acrylate , 1,9-nonanediol di(meth)acrylate, and 1,10-decanediol di(meth)acrylate, and 1,9-nonanediol di(meth)acrylate is more preferable. More preferably, it is at least one compound selected from the group consisting of diol di(meth)acrylate and 1,10-decanediol di(meth)acrylate.

Furthermore, one of the preferred embodiments of the ethylenically unsaturated compound is an ethylenically unsaturated compound having two or more functionalities.
As used herein, the term "bifunctional or more ethylenically unsaturated compound" means a compound having two or more ethylenically unsaturated groups in one molecule.
As the ethylenically unsaturated group in the ethylenically unsaturated compound, a (meth)acryloyl group is preferable.
As the ethylenically unsaturated compound, (meth)acrylate compounds are preferred.

The bifunctional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.
Examples of bifunctional ethylenically unsaturated compounds other than the above compound M include tricyclodecane dimethanol di(meth)acrylate and 1,4-cyclohexanediol di(meth)acrylate.

Commercially available bifunctional ethylenically unsaturated compounds include tricyclodecane dimethanol diacrylate (product name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.) and tricyclodecane dimethanol dimethacrylate (product name: NK Ester A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.). Name: NK Ester DCP, manufactured by Shin Nakamura Chemical Co., Ltd.), 1,9-nonanediol diacrylate (Product name: NK Ester A-NOD-N, manufactured by Shin Nakamura Chemical Co., Ltd.), 1,6-hexanediol Diacrylate (trade name: NK Ester A-HD-N, manufactured by Shin-Nakamura Chemical Co., Ltd.) is mentioned.

The trifunctional or higher-functional ethylenically unsaturated compound is not particularly limited and can be appropriately selected from known compounds.
Examples of trifunctional or higher-functional ethylenically unsaturated compounds include dipentaerythritol (tri/tetra/penta/hexa) (meth)acrylate, pentaerythritol (tri/tetra) (meth)acrylate, trimethylolpropane tri(meth)acrylate, Examples include ditrimethylolpropane tetra(meth)acrylate, isocyanuric acid (meth)acrylate, and (meth)acrylate compounds having a glycerin tri(meth)acrylate skeleton.

Examples of ethylenically unsaturated compounds include (meth)acrylate compounds modified with caprolactone (KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin Nakamura Chemical Co., Ltd.), (meth) ) Alkylene oxide modified compounds of acrylate compounds (KAYARAD (registered trademark) RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Allnex Co., Ltd.) etc.), and ethoxylated glycerin triacrylate (such as NK Ester A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd.).

Ethylenically unsaturated compounds also include urethane (meth)acrylate compounds.
Examples of urethane (meth)acrylates include urethane di(meth)acrylates, such as propylene oxide-modified urethane di(meth)acrylates, and ethylene oxide- and propylene oxide-modified urethane di(meth)acrylates.
Furthermore, examples of urethane (meth)acrylates include trifunctional or higher functional urethane (meth)acrylates. The lower limit of the number of functional groups is more preferably 6 functional groups or more, and even more preferably 8 functional groups or more. Note that the upper limit of the number of functional groups is preferably 20 or less functional groups. Examples of trifunctional or higher functional urethane (meth)acrylates include 8UX-015A (manufactured by Taisei Fine Chemical Co., Ltd.), UA-32P (manufactured by Shin Nakamura Chemical Co., Ltd.), and U-15HA (manufactured by Shin Nakamura Chemical Co., Ltd.). , UA-1100H (manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), AH-600 (product name) manufactured by Kyoeisha Chemical Co., Ltd., and UA-306H, UA-306T, UA-306I, UA-510H, and UX-5000. (all manufactured by Nippon Kayaku Co., Ltd.), etc.

One of the preferred embodiments of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an acid group.
Examples of acid groups include phosphoric acid groups, sulfo groups, and carboxy groups.
Among these, a carboxy group is preferable as the acid group.
Examples of ethylenically unsaturated compounds having an acid group include trifunctional to tetrafunctional ethylenically unsaturated compounds having an acid group [pentaerythritol tri- and tetraacrylate (PETA) with a carboxy group introduced into the skeleton (acid value: 80 mgKOH) /g to 120mgKOH/g)], a pentafunctional to hexafunctional ethylenically unsaturated compound having an acid group (dipentaerythritol penta and hexaacrylate (DPHA) with a carboxy group introduced into the skeleton [acid value: 25mgKOH/g) ~70mgKOH/g)].
These trifunctional or higher functional ethylenically unsaturated compounds having an acid group may be used in combination with a bifunctional ethylenically unsaturated compound having an acid group, if necessary.

The ethylenically unsaturated compound having an acid group is preferably at least one selected from the group consisting of bifunctional or more ethylenically unsaturated compounds having a carboxy group and their carboxylic acid anhydrides.
When the ethylenically unsaturated compound having an acid group is at least one selected from the group consisting of bifunctional or more ethylenically unsaturated compounds having a carboxy group and their carboxylic acid anhydrides, developability and film strength are improved. It increases.
The bifunctional or more ethylenically unsaturated compound having a carboxy group is not particularly limited, and can be appropriately selected from known compounds.
Examples of the bifunctional or more ethylenically unsaturated compound having a carboxyl group include Aronix (registered trademark) TO-2349 (manufactured by Toagosei Co., Ltd.), Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.), and Aronix (registered trademark) M-520 (manufactured by Toagosei Co., Ltd.). (registered trademark) M-510 (manufactured by Toagosei Co., Ltd.).

The ethylenically unsaturated compound having an acid group is preferably a polymerizable compound having an acid group described in paragraphs 0025 to 0030 of JP-A No. 2004-239942, and the contents of this publication are not incorporated herein. It will be done.

Examples of ethylenically unsaturated compounds include compounds obtained by reacting polyhydric alcohols with α,β-unsaturated carboxylic acids, and compounds obtained by reacting glycidyl group-containing compounds with α,β-unsaturated carboxylic acids. , urethane monomers such as (meth)acrylate compounds having urethane bonds, γ-chloro-β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, β-hydroxyethyl-β'-(meth)acryloyl Also included are phthalic acid compounds such as oxyethyl-o-phthalate and β-hydroxypropyl-β'-(meth)acryloyloxyethyl-o-phthalate, and (meth)acrylic acid alkyl esters.
These may be used alone or in combination of two or more.

Examples of compounds obtained by reacting polyhydric alcohols with α,β-unsaturated carboxylic acids include 2,2-bis(4-((meth)acryloxypolyethoxy)phenyl)propane, 2,2-bis Bisphenol A-based (meth)acrylate compounds such as (4-((meth)acryloxypolypropoxy)phenyl)propane and 2,2-bis(4-((meth)acryloxypolyethoxypolypropoxy)phenyl)propane , polyethylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups, polypropylene glycol di(meth)acrylate having 2 to 14 propylene oxide groups, and polypropylene glycol di(meth)acrylate having 2 to 14 ethylene oxide groups. , and polyethylene polypropylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane ethoxytri(meth)acrylate having 2 to 14 propylene oxide groups. , trimethylolpropane diethoxytri(meth)acrylate, trimethylolpropane triethoxytri(meth)acrylate, trimethylolpropane tetraethoxytri(meth)acrylate, trimethylolpropane pentaethoxytri(meth)acrylate, di(trimethylolpropane) ) Tetraacrylate, tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate can be mentioned.
Among these, ethylenically unsaturated compounds having a tetramethylolmethane structure or a trimethylolpropane structure are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di- (Trimethylolpropane)tetraacrylate is more preferred.

Examples of the ethylenically unsaturated compound include caprolactone-modified compounds of ethylenically unsaturated compounds (for example, KAYARAD (registered trademark) DPCA-20 manufactured by Nippon Kayaku Co., Ltd., A-9300-1CL manufactured by Shin Nakamura Chemical Co., Ltd.), Alkylene oxide-modified compounds of ethylenically unsaturated compounds (for example, KAYARAD RP-1040 manufactured by Nippon Kayaku Co., Ltd., ATM-35E, A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd., EBECRYL (registered trademark) 135 manufactured by Daicel Allnex Corporation) etc.), ethoxylated glycerin triacrylate (A-GLY-9E manufactured by Shin-Nakamura Chemical Co., Ltd., etc.), and the like.

As the ethylenically unsaturated compound, those containing an ester bond are also preferred from the viewpoint of excellent developability.
The ethylenically unsaturated compound containing an ester bond is not particularly limited as long as it contains an ester bond in the molecule, but from the viewpoint of excellent curability and developability, ethylene having a tetramethylolmethane structure or trimethylolpropane structure is used. Unsaturated compounds are preferred, and tetramethylolmethane tri(meth)acrylate, tetramethylolmethanetetra(meth)acrylate, trimethylolpropane tri(meth)acrylate, or di(trimethylolpropane)tetraacrylate is more preferred.
From the standpoint of imparting reliability, the ethylenically unsaturated compounds include ethylenically unsaturated compounds having an aliphatic group having 6 to 20 carbon atoms, and ethylenically unsaturated compounds having the above-mentioned tetramethylolmethane structure or trimethylolpropane structure. It is preferable to include a compound.
Examples of ethylenically unsaturated compounds having an aliphatic structure having 6 or more carbon atoms include 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, and tricyclodecane dimethanol di(meth)acrylate. (Meth)acrylates are mentioned.

One preferred embodiment of the ethylenically unsaturated compound is an ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure (preferably a difunctional ethylenically unsaturated compound).
The ethylenically unsaturated compound is an ethylenic compound having a ring structure in which two or more aliphatic hydrocarbon rings are condensed (preferably a structure selected from the group consisting of a tricyclodecane structure and a tricyclodecene structure). Unsaturated compounds are preferred, bifunctional ethylenically unsaturated compounds having a ring structure in which two or more aliphatic hydrocarbon rings are condensed are more preferred, and tricyclodecane dimethanol di(meth)acrylate is even more preferred.
The above-mentioned aliphatic hydrocarbon ring structures include a cyclopentane structure, a cyclohexane structure, a tricyclodecane structure, and a tricyclodecene structure, from the viewpoint of moisture permeability and bending resistance of the obtained cured film, and adhesiveness of the obtained uncured film. structure, norbornane structure, or isoborone structure.

The molecular weight of the ethylenically unsaturated compound is preferably 200 to 3,000, more preferably 250 to 2,600, even more preferably 280 to 2,200, particularly preferably 300 to 2,200.
Among the ethylenically unsaturated compounds contained in the photosensitive resin layer, the content ratio of ethylenically unsaturated compounds with a molecular weight of 300 or less is relative to the content of all ethylenically unsaturated compounds contained in the photosensitive resin layer. The content is preferably 30% by mass or less, more preferably 25% by mass or less, and even more preferably 20% by mass or less.

As one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a bifunctional or more ethylenically unsaturated compound, more preferably contains a trifunctional or more ethylenically unsaturated compound, It is further preferred that a functional or tetrafunctional ethylenically unsaturated compound is included.

In addition, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer includes a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure and an alkali-soluble compound having a structural unit having an aliphatic hydrocarbon ring. It is preferable to include a resin.

Further, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer preferably contains a compound represented by formula (M) and an ethylenically unsaturated compound having an acid group, - more preferably contains nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group; More preferably, it contains methanol diacrylate and a succinic acid modified product of dipentaerythritol pentaacrylate.

In addition, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer contains a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a thermally crosslinkable compound described below. It is preferable to include a compound represented by formula (M), an ethylenically unsaturated compound having an acid group, and a block isocyanate compound described below.

In addition, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer is made of a difunctional ethylenically unsaturated compound (preferably a difunctional ( meth)acrylate compound) and a trifunctional or more functional ethylenically unsaturated compound (preferably a trifunctional or more functional (meth)acrylate compound).
The mass ratio of the content of the bifunctional ethylenically unsaturated compound and the trifunctional or higher functional ethylenically unsaturated compound is preferably 10:90 to 90:10, more preferably 30:70 to 70:30.
The content of the bifunctional ethylenically unsaturated compound relative to the total amount of all ethylenically unsaturated compounds is preferably 20% by mass to 80% by mass, more preferably 30% by mass to 70% by mass.
The content of the bifunctional ethylenically unsaturated compound in the photosensitive resin layer is preferably 10% by mass to 60% by mass, more preferably 15% by mass to 40% by mass, based on the total mass of the photosensitive resin layer.

Further, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer contains the compound M and a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure from the viewpoint of rust prevention. is preferred.
In addition, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer contains Compound M and an ethylenic non-containing compound having an acid group, from the viewpoints of substrate adhesion, development residue suppression, and rust prevention. It is preferable to contain a saturated compound, and it is more preferable to contain a compound M, a bifunctional ethylenically unsaturated compound having an aliphatic hydrocarbon ring structure, and an ethylenically unsaturated compound having an acid group. It is more preferable to include a bifunctional ethylenically unsaturated compound having a hydrocarbon ring structure, a trifunctional or more functional ethylenically unsaturated compound, and an ethylenically unsaturated compound having an acid group, and compound M, an aliphatic hydrocarbon ring It is particularly preferable to include a bifunctional ethylenically unsaturated compound having a structure, a trifunctional or more functional ethylenically unsaturated compound, an ethylenically unsaturated compound having an acid group, and a urethane (meth)acrylate compound.
In addition, as one of the preferred embodiments of the photosensitive resin layer, the photosensitive resin layer contains 1,9-nonanediol diacrylate and carbon dioxide, from the viewpoints of substrate adhesion, development residue suppression, and rust prevention. It preferably contains a polyfunctional ethylenically unsaturated compound having an acid group, and includes 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, and a polyfunctional ethylenically unsaturated compound having a carboxylic acid group. It is preferable that 1,9-nonanediol diacrylate, tricyclodecane dimethanol diacrylate, dipentaerythritol hexaacrylate, and an ethylenically unsaturated compound having a carboxylic acid group are included, and 1,9- It is particularly preferable to include nonanediol diacrylate, tricyclodecane dimethanol diacrylate, an ethylenically unsaturated compound having a carboxylic acid group, and a urethane acrylate compound.

The photosensitive resin layer may contain a monofunctional ethylenically unsaturated compound as the ethylenically unsaturated compound.
The content of the bifunctional or more ethylenically unsaturated compound in the ethylenically unsaturated compound is 60% by mass to 100% by mass based on the total content of all ethylenically unsaturated compounds contained in the photosensitive resin layer. It is preferably 80% by mass to 100% by mass, more preferably 90% by mass to 100% by mass.

The ethylenically unsaturated compounds may be used alone or in combination of two or more.
The content of the ethylenically unsaturated compound in the photosensitive resin layer is preferably 1% by mass to 70% by mass, more preferably 5% by mass to 70% by mass, and 5% by mass based on the total mass of the photosensitive resin layer. It is more preferably 60% by weight, particularly preferably 5% by weight to 50% by weight.

-Polymerization initiator-
The photosensitive resin layer may contain a polymerization initiator.
As the polymerization initiator, a photopolymerization initiator is preferred.
The preferred embodiments of the photopolymerization initiator are the same as the preferred embodiments of the photopolymerization initiator explained in the section of "Photosensitive resin layer" above.
The polymerization initiators may be used alone or in combination of two or more.
The content of the polymerization initiator is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and 1.0% by mass or more based on the total mass of the photosensitive resin layer. It is more preferable that Further, the upper limit thereof is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total mass of the photosensitive resin layer.

-Heterocyclic compounds-
The photosensitive resin layer may contain a heterocyclic compound.
The heterocycle possessed by the heterocyclic compound may be either a monocyclic or polycyclic heterocycle.
Examples of the heteroatom contained in the heterocyclic compound include a nitrogen atom, an oxygen atom, and a sulfur atom. The heterocyclic compound preferably contains at least one atom selected from the group consisting of a nitrogen atom, an oxygen atom, and a sulfur atom, and more preferably a nitrogen atom.

Examples of the heterocyclic compound include a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a triazine compound, a rhodanine compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, a benzoxazole compound, and a pyrimidine compound.
Among the above, the heterocyclic compound is at least one selected from the group consisting of triazole compounds, benzotriazole compounds, tetrazole compounds, thiadiazole compounds, triazine compounds, rhodanine compounds, thiazole compounds, benzimidazole compounds, and benzoxazole compounds. Preferably, at least one compound selected from the group consisting of a triazole compound, a benzotriazole compound, a tetrazole compound, a thiadiazole compound, a thiazole compound, a benzothiazole compound, a benzimidazole compound, and a benzoxazole compound is more preferable.

Preferred specific examples of the heterocyclic compound are shown below. Examples of the triazole compound and benzotriazole compound include the following compounds.

Examples of the tetrazole compound include the following compounds.

Examples of thiadiazole compounds include the following compounds.

Examples of triazine compounds include the following compounds.

Examples of rhodanine compounds include the following compounds.

Examples of thiazole compounds include the following compounds.

Examples of benzothiazole compounds include the following compounds.

Examples of benzimidazole compounds include the following compounds.

Examples of benzoxazole compounds include the following compounds.

The heterocyclic compounds may be used alone or in combination of two or more.
When the photosensitive resin layer contains a heterocyclic compound, the content of the heterocyclic compound is preferably 0.01% by mass to 20.0% by mass, and 0.10% by mass based on the total mass of the photosensitive resin layer. It is more preferably from 10.0% by weight, even more preferably from 0.30% to 8.0% by weight, and particularly preferably from 0.50% to 5.0% by weight.

-Aliphatic thiol compounds-
The photosensitive resin layer may contain an aliphatic thiol compound.
When the photosensitive resin layer contains an aliphatic thiol compound, the aliphatic thiol compound undergoes an ene-thiol reaction with the ethylenically unsaturated compound, which suppresses curing shrinkage of the formed film and relieves stress. be done.

As the aliphatic thiol compound, a monofunctional aliphatic thiol compound or a polyfunctional aliphatic thiol compound (that is, an aliphatic thiol compound having two or more functionalities) is preferable.
Among the above aliphatic thiol compounds, polyfunctional aliphatic thiol compounds are more preferable from the viewpoint of the adhesion of the formed pattern (particularly the adhesion after exposure).
As used herein, the term "polyfunctional aliphatic thiol compound" means an aliphatic compound having two or more thiol groups (also referred to as "mercapto groups") in the molecule.

As the polyfunctional aliphatic thiol compound, a low molecular compound having a molecular weight of 100 or more is preferable. Specifically, the molecular weight of the polyfunctional aliphatic thiol compound is more preferably 100 to 1,500, and even more preferably 150 to 1,000.

The number of functional groups in the polyfunctional aliphatic thiol compound is, for example, preferably from 2 to 10 functional, more preferably from 2 to 8 functional, more preferably from 2 to 6 functional, from the viewpoint of adhesion of the formed pattern. preferable.

Examples of polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, trimethylolethane tris(3-mercaptobutyrate) ), tris[(3-mercaptopropionyloxy)ethyl]isocyanurate, trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), tetraethylene glycol bis(3-mercaptopropionate) pionate), dipentaerythritol hexakis (3-mercaptopropionate), ethylene glycol bisthiopropionate, 1,4-bis(3-mercaptobutyryloxy)butane, 1,2-ethanedithiol, 1, Examples include 3-propanedithiol, 1,6-hexamethylene dithiol, 2,2'-(ethylenedithio)diethanethiol, meso-2,3-dimercaptosuccinic acid, and di(mercaptoethyl) ether.

Among the above, polyfunctional aliphatic thiol compounds include trimethylolpropane tris(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, and 1,3,5-tris At least one compound selected from the group consisting of (3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione is preferred.

Examples of monofunctional aliphatic thiol compounds include 1-octanethiol, 1-dodecanethiol, β-mercaptopropionic acid, methyl-3-mercaptopropionate, 2-ethylhexyl-3-mercaptopropionate, n- Examples include octyl-3-mercaptopropionate, methoxybutyl-3-mercaptopropionate, and stearyl-3-mercaptopropionate.

The photosensitive resin layer may contain one type of aliphatic thiol compound alone, or may contain two or more types of aliphatic thiol compounds.
When the photosensitive resin layer contains an aliphatic thiol compound, the content of the aliphatic thiol compound is preferably 5% by mass or more, more preferably 5% by mass to 50% by mass, based on the total mass of the photosensitive resin layer. , more preferably 5% to 30% by weight, particularly preferably 8% to 20% by weight.

-Thermal crosslinkable compound-
The photosensitive resin layer preferably contains a thermally crosslinkable compound from the viewpoint of the strength of the resulting cured film and the tackiness of the resulting uncured film.
Examples of the thermally crosslinkable compound include the thermally crosslinkable compounds described in the section of "Photosensitive resin layer" above.
Thermal crosslinkable compounds may be used alone or in combination of two or more.
When the photosensitive resin layer contains a thermally crosslinkable compound, the content of the thermally crosslinkable compound is preferably 1% by mass to 50% by mass, and 5% by mass to 30% by mass, based on the total mass of the photosensitive resin layer. is more preferable.

-Surfactant-
The photosensitive resin layer may contain a surfactant.
Examples of the surfactant include the surfactants described in the above "Photosensitive resin layer" section.
The surfactants may be used alone or in combination of two or more.
When the photosensitive resin layer contains a surfactant, the content of the surfactant is preferably 0.01% by mass to 3.0% by mass, and 0.01% by mass based on the total mass of the photosensitive resin layer. It is more preferably 1.0% by mass, and even more preferably 0.05% by mass to 0.80% by mass.

-Radical polymerization inhibitor-
The photosensitive resin layer may contain a radical polymerization inhibitor.
Examples of the radical polymerization inhibitor include the radical polymerization inhibitors described in the section of "Photosensitive resin layer" above.
The radical polymerization inhibitors may be used alone or in combination of two or more.
When the photosensitive resin layer contains a radical polymerization inhibitor, the content of the radical polymerization inhibitor is preferably 0.01% by mass to 3% by mass, and 0.05% by mass based on the total mass of the photosensitive resin layer. More preferably 1% by mass. When the content is 0.01% by mass or more, the storage stability of the photosensitive resin layer is better. On the other hand, when the content is 3% by mass or less, sensitivity can be maintained and dye decolorization can be suppressed more effectively.

-Hydrogen donating compound-
The photosensitive resin layer may contain a hydrogen donating compound.
The hydrogen-donating compound has effects such as further improving the sensitivity of the photopolymerization initiator to actinic rays and suppressing inhibition of polymerization of the polymerizable compound by oxygen.
Examples of hydrogen-donating compounds include amines and amino acid compounds.

Examples of amines include M. R. "Journal of Polymer Society" Vol. 10, p. 3173 (1972) by Sander et al. Examples include compounds described in JP-A-60-084305, JP-A-62-018537, JP-A-64-033104, and Research Disclosure 33825. More specifically, 4,4'-bis(diethylamino)benzophenone, tris(4-dimethylaminophenyl)methane (also known as leuco crystal violet), triethanolamine, p-dimethylaminobenzoic acid ethyl ester, p-formyl Dimethylaniline and p-methylthiodimethylaniline are mentioned.
Among these, from the viewpoints of sensitivity, curing speed, and curability, the amines include at least one selected from the group consisting of 4,4'-bis(diethylamino)benzophenone and tris(4-dimethylaminophenyl)methane. Seeds are preferred.

Examples of the amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
Among these, N-phenylglycine is preferred as the amino acid compound from the viewpoints of sensitivity, curing speed, and curability.

Examples of hydrogen-donating compounds include organometallic compounds (tributyltin acetate, etc.) described in Japanese Patent Publication No. 48-042965, hydrogen donors described in Japanese Patent Publication No. 55-034414, and JP-A-6 Also included are sulfur compounds (such as trithiane) described in JP-A-308727.

The hydrogen donating compounds may be used alone or in combination of two or more.
When the photosensitive resin layer contains a hydrogen-donating compound, the content of the hydrogen-donating compound is determined based on the total mass of the photosensitive resin layer from the viewpoint of improving the curing speed by balancing the polymerization growth rate and chain transfer. , is preferably 0.01% by mass to 10.0% by mass, more preferably 0.01% by mass to 8.0% by mass, and even more preferably 0.03% by mass to 5.0% by mass.

-impurities-
The photosensitive resin layer may contain a predetermined amount of impurities.
Examples of impurities include the impurities described in the section of the "photosensitive resin layer" above.

-Residual monomer-
The photosensitive resin layer may contain residual monomers corresponding to each structural unit of the polymer A described above.
Examples of the remaining monomers corresponding to each structural unit of the polymer A in the photosensitive resin layer include the remaining monomers corresponding to each structural unit of the polymer A explained in the section of "Photosensitive resin layer" above.

-Other ingredients-
The photosensitive resin layer may contain components other than the components described above (hereinafter also referred to as "other components"). Other components include, for example, colorants, antioxidants, and particles (eg, metal oxide particles). Further, other components include other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.

As the particles, metal oxide particles are preferred.
Metals in the metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.
The average primary particle diameter of the particles is, for example, preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, from the viewpoint of transparency of the cured film.
The average primary particle diameter of the particles is calculated by measuring the particle diameter of 200 arbitrary particles using an electron microscope and taking the arithmetic average of the measurement results. In addition, when the shape of the particle is not spherical, the longest side is taken as the particle diameter.

When the photosensitive resin layer contains particles, it may contain only one type of particles having different metal types and sizes, or may contain two or more types of particles.
The photosensitive resin layer does not contain particles, or if the photosensitive resin layer contains particles, the content of particles is more than 0% by mass and 35% by mass or less based on the total mass of the photosensitive resin layer. It is preferable that the layer contains no particles, or the content of particles is more than 0% by mass and 10% by mass or less based on the total mass of the photosensitive resin layer, and it contains no particles or contains particles. More preferably, the amount is more than 0% by mass and 5% by mass or less based on the total mass of the photosensitive resin layer, and either no particles are included or the content of particles is 0% by mass based on the total mass of the photosensitive resin layer. More preferably, the content is more than 1% by mass or less, and it is particularly preferable that no particles are included.

Although the photosensitive resin layer may contain a colorant (pigment, dye, etc.), for example, from the viewpoint of transparency, it is preferable that the photosensitive resin layer does not substantially contain a colorant.
When the photosensitive resin layer contains a colorant, the content of the colorant is preferably less than 1% by mass, more preferably less than 0.1% by mass, based on the total mass of the photosensitive resin layer.

Examples of antioxidants include 1-phenyl-3-pyrazolidone (also known as phenidone), 1-phenyl-4,4-dimethyl-3-pyrazolidone, and 1-phenyl-4-methyl-4-hydroxymethyl- 3-pyrazolidones such as 3-pyrazolidone; polyhydroxybenzenes such as hydroquinone, catechol, pyrogallol, methylhydroquinone, and chlorohydroquinone; paramethylaminophenol, paraaminophenol, parahydroxyphenylglycine, and paraphenylenediamine. It will be done.
Among these, from the viewpoint of storage stability and curability, as the antioxidant, 3-pyrazolidones are preferred, and 1-phenyl-3-pyrazolidone is more preferred.

When the photosensitive resin layer contains an antioxidant, the content of the antioxidant is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, based on the total mass of the photosensitive resin layer. More preferably, the content is 0.01% by mass or more. The upper limit is not particularly limited, but is preferably 1% by mass or less.

-Thickness of photosensitive resin layer-
The thickness (layer thickness) of the photosensitive resin layer is not particularly limited, but from the viewpoint of developability and resolution, it is preferably 30 μm or less, more preferably 20 μm or less, even more preferably 15 μm or less, particularly preferably 10 μm or less, Most preferably, it is 5.0 μm or less. The lower limit is preferably 0.60 μm or more, more preferably 1.5 μm or more, since the strength of the film obtained by curing the photosensitive resin layer is excellent.

-Refractive index of photosensitive resin layer-
The refractive index of the photosensitive resin layer is preferably 1.47 to 1.56, more preferably 1.49 to 1.54.

-Color of photosensitive resin layer-
The photosensitive resin layer is preferably achromatic. Specifically, total internal reflection (incident angle 8°, light source: D-65 (2° field of view)) has an L ^* value of 10 to 90 in the CIE1976 (L ^* , a ^* , b ^* ) color space. The a ^* value is preferably -1.0 to 1.0, and the b ^* value is preferably -1.0 to 1.0.

Note that the pattern obtained by curing the photosensitive resin layer (cured film of the photosensitive resin layer) is preferably achromatic.
Specifically, total internal reflection (incident angle 8°, light source: D-65 (2° field of view)) is such that the L ^* value of the pattern is 10 to 90 in the CIE1976 (L ^* , a ^* , b ^* ) color space. The a ^* value of the pattern is preferably from -1.0 to 1.0, and the b ^* value of the pattern is preferably from -1.0 to 1.0.

- Moisture permeability of photosensitive resin layer -
The moisture permeability of the pattern obtained by curing the photosensitive resin layer (cured film of the photosensitive resin layer) at a layer thickness of 40 μm is preferably 500 g/(m ² 24 hr) or less from the viewpoint of rust prevention. It is preferably at most 300 g/(m ² ·24 hr), more preferably at most 100 g/(m ² ·24 hr).
The moisture permeability is determined by exposing the photosensitive resin layer to i-line at an exposure dose of 300 mJ/cm ² and then post-baking at 145°C for 30 minutes to cure the photosensitive resin layer. Measure with.

(Refractive index adjustment layer)
It is preferable that the photosensitive transfer material has a refractive index adjusting layer.
A known refractive index adjusting layer can be used as the refractive index adjusting layer. Examples of materials included in the refractive index adjusting layer include alkali-soluble resins, ethylenically unsaturated compounds, metal salts, and particles.
The method of controlling the refractive index of the refractive index adjustment layer is not particularly limited, and examples include a method of using a resin having a predetermined refractive index alone, a method of using a resin and particles, and a method of using a composite of a metal salt and a resin. An example of this method is to use

Examples of the alkali-soluble resin and ethylenically unsaturated compound include the alkali-soluble resin and ethylenically unsaturated compound described in the section of the "photosensitive resin layer" above.

Examples of the particles include metal oxide particles and metal particles.
The type of metal oxide particles is not particularly limited, and examples thereof include known metal oxide particles. Metals in the metal oxide particles also include semimetals such as B, Si, Ge, As, Sb, and Te.

The average primary particle diameter of the particles is, for example, preferably 1 nm to 200 nm, more preferably 3 nm to 80 nm, from the viewpoint of transparency of the cured film.
The average primary particle diameter of the particles is calculated by measuring the particle diameter of 200 arbitrary particles using an electron microscope and taking the arithmetic average of the measurement results. In addition, when the shape of the particle is not spherical, the longest side is taken as the particle diameter.

Specifically, the metal oxide particles include zirconium oxide particles (ZrO ₂ particles), Nb ₂ O ₅ particles, titanium oxide particles (TiO ₂ particles), silicon dioxide particles (SiO ₂ particles), and composites thereof. At least one kind selected from the group consisting of particles is preferable.
Among these, as the metal oxide particles, at least one selected from the group consisting of zirconium oxide particles and titanium oxide particles is more preferable, for example, because the refractive index can be easily adjusted.

Commercially available metal oxide particles include calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F04), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F74), Calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F75), calcined zirconium oxide particles (manufactured by CIK Nanotech Co., Ltd., product name: ZRPGM15WT%-F76), zirconium oxide particles (Nano Youth OZ-S30M, Nissan and zirconium oxide particles (Nano Youth OZ-S30K, manufactured by Nissan Chemical Industries, Ltd.).

The particles may be used alone or in combination of two or more.
The content of particles in the refractive index adjusting layer is preferably 1% by mass to 95% by mass, more preferably 20% to 90% by mass, and 40% to 85% by mass, based on the total mass of the refractive index adjusting layer. More preferred.
When using titanium oxide as the metal oxide particles, the content of titanium oxide particles is preferably 1% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, based on the total mass of the refractive index adjusting layer. , more preferably 40% by mass to 85% by mass.

The refractive index of the refractive index adjusting layer is preferably higher than the refractive index of the photosensitive resin layer.
The refractive index of the refractive index adjusting layer is preferably 1.50 or more, more preferably 1.55 or more, even more preferably 1.60 or more, and particularly preferably 1.65 or more. The upper limit of the refractive index of the refractive index adjusting layer is preferably 2.10 or less, more preferably 1.85 or less, and particularly preferably 1.78 or less.

The thickness of the refractive index adjusting layer is preferably 50 nm to 500 nm, more preferably 55 nm to 110 nm, even more preferably 60 nm to 100 nm.

The refractive index adjustment layer is formed using, for example, a refractive index adjustment layer. It is preferable that the composition for forming a refractive index adjustment layer contains the various components for forming the refractive index adjustment layer described above and a solvent. In addition, in the composition for forming a refractive index adjustment layer, the preferred range of the content of each component relative to the total solid content of the composition is the same as the preferred range of the content of each component relative to the total mass of the refractive index adjustment layer described above. be.
The solvent is not particularly limited as long as it is capable of dissolving or dispersing the components contained in the refractive index adjusting layer, and is preferably at least one selected from the group consisting of water and water-miscible organic solvents. A mixed solvent with a water-miscible organic solvent is more preferred.
Examples of the water-miscible organic solvent include alcohols having 1 to 3 carbon atoms, acetone, ethylene glycol, and glycerin, with alcohols having 1 to 3 carbon atoms being preferred, and methanol or ethanol being more preferred.
One type of solvent may be used alone, or two or more types may be used.
The content of the solvent is preferably 50 parts by mass to 2,500 parts by mass, more preferably 50 parts by mass to 1,900 parts by mass, and 100 parts by mass to 900 parts by mass, based on 100 parts by mass of the total solid content of the composition. Part is more preferable.

The method for forming the refractive index adjusting layer is not particularly limited as long as it is a method that can form a layer containing the above components, and examples thereof include known coating methods (slit coating, spin coating, curtain coating, inkjet coating, etc.). It will be done.

(Relationship between temporary support, photosensitive resin layer and protective film)
Also in the photosensitive transfer material preferably used as a photosensitive transfer material for a wiring protective film, it is preferable that the above-mentioned relationship between the temporary support, the photosensitive resin layer and the protective film is satisfied.

<Resin pattern manufacturing method>
A method for manufacturing a resin pattern according to an embodiment of the present disclosure is a method for manufacturing a resin pattern using a photosensitive transfer material according to the present disclosure. According to an embodiment of the present disclosure, a method for manufacturing a resin pattern in which the generation of pinholes is suppressed is provided. A method for manufacturing a resin pattern according to an embodiment of the present disclosure includes a step of preparing a substrate (hereinafter sometimes referred to as a "preparation step"), and a step of bringing a photosensitive transfer material into contact with the substrate. A process of arranging a photosensitive resin layer and a temporary support in this order on top (hereinafter sometimes referred to as "bonding process"), and a process of exposing the photosensitive resin layer in a pattern (hereinafter referred to as "exposure process") ) and a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter sometimes referred to as a "developing step").

＜＜Preparation process＞＞
In the preparation step, a substrate is prepared. The type of substrate is not limited. Preferably, the substrate is a substrate including a conductive layer. Further, the substrate preferably includes a base material and a conductive layer on the base material, more preferably a base material and a conductive layer in contact with the base material. preferable. The conductive layer may be placed on one side of the substrate. The conductive layers may be arranged on both sides of the base material. The substrate may include layers other than the conductive layer.

Examples of the base material include glass, silicon, and resin film. Preferably, the base material is transparent. In the present disclosure, "transparent" means that the transmittance at a wavelength of 400 nm to 700 nm is 80% or more. The refractive index of the base material is preferably 1.50 to 1.52.

Examples of transparent glass include tempered glass represented by Corning's Gorilla Glass. As the transparent glass, materials used in JP-A No. 2010-86684, JP-A No. 2010-152809, and JP-A No. 2010-257492 may be used.

It is preferable that the resin film has low optical distortion or high transparency. Examples of the resin film described above include polyethylene terephthalate (PET), polyethylene naphthalate, polycarbonate, triacetylcellulose, and cycloolefin polymer.

In the method for manufacturing a resin pattern using a roll-to-roll method, the base material is preferably a resin film.

Examples of the conductive layer include conductive layers used for general circuit wiring or touch panel wiring. The conductive layer is preferably an electrode pattern corresponding to a sensor of a visual recognition part used in a capacitive touch panel or wiring of a peripheral extraction part.

From the viewpoint of electrical conductivity and fine line forming properties, the electrically conductive layer is preferably at least one selected from the group consisting of a metal layer, a conductive metal oxide layer, a graphene layer, a carbon nanotube layer, and a conductive polymer layer, A metal layer is more preferable, and a copper layer or a silver layer is particularly preferable.

Components of the conductive layer include, for example, metals and conductive metal oxides. Examples of metals include Al, Zn, Cu, Fe, Ni, Cr, Mo, Ag, and Au. Examples of the conductive metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ₂ . In the present disclosure, "conductivity" means a property in which the volume resistivity is less than 1×10 ⁶ Ωcm. The volume resistivity of the conductive metal oxide is preferably less than 1×10 ⁴ Ωcm.

When manufacturing a resin pattern using a substrate including a plurality of conductive layers, it is preferable that at least one conductive layer among the plurality of conductive layers contains a conductive metal oxide.

The substrate may include one or more conductive layers. When the substrate includes two or more conductive layers, the substrate preferably includes two or more conductive layers formed of different materials.

Preferred embodiments of the conductive layer are described, for example, in paragraph 0141 of WO 2018/155193, the contents of which are incorporated herein by reference.

As the substrate including the conductive layer, a substrate having at least one of a transparent electrode and a lead-out wiring is preferable. The above substrate can be suitably used as a touch panel substrate. The transparent electrode can suitably function as an electrode for a touch panel. The transparent electrode is preferably composed of a metal oxide film such as ITO (indium tin oxide) and IZO (indium zinc oxide), a metal mesh, and a metal thin wire such as metal nanowire. Examples of the thin metal wire include thin wires made of silver, copper, and the like. Among these, silver conductive materials such as silver mesh and silver nanowires are preferred.

Metal is preferable as the material for the lead-out wiring. Examples of the metal that is the material of the routing wiring include gold, silver, copper, molybdenum, aluminum, titanium, chromium, zinc, and manganese, as well as alloys made of two or more of these metal elements. The material for the lead-out wiring is preferably copper, molybdenum, aluminum, or titanium, with copper being particularly preferred.

<<Lamination process>>
In the bonding step, a photosensitive transfer material is brought into contact with the substrate, and a photosensitive resin layer and a temporary support are placed on the substrate in this order.

The photosensitive transfer material is as described in the section of "Photosensitive transfer material" above. Preferred embodiments of the photosensitive transfer material used in the bonding step are the same as the preferred embodiments of the photosensitive transfer material explained in the section of "Photosensitive transfer material" above.

In the bonding step, the photosensitive resin layer and temporary support disposed on the substrate are respectively included in the photosensitive transfer material. That is, the layer structure of the laminate obtained by the bonding process changes depending on the layer structure of the photosensitive transfer material. For example, in the bonding process, when a photosensitive transfer material containing a temporary support, a thermoplastic resin layer, an intermediate layer, and a photosensitive resin layer in this order is brought into contact with the substrate, on the substrate, A photosensitive resin layer, an intermediate layer, a thermoplastic resin layer, and a temporary support are arranged in this order. When the photosensitive transfer material includes a protective film, the protective film is removed from the photosensitive transfer material, and then the photosensitive transfer material is brought into contact with the substrate.

In the bonding step, it is preferable to bring the photosensitive transfer material into contact with the substrate and press the photosensitive transfer material onto the substrate. For example, it is preferable to press the photosensitive transfer material onto the substrate by bringing the photosensitive transfer material into contact with the substrate and applying pressure and heat to the substrate and the photosensitive transfer material using a means such as a roll. .

In the method of bringing the photosensitive transfer material into contact with the substrate (including the method of press-bonding the photosensitive transfer material to the substrate), for example, a known transfer method or a known lamination method is used. In the method of bringing the photosensitive transfer material into contact with the substrate, for example, a laminator, a vacuum laminator, or an auto-cut laminator that can further improve productivity is used.

<<Exposure process>>
In the exposure step, the photosensitive resin layer is exposed in a pattern. The arrangement and dimensions of patterns in pattern exposure are not limited. At least a portion of the pattern (preferably a portion corresponding to the electrode pattern or lead-out wiring of the touch panel) preferably includes a thin line having a width of 20 μm or less, and more preferably includes a thin line having a width of 10 μm or less.

Examples of the light source in the exposure step include a light source that irradiates light with a wavelength that can expose the photosensitive resin layer (for example, 365 nm or 405 nm). Examples of the light source include an ultra-high-pressure mercury lamp, a high-pressure mercury lamp, a metal halide lamp, and an LED (Light Emitting Diode).

The exposure amount is preferably 5 mJ/cm ² to 300 mJ/cm ² , more preferably 10 mJ/cm ² to 200 mJ/cm ² .

In the exposure step, the photosensitive resin layer may be exposed in a pattern after the temporary support is peeled off. In the exposure step, the photosensitive resin layer may be pattern-exposed through the temporary support, and then the temporary support may be peeled off.

When the temporary support is peeled off before pattern exposure in an exposure method using a photomask, the photosensitive resin layer may be exposed by bringing the photomask into contact with the photosensitive resin layer, or the photomask may be brought into contact with the photosensitive resin layer. The photosensitive resin layer may be exposed by bringing the photomask close to the photosensitive resin layer without contacting it. When exposing a photosensitive resin layer to light through a temporary support in an exposure method using a photomask, the photosensitive resin layer may be exposed by bringing the photomask into contact with the temporary support; The photosensitive resin layer may be exposed by bringing the photomask close to the temporary support without contacting it. In order to prevent contamination of the photomask due to contact between the photosensitive resin layer and the photomask, and to avoid the influence of foreign matter adhering to the photomask on exposure, the photosensitive resin layer is exposed in a pattern through a temporary support. It is preferable.

The exposure method is not limited. Examples of the exposure method include a contact exposure method and a non-contact exposure method. Examples of the contact exposure method include a method in which a photosensitive resin layer is pattern-exposed using a photomask. Examples of the non-contact exposure method include a proximity exposure method, a lens-based or mirror-based projection exposure method, and a direct exposure method using an exposure laser. In the lens-based or mirror-based projection exposure method, an exposure machine having an appropriate numerical aperture (NA) of the lens may be used depending on the required resolving power and depth of focus. In the direct exposure method, drawing may be performed directly on the photosensitive layer, or reduction projection exposure may be performed on the photosensitive layer through a lens. Exposure may be performed under air, reduced pressure, or vacuum. Exposure may be performed with a liquid such as water interposed between the light source and the photosensitive resin layer.

<<Developing process>>
In the development step, the exposed photosensitive resin layer is developed to form a resin pattern. When the photosensitive resin layer is a negative photosensitive resin layer, the non-exposed portions of the photosensitive resin layer are removed and the exposed portions of the photosensitive resin layer form a resin pattern. When the photosensitive resin layer is a positive type photosensitive resin layer, the exposed portion of the photosensitive resin layer is removed, and the non-exposed portion of the photosensitive resin layer forms a resin pattern. Further, in the bonding process, the thermoplastic resin layer and intermediate layer disposed on the substrate are removed together with the photosensitive resin layer. The thermoplastic resin layer and intermediate layer may be removed by dissolving or dispersing in a developer.

Development is performed using, for example, a developer. The developer is not limited as long as it can remove the target photosensitive resin layer. A known developer is used as the developer. Examples of the developer include the developer described in JP-A-5-72724. The developer is preferably an alkaline aqueous developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol/L to 5 mol/L. The developer may contain a water-soluble organic solvent and/or a surfactant. As the developer, the developer described in paragraph 0194 of International Publication No. 2015/093271 is also preferable.

The temperature of the developer is not limited. The temperature of the developer is preferably 20°C to 40°C.

The developing method is not limited. The development method may be, for example, paddle development, shower development, shower and spin development, or dip development. Shower development is a method of removing the target photosensitive resin layer by spraying a developer onto the exposed photosensitive resin layer by showering.

After the development step, it is preferable to spray a cleaning agent with a shower and remove the development residue while rubbing with a brush.

The line width of the resin pattern obtained through the above steps is preferably 20 μm or less, more preferably 10 μm or less, and particularly preferably 8 μm or less. The lower limit of the line width of the resin pattern is not limited. The line width of the resin pattern may be, for example, 1 μm or more. The line width of the resin pattern is measured by the following method. The resin pattern is observed using a scanning electron microscope (SEM), and the line widths at 30 locations on the resin pattern are measured. The arithmetic mean of the measured values is taken as the line width of the resin pattern.

The resin pattern obtained through the above steps may be used as a permanent film or a protective film for etching.

<<Roll-to-roll method>>
The resin pattern manufacturing method is preferably performed by a roll-to-roll method. The roll-to-roll method is a process in which a substrate that can be rolled up and unrolled is used, and the substrate or a laminate including the substrate is rolled out ("unrolled") before any of the steps included in the resin pattern manufacturing method. ) and a step of winding up the substrate or a laminate including the substrate after any of the steps (hereinafter sometimes referred to as the "winding step"). A method in which the steps (preferably all steps) are carried out while transporting the substrate or a laminate including the substrate. As the unwinding method in the unwinding step and the winding method in the winding step, for example, a known method applied to a roll-to-roll method is used.

<Method for manufacturing conductive pattern>
A method for manufacturing a conductive pattern according to an embodiment of the present disclosure is a method for manufacturing a conductive pattern using a photosensitive transfer material according to the present disclosure. According to an embodiment of the present disclosure, a method for manufacturing a conductive pattern in which pinholes are suppressed is provided. A method for manufacturing a conductive pattern according to an embodiment of the present disclosure includes a step of preparing a substrate including a conductive layer (hereinafter sometimes referred to as a "preparation step"), and bringing a photosensitive transfer material into contact with the substrate. , a step of arranging a photosensitive resin layer and a temporary support on the substrate in this order (hereinafter sometimes referred to as a "bonding step"), and a step of exposing the photosensitive resin layer in a pattern (hereinafter referred to as "bonding step"). ), a step of developing the exposed photosensitive resin layer to form a resin pattern (hereinafter, sometimes referred to as "developing process"), and It is preferable to include a step of etching the uncovered conductive layer to form a conductive pattern (hereinafter sometimes referred to as an "etching step").

＜＜Preparation process＞＞
In the preparation step, a substrate including a conductive layer is prepared. The substrate including the conductive layer is as described in the above section of "Resin pattern manufacturing method". The preferred embodiment of the substrate including the conductive layer is the same as the preferred embodiment of the substrate including the conductive layer described in the above section of "Resin pattern manufacturing method."
<<Lamination process>>
In the bonding step, a photosensitive transfer material is brought into contact with the substrate, and a photosensitive resin layer and a temporary support are placed on the substrate in this order. The bonding process is as explained in the above section of "Resin pattern manufacturing method". A preferred embodiment of the bonding process is the same as the preferred embodiment of the bonding process described in the section of "Resin pattern manufacturing method" above.

<<Exposure process>>
In the exposure step, the photosensitive resin layer is exposed in a pattern. The exposure process is as described in the above section of "Resin pattern manufacturing method". A preferred embodiment of the exposure process is the same as the preferred embodiment of the exposure process described in the above section of "Resin pattern manufacturing method."

<<Developing process>>
In the development step, the exposed photosensitive resin layer is developed to form a resin pattern. The developing process is as described in the above section of "Resin pattern manufacturing method". The preferred embodiment of the developing step is the same as the preferred embodiment of the developing step explained in the section of "Resin pattern manufacturing method" above.

<<Etching process>>
In the etching process, the conductive layer not covered by the resin pattern is etched to form a conductive pattern. In the etching process, the resin pattern functions as a protective film for the conductive layer. In the etching process, the conductive layer not covered by the resin pattern is removed by etching, and the conductive layer covered by the resin pattern forms a conductive pattern.

For example, a known method is used as the etching method. Examples of etching treatment methods include the method described in paragraphs 0209 to 0210 of JP2017-120435A, the method described in JP2010-152155A, paragraphs 0048 to 0054, and the method described in JP2010-152155A, paragraphs 0048 to 0054, Examples include a wet etching method using immersion and a dry etching method (eg, plasma etching).

Regarding the etching liquid used in the wet etching method, an acidic or alkaline etching liquid may be appropriately selected depending on the object to be etched. Examples of the acidic etching solution include an aqueous solution containing at least one acidic component selected from the group consisting of hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, and phosphoric acid. Examples of the acidic etching solution include an aqueous solution containing the above-described acidic component and at least one salt selected from the group consisting of ferric chloride, ammonium fluoride, and potassium permanganate. The acidic component may be a combination of multiple acidic components. The alkaline etching solution may contain, for example, at least one alkaline component selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia, organic amines, and salts of organic amines (e.g., tetramethylammonium hydroxide). Examples include aqueous solutions containing. Examples of the alkaline etching solution include an aqueous solution containing the above-described alkaline component and a salt (eg, potassium permanganate). The alkaline component may be a combination of a plurality of alkaline components.

<<Removal process>>
The method for manufacturing a conductive pattern according to an embodiment of the present disclosure preferably includes a step of removing the remaining resin pattern after the etching step.

Examples of the method for removing the resin pattern include a method of removing the resin pattern using chemical treatment. A method of removing the resin pattern using a removal liquid is preferred. As a method for removing a resin pattern using a removal liquid, for example, a substrate containing a resin pattern is placed in a stirring removal liquid at a temperature of 30°C to 80°C (preferably 50 to 80°C) for 1 minute to 80°C. An example is a method of soaking for 30 minutes.

Examples of the removal liquid include a removal liquid containing an inorganic alkali component or an organic alkali component and at least one member selected from the group consisting of water, dimethyl sulfoxide, and N-methylpyrrolidone. Examples of the inorganic alkali component include sodium hydroxide and potassium hydroxide. Examples of the organic alkali component include primary amine compounds, secondary amine compounds, tertiary amine compounds, and quaternary ammonium salt compounds.

The remaining resin pattern may be removed using known methods such as a spray method, a shower method, and a paddle method.

<<Other processes>>
The method for manufacturing a conductive pattern according to an embodiment of the present disclosure may further include other steps in addition to the steps described above. Other steps include, for example, the steps shown below. Furthermore, the exposure process, development process, and other processes applicable to the method for manufacturing a conductive pattern according to an embodiment of the present disclosure are described in paragraphs 0035 to 0051 of JP-A No. 2006-23696. The contents described in the above publications are incorporated herein by reference.

(Process of reducing visible light reflectance)
A method for manufacturing a conductive pattern according to an embodiment of the present disclosure may include a step of performing a process of reducing the visible light reflectance of some or all of the plurality of conductive layers of the substrate. Examples of the treatment for reducing visible light reflectance include oxidation treatment. For example, when the conductive layer contains copper, the visible light reflectance of the conductive layer can be reduced by oxidizing the copper to form copper oxide and blackening the conductive layer. The treatment for reducing visible light reflectance is described in paragraphs 0017 to 0025 of JP-A No. 2014-150118 and paragraphs 0041, 0042, 0048, and 0058 of JP-A No. 2013-206315. The contents described in these publications are incorporated herein by reference.

(Step of forming an insulating film and forming a new conductive layer on the surface of the insulating film)
The method for manufacturing a conductive pattern according to an embodiment of the present disclosure preferably includes the steps of forming an insulating film on the surface of the conductive pattern, and forming a new conductive layer on the surface of the insulating film. Through the above steps, it is possible to form a second electrode pattern that is insulated from the first electrode pattern. Examples of the method for forming the insulating film include a known method for forming a permanent film. An insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties. As a method for forming a new conductive layer on the surface of the insulating film, for example, a new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

In a method for manufacturing a conductive pattern according to an embodiment of the present disclosure, a substrate having a plurality of conductive layers on both surfaces of the base material is used, and circuits are sequentially or simultaneously formed on the conductive layers formed on both surfaces of the base material. It is also preferable to do so. According to the method described above, the first conductive pattern can be formed on one surface of the base material, and the second conductive pattern can be formed on the other surface of the base material. The conductive pattern as described above is used, for example, as circuit wiring for a touch panel. The conductive pattern as described above is preferably formed by a roll-to-roll method.

<<Roll-to-roll method>>
The method for manufacturing a conductive pattern according to an embodiment of the present disclosure is preferably performed by a roll-to-roll method. The roll-to-roll method is as described in the above section of "Resin pattern manufacturing method."

<<Uses of circuit wiring>>
A conductive pattern obtained by a method for manufacturing a conductive pattern according to an embodiment of the present disclosure is applied to various devices. Examples of the device including a conductive pattern include an input device, preferably a touch panel, and more preferably a capacitive touch panel. The input device can be applied to display devices such as organic EL display devices and liquid crystal display devices. Moreover, it is preferable that the conductive pattern obtained by the method for manufacturing a conductive pattern according to an embodiment of the present disclosure is applied to a touch sensor.

<Touch sensor>
A touch sensor according to an embodiment of the present disclosure includes a conductive pattern obtained by a method for manufacturing a conductive pattern according to an embodiment of the present disclosure. Components of the touch sensor according to an embodiment of the present disclosure are not limited, except that they include a conductive pattern obtained by a method for manufacturing a conductive pattern according to an embodiment of the present disclosure. The conductive pattern is used, for example, as a transparent electrode of a touch sensor or a frame wiring. The shape and dimensions of the conductive pattern are determined, for example, depending on the intended touch sensor. Examples of photomask patterns used for manufacturing the conductive pattern include pattern A and pattern B described in JP-A-2019-204070. As components other than the conductive pattern, for example, components included in a known touch sensor are used. Touch sensors are described in, for example, Japanese Patent No. 6486341 and Japanese Patent Application Publication No. 2016-155978. These publications are incorporated herein by reference. Known touch sensor manufacturing methods may be referenced to form touch sensor components other than the conductive pattern.

Touch sensors are applied to various input devices, for example. Examples of the input device include a touch panel.

Examples of touch panel detection methods include a resistive film method, a capacitive method, an ultrasonic method, an electromagnetic induction method, and an optical method. Among the above, the capacitive method is preferable.

Examples of the touch panel type include an in-cell type (for example, the configurations shown in FIGS. 5, 6, 7, and 8 of Japanese Patent Publication No. 2012-517051), and an on-cell type (for example, the configurations shown in Japanese Patent Application Laid-open No. 2013-168125). 19 and the configuration described in FIGS. 1 and 5 of JP-A-2012-89102), OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP-A-2013 -54727 publication), various outsell types (for example, GG, G1/G2, GFF, GF2, GF1, and G1F), and other configurations (for example, the diagram of JP-A-2013-164871) 6).

Hereinafter, the present disclosure will be described in detail based on Examples. However, the present disclosure is not limited to the following examples. The contents of the examples shown below (for example, materials, amounts used, proportions, processing details, and processing procedures) may be changed as appropriate within the scope of the purpose of the present disclosure.

<Preparation of particle-containing layer forming composition 1>
The mixture obtained by mixing the components shown below was filtered using a 6 μm filter (F20, MAHLE Filter Systems Co., Ltd.), and then subjected to membrane desorption using a 2x6 Radial Flow Super Phobic (Polypore Co., Ltd.). I felt it. By the above procedure, composition 1 for forming a particle-containing layer was obtained.

・Acrylic polymer (AS-563A, Daicel Millize Co., Ltd., solid content: 27.5% by mass): 167 parts by mass ・Nonionic surfactant (NAROACTY CL95, Sanyo Chemical Industries, Ltd., solid content: 100% by mass) : 0.7 parts by mass ・Anionic surfactant (Rapisol A-90, NOF Corporation, water diluted liquid with a solid content concentration of 1% by mass): 114.4 parts by mass ・Carnauba wax dispersion (Cellosol 524) , Chukyo Yushi Co., Ltd., Solid content: 30% by mass): 7 parts by mass Carbodiimide compound (Carbodilite V-02-L2, Nisshinbo Chemical Co., Ltd., diluted with water with a solid content concentration of 10% by mass): 20.9 mass Parts: Matting agent (Snowtex XL, Nissan Chemical Co., Ltd., solid content: 40% by mass, average particle size: 50nm): 2.8 parts by mass, Water: 690.2 parts by mass

<Manufacture of temporary support 1>
Temporary support 1 was manufactured by the following method.

(extrusion molding)
Pellets of polyethylene terephthalate (PET) produced using the citric acid chelate organic titanium complex described in Japanese Patent No. 5,575,671 as a polymerization catalyst were dried to reduce the water content of the pellets to 50 ppm or less. The dried pellets were put into a hopper of a single-screw extruder having a diameter of 30 mm and melted at 280°C. The melt was passed through a filter (pore size: 2 μm) and then extruded from a die onto a cooling roll at 25° C. to obtain an unstretched film. In the above method, the melt was brought into close contact with the cooling roll using an electrostatic application method.

(Stretching and coating)
The solidified unstretched film was sequentially biaxially stretched by the following method to form a particle-containing layer with a thickness of 40 nm on a polyethylene terephthalate film with a thickness of 16 μm.

(a) Longitudinal Stretching The unstretched film was passed between two pairs of nip rolls having different circumferential speeds and stretched in the longitudinal direction (transport direction). The conditions for longitudinal stretching are shown below.
・Preheating temperature: 75℃
・Stretching temperature: 90℃
・Stretching ratio: 3.4 times ・Stretching speed: 1,300%/sec

(b) Coating Composition 1 for forming a particle-containing layer was coated on one side of the longitudinally stretched film using a bar coater so that the thickness after film formation was 40 nm.

(c) Lateral Stretching The film coated with particle-containing layer forming composition 1 was laterally stretched using a tenter under the following conditions.
・Preheating temperature: 110℃
・Stretching temperature: 120℃
・Stretching ratio: 4.2 times ・Stretching speed: 50%/sec

(Heat fixation and heat relaxation)
The biaxially stretched film that had undergone longitudinal stretching and transverse stretching was heat-set under the following conditions.
・Heat fixing temperature: 227℃
・Heat setting time: 6 seconds

After heat setting, the tenter width was reduced, and the biaxially stretched film was thermally relaxed under the following conditions.
・Thermal relaxation temperature: 190℃
・Thermal relaxation rate: 4%

(Take-up)
After heat setting and heat relaxation, both ends of the film were trimmed, the ends of the film were extruded (knurled) to a width of 10 mm, and then the film was wound up with a tension of 40 kg/m. The width of the film was 1.5 m, and the length of the film was 6,300 m. The obtained film roll was used as temporary support 1.

The temporary support 1 includes a polyethylene terephthalate film (substrate) and a particle-containing layer in this order. The haze of temporary support 1 was 0.2%. Haze was measured as total optical haze using a haze meter (Nippon Denshoku Industries Co., Ltd., NDH2000). The thermal shrinkage rate by heating at 150°C for 30 minutes is 1.0% on the MD (Machine Direction) side and 0 on the TD (Transverse Direction, a direction perpendicular to the conveyance direction on the surface of the film) side. It was .2%. The thickness of the particle-containing layer measured from a cross-sectional TEM photograph was 40 nm. The average particle diameter of the particles contained in the particle-containing layer was 50 nm, as measured by the method described above using an HT-7700 transmission electron microscope (TEM) manufactured by Hitachi High-Technologies Corporation.

<Manufacture of temporary support 2>
Temporary support 2 was obtained by the same method as for temporary support 1 except that the number of times the melt passed through the filter during extrusion molding was changed to two.

<Manufacture of temporary support 3>
Temporary support 3 was obtained by the same method as for temporary support 1 except that the pore diameter of the filter in the filter was changed to 3 μm in the extrusion molding.

<Manufacture of temporary support 4>
Temporary support 4 was obtained by the same method as for temporary support 3, except that the number of times the melt passed through the filter during extrusion molding was changed to two.

<Manufacture of temporary support 5>
Temporary support 5 was obtained by the same method as for temporary support 3, except that the number of times the melt passed through the filter during extrusion molding was changed to three.

<Manufacture of temporary support 6>
Temporary support 6 was obtained in the same manner as for temporary support 4 except that the extrusion rate was adjusted so that the thickness of the temporary support was 10 μm.

<Manufacture of temporary support 7>
Temporary support 7 was obtained by the same method as for temporary support 1 except that the pore diameter of the filter in the filter was changed to 5 μm in the extrusion molding.

<Number of particles>
Ten arbitrary regions (size of each region: 10 mm x 10 mm, total area: 1000 mm ² ) on the surface of the temporary support were visually observed using an optical microscope. The number of particles with a diameter of 3 μm or more contained in each region was measured. Based on the total number of particles measured in 10 areas, the number of particles per 1 cm ² of the measurement area (particles/cm ² ) was calculated. The measurement results are shown below.
In Table 1, the column "3μm~" shows the number of particles (particles/ ^cm2 ) with a diameter of 3μm or more and less than 4.5μm, and the column "4.5μm~" shows the number of particles with a diameter of 4.5μm or more. The number of particles (pieces/cm ² ) with a diameter of 6 μm or more and less than 7.5 μm is entered in the "6 μm ~" column, and the number of particles (particles/cm ² ) with a diameter of 6 μm or more and less than 7.5 μm in the "9 μm ~" column. indicates the number of particles (particles/cm ² ) with a diameter of 9 μm or more and less than 10.5 μm, and the “10.5 μm~” column indicates the number of particles (particles/cm ² ) with a diameter of 10.5 μm or more. , respectively.

<Preparation of photosensitive resin layer forming compositions 1 to 4>
Methyl ethyl ketone (400 parts by mass), propylene glycol monomethyl ether (40 parts by mass), propylene glycol monomethyl ether acetate (200 parts by mass), methyl alcohol (20 parts by mass) and the following components were mixed to form a composition for forming a photosensitive resin layer. Items 1 to 4 were prepared.

<Preparation of composition 1 for forming thermoplastic resin layer>
Methyl ethyl ketone (500 parts by mass), propylene glycol monomethyl ether (20 parts by mass), propylene glycol monomethyl ether acetate (200 parts by mass) and the following components were mixed to prepare thermoplastic resin layer forming composition 1.

The meanings of the abbreviations listed in the above table are shown below.
・A-2: Benzyl methacrylate/methacrylic acid/acrylic acid copolymer (75% by mass/10% by mass/15% by mass, weight average molecular weight: 30,000, Tg: 75°C, acid value: 186mgKOH/g)
・B-1: Compound with the structure shown below (dye that develops color with acid)

・C-1: Compound with the structure shown below (photoacid generator, compound described in paragraph 0227 of JP-A-2013-47765, synthesized according to the method described in paragraph 0227.)

・D-3: NK ester A-DCP (tricyclodecane dimethanol diacrylate, Shin Nakamura Chemical Co., Ltd.)
・D-4:8UX-015A (polyfunctional urethane acrylate compound, Taisei Fine Chemical Co., Ltd.)
・D-5: Aronix TO-2349 (polyfunctional acrylate compound having a carboxy group, Toagosei Co., Ltd.)
・E-1: Megafac F-552 (fluorosurfactant, DIC Corporation)
・F-1: Phenothiazine (Fujifilm Wako Pure Chemical Industries, Ltd.)
・F-2: CBT-1 (carboxybenzotriazole, Johoku Chemical Industry Co., Ltd.)

<Preparation of composition 1 for forming water-soluble resin layer>
A water-soluble resin layer forming composition 1 was prepared by mixing the following components.
・Ion exchange water: 38.12 parts by mass ・Methanol (Mitsubishi Gas Chemical Co., Ltd.): 57.17 parts by mass ・Kuraray Poval 4-88LA (polyvinyl alcohol, Kuraray Co., Ltd.): 3.22 parts by mass ・Polyvinylpyrrolidone K- 30 (Nippon Shokubai Co., Ltd.): 1.49 parts by mass / Megafac F-444 (fluorosurfactant, DIC Corporation): 0.0035 parts

<Example 1>
Thermoplastic resin layer forming composition 1 was applied using a slit-shaped nozzle to the opposite side of the particle-containing layer forming surface of the base material (polyethylene terephthalate film) of the temporary support. The applied composition 1 for forming a thermoplastic resin layer was dried at 100° C. for 120 seconds to form a thermoplastic resin layer having a thickness of 2.0 μm.

Composition 1 for forming a water-soluble resin layer was applied onto the thermoplastic resin layer using a slit-shaped nozzle. The applied water-soluble resin layer forming composition 1 was dried at 120° C. for 120 seconds to form a water-soluble resin layer having a thickness of 1.0 μm. The water-soluble resin layer is an intermediate layer.

Composition 2 for forming a photosensitive resin layer was applied onto the water-soluble resin layer using a slit-shaped nozzle. The applied photosensitive resin layer forming composition 2 was dried at 100° C. for 120 seconds to form a photosensitive resin layer having a thickness of 4.0 μm.

The photosensitive transfer material obtained by the above procedure includes a temporary support, a thermoplastic resin layer, a water-soluble resin layer, and a photosensitive resin layer in this order. Tables 4 and 5 show the layer configurations of the thermoplastic resin layer, water-soluble resin layer, and photosensitive resin layer.

<Examples 2 to 10 and Comparative Example 1>
A photosensitive transfer material was obtained by the same procedure as described in Example 1, except that the type of temporary support and layer structure were changed as appropriate according to the descriptions in Tables 4 and 5.

<Resolution>
(1) A PET substrate with a copper layer was produced by forming a copper layer with a thickness of 200 nm on a polyethylene terephthalate (PET) film with a thickness of 100 μm by sputtering. The photosensitive transfer material and the PET substrate with the copper layer were bonded by a roll-to-roll method using a vacuum laminator (MCK Co., Ltd., roll temperature: 100°C, linear pressure: 1.0 MPa, linear speed: 0.5 m/min). Pasted together. The obtained laminate includes at least a PET film, a copper layer, a photosensitive resin layer, and a temporary support in this order. (2) The obtained laminate was degassed under pressure for 30 minutes at 0.6 MPa and 60° C. using an autoclave device. (3) Line and space pattern mask (Duty ratio is 1:1, line width changes stepwise at 1 μm intervals from 1 μm to 20 μm, without peeling off the temporary support) using an ultra-high pressure mercury lamp .) The photosensitive resin layer was exposed to light. (4) After peeling off the temporary support, development was performed. Development was performed using a 1.0 mass % sodium carbonate aqueous solution at 25° C. for 30 seconds by shower development. A resin pattern was formed by developing the photosensitive resin layer. Repeat the above series while adjusting the exposure amount (unit: mJ/cm ² ) each time until a resin pattern with the minimum line width corresponding to the mask pattern (hereinafter referred to as the "reference pattern" in this paragraph) is obtained. Steps (1) to (4) were carried out. The minimum line width of the reference pattern was adopted as the critical resolution (X) of the photosensitive resin layer. The evaluation results are shown in Table 5.

<Pinhole in wiring pattern>
Wiring formation mask (Duty ratio is 1:1, line width changes stepwise from 1 μm to 20 μm every 1 μm. Length of wiring pattern is 50 mm. Number of wires is 10. ) The wiring pattern was formed using the same method as described in the "Resolution" section above (i.e., the method of exposing the photosensitive resin layer at a standard exposure amount to form a resin pattern). (that is, a resin pattern) was formed. The wiring pattern was visually observed using an optical microscope, and the pinholes in the wiring pattern were evaluated based on the maximum size and number of pinholes according to the following criteria. The evaluation results are shown in Table 5.
A: No pinholes were observed, or pinholes smaller than 1/4 of the wiring width were observed.
B: A pinhole with a size of more than 1/4 and less than 1/2 of the wiring width was confirmed.
C: A pinhole with a size of more than 1/2 and less than 3/4 of the wiring width was confirmed.
D: A pinhole larger than 3/4 of the wiring width was observed.

Table 5 shows that, compared to Comparative Example 1, the occurrence of pinholes in the wiring patterns in Examples 1 to 10 was suppressed.

<Examples 11 to 21>
(Preparation of polyester A pellets)
An esterification reaction is carried out with 86.5 parts by mass of terephthalic acid and 37.1 parts by mass of ethylene glycol at 255° C. while distilling off water. After the esterification reaction was completed, 0.02 parts by mass of trimethyl phosphoric acid, 0.06 parts by mass of magnesium acetate, 0.01 parts by mass of lithium acetate, and 0.0085 parts by mass of antimony trioxide were added, and then the mixture was heated to 290 parts by mass under reduced pressure. A polycondensation reaction was carried out by heating and raising the temperature to .degree. C. to obtain polyester A pellets (denoted as polyester A in Table 6) having an intrinsic viscosity of 0.63 dl/g.

(Preparation of polyester C pellets)
Using terephthalic acid as the dicarboxylic acid component and CHDM (cyclohexanedimethanol) as the diol component, a polycondensation reaction was performed in the presence of 200 ppm of butyltin tris (2-ethylhexanoate) to produce polyester C pellets with an alicyclic structure. (Described as polyester C in Table 6) was obtained.

(Preparation of polyester E pellets)
In producing polyester A pellets in the same manner as above, after completion of the esterification reaction, the volume average particle diameter is 0.2 μm, the volume shape coefficient f is 0.51, the volume average particle diameter is 0.06 μm, and the volume shape coefficient f is 0. 51 and spherical silica with a Mohs hardness of 7 were respectively added, followed by a polycondensation reaction, and silica-containing polyester E pellets containing 1% by mass of each of the two types of spherical silica based on the mass of polyester A (in Table 6, , polyester E) was obtained.
The above-mentioned spherical silica is produced by adding a mixed solution of ethanol, pure water, and aqueous ammonia to the mixed solution of ethanol and ethyl silicate while stirring, and stirring the resulting reaction solution. These are monodispersed silica particles obtained by performing a hydrolysis reaction of silicate and a polycondensation reaction of the hydrolysis product, followed by stirring after the reaction.

(Preparation of polyester G pellets)
0.04 parts by mass of manganese acetate and 0.03 parts by mass of antimony trioxide are added as catalysts to 100 parts by mass of dimethyl terephthalate and 64 parts by mass of ethylene glycol to perform a transesterification reaction, and then agglomerated alumina is added to the reaction product. Then, antimony trioxide was added to carry out a polycondensation reaction, and polyester G pellets containing 2% by mass of agglomerated alumina and having an intrinsic viscosity of 0.62 dl/g (in Table 6, polyester G and notation) was obtained.
The above-mentioned slurry containing agglomerated alumina is made into a 10% by mass ethylene glycol slurry using δ-alumina as the agglomerated alumina, pulverized and dispersed using a sand grinder, and then passed through a 3 μm filter with a collection efficiency of 95%. This is a slurry obtained by filtration.

(Preparation of polyester Z pellets)
In producing polyester A pellets in the same manner as above, after the esterification reaction is completed, spherical silica (SO-C1 manufactured by Admatec Co., Ltd., particle size: 0.2 μm to 0.4 μm) is added, and then the polycondensation reaction is carried out. A silica-containing polyester Z pellet containing 1% by mass of spherical silica based on the mass of polyester A (indicated as polyester Z in Table 6) was obtained.

(Preparation of temporary support 8)
Temporary support 8 (single-layer polyethylene terephthalate film with a thickness of 16 μm) was produced in the same manner as temporary support 1 except that the particle-containing layer was not formed.
The arithmetic mean roughness Ra of the first surface of the temporary support 8 was 0.2 nm.

(Preparation of temporary support 9)
Surface irregularities are formed on the first surface of the temporary support 8 by thermal nanoimprinting (heating temperature: 130°C, pressure: 0.1 MPa), and the temporary support 9 (single-layer polyethylene terephthalate film with a thickness of 16 μm) is formed. Created.
The arithmetic mean roughness Ra of the first surface of the temporary support 9 was 35 nm.

(Preparation of temporary supports 10 to 15)
A mixture of raw materials prepared in the formulation shown in Table 6 for each layer was stirred in a blender and then supplied to a vented twin-screw extruder for layers A and B. The mixture was melt-extruded at 275° C., filtered twice through a filter with a pore size of 3 μm, and then laminated in a rectangular 3-layer merging block to form a 3-layer laminate consisting of layer A/layer B/layer A. Thereafter, it was wound onto a cooling roll through a slit die kept at 285° C. using an electrostatic casting method, and then wound around a casting drum whose surface temperature was 25° C., and cooled and solidified to obtain an unstretched laminated film.
The unstretched laminated film was sequentially stretched (in the longitudinal direction and the width direction). First, stretching was performed in the longitudinal direction, and then stretching was performed in the width direction. For stretching in the longitudinal direction, the film was conveyed at 105° C. using Teflon (registered trademark) rolls, and then stretched 4.0 times at 120° C. using a difference in the circumferential speed of the rolls to obtain a uniaxially stretched film. Subsequently, this uniaxially stretched film was stretched 4.0 times in the transverse direction at 115° C. in a stenter, then heat-set at 230° C., relaxed by 5% in the width direction, and cooled in the conveying process. Thereafter, the edges were cut and then wound up to obtain an intermediate biaxially stretched film having the thickness of each layer listed in Table 6. This intermediate product was slit using a slitter to obtain a roll of polyester film consisting of three layers.
The resulting three-layer laminated polyester film consisting of layer A/layer B/layer A was used as temporary supports 10 to 15.

(Preparation of temporary supports 16 and 18)
A mixture of raw materials prepared according to the formulation shown in Table 6 for each layer was stirred in a blender and then supplied to a vented twin-screw extruder for A layer, B layer, and C layer. After melt extrusion at 275°C and filtration with a high-precision filter that captures 95% or more of foreign matter of 5 μm or more, the 3-layer mixture is laminated using a rectangular 3-layer merging block, consisting of layer A, layer B, and layer C. A roll of polyester film consisting of three layers was obtained in the same manner as in the production of temporary support 12, except that the layers were laminated.

(Preparation of temporary support 17)
For each layer, a mixture of raw materials prepared according to the formulation shown in Table 6 was used, and a rectangular two-layer merging block was used to form a two-layer laminate consisting of layer A/layer B. Similarly, a roll of polyester film consisting of two layers was obtained.

Regarding the obtained temporary supports 10 to 18, the thickness (thickness of each layer), the presence or absence of particles in the surface layer, and the arithmetic mean roughness Ra of the first surface were measured by the methods described above.
The results are shown in Table 6.
Table 6 also shows the layer structure of temporary supports 10 to 18, where A/B/A refers to the layer structure of the polyester film consisting of three layers: A layer/B layer/A layer. A/B/C refers to the layer structure of a polyester film consisting of three layers: A layer/B layer/C layer, and A/B refers to a polyester film layer consisting of two layers: A layer/B layer. Refers to the composition.
In addition, for all temporary supports 10 to 18, A described on the left side of the layer structure column in Table 6 (i.e., A layer) is a layer arranged as the outermost layer on the second surface side. .

<Number of particles>
Regarding the obtained temporary support, the number of particles having a diameter of 3 μm or more was measured by the method described above, and the number of particles per 1 cm ² of the measurement area (particles/cm ² ) was calculated. The measurement results are shown below.
In Table 7, the column "3μm~" shows the number of particles (particles/ ^cm2 ) with a diameter of 3μm or more and less than 4.5μm, and the column "4.5μm~" shows the number of particles with a diameter of 4.5μm or more. The number of particles (pieces/cm ² ) with a diameter of 6 μm or more and less than 7.5 μm is entered in the "6 μm ~" column, and the number of particles (particles/cm ² ) with a diameter of 6 μm or more and less than 7.5 μm in the "9 μm ~" column. indicates the number of particles (particles/cm ² ) with a diameter of 9 μm or more and less than 10.5 μm, and the “10.5 μm~” column indicates the number of particles (particles/cm ² ) with a diameter of 10.5 μm or more. , respectively.

<Preparation of photosensitive transfer material>
According to the description in Table 7, a photosensitive transfer material having the layer structure 4 shown in Table 4 was obtained by the same procedure as described in Example 1 using any of temporary supports 8 to 18. For temporary supports 10 to 18, the photosensitive resin layer was formed on the second surface side of the temporary supports. When Temporary Supports 8 and 9 were used, the side opposite to the surface on which the particle-containing layer was formed on Temporary Support 1 was used as the second surface, and the photosensitive resin layer was formed on this surface.
The photosensitive transfer material obtained by the above procedure includes a temporary support and a photosensitive resin layer in this order.

Regarding the obtained photosensitive transfer material, the critical resolution (X) of the photosensitive resin layer, the standard diameter (Y = 0.75 The number of particles was determined. Further, the resulting photosensitive transfer material was evaluated for pinholes in the wiring pattern by the method described above.
The results are shown in Table 8.

<Lamination property>
In evaluating resolution, after laminating the photosensitive transfer material and the PET substrate with a copper layer, the presence or absence of wrinkles and misalignment in the laminate was checked, and the lamination properties were evaluated according to the following criteria. did. The results are shown in Table 8.
A: There are no wrinkles in the laminate, and the photosensitive transfer material of the laminate and the PET substrate with a copper layer are bonded together with their end positions aligned (that is, without misalignment).
B: A part of the laminate of the photosensitive transfer material and the PET substrate with a copper layer has wrinkles along the transport direction.
C: Misalignment occurs at the end of the photosensitive transfer material of the laminate and the PET substrate with a copper layer.

Table 8 shows that the occurrence of pinholes in the wiring patterns in Examples 11 to 21 was suppressed.
The reason why the lamination property of Example 11 is B is that Ra of the first surface of the temporary support 8 is small, so that the first surface of the temporary support 8 is difficult to slip, and it is difficult to slip on the first surface of the temporary support 8, which makes it difficult to move with the rubber roll in the vacuum laminator. It is presumed that this is due to a mechanism in which a difference in slippage occurs, causing wrinkles.
Further, the reason why the lamination property of Example 17 is C is that the first surface of the temporary support 14 has a large Ra, so the first surface of the temporary support 14 is easy to slip, and the rubber roll in the vacuum laminator It is presumed that this is due to a mechanism in which slipping occurs between the copper layer and the photosensitive transfer material including the temporary support 14 and the position of the photosensitive transfer material is shifted relative to the PET substrate with the copper layer.

[Explanation of symbols]
10, 11: Temporary support 10a, 11a: First surface of temporary support 10b, 11b: Second surface of temporary support 11-1: Particle-containing layer 11-2: Base material 20: Photosensitive resin layer 30: Protective film 40: Thermoplastic resin layer 50: Intermediate layer 100, 110, 120: Photosensitive transfer material

Japanese Patent Application No. 2020-142747 filed on August 26, 2020, Japanese Patent Application No. 2020-172157 filed on October 12, 2020, and Japan Patent Application No. 2020-172157 filed on July 6, 2021. The disclosure of National Patent Application No. 2021-112369 is incorporated herein by reference in its entirety. All documents, patent applications, and technical standards mentioned herein are incorporated by reference to the same extent as if each individual document, patent application, and technical standard were specifically and individually indicated to be incorporated by reference. Incorporated herein by reference.

Claims (10)

comprising a temporary support and a photosensitive resin layer in this order,
The temporary support is a polyester film consisting of two or more layers, and at least one surface layer does not contain filler.
Photosensitive transfer material. The photosensitive transfer material according to claim 1, wherein the surface layer of the temporary support on the photosensitive resin layer side does not contain a filler. The photosensitive transfer material according to claim 1 or 2, wherein the surface of the temporary support opposite to the photosensitive resin layer has an arithmetic mean roughness Ra of 1 nm to 50 nm. The photosensitive transfer material according to any one of claims 1 to 3, wherein the surface layer has a phase-separated structure. The photosensitive transfer material according to any one of claims 1 to 4, wherein the surface layer contains a polyester resin having an alicyclic structure. The photosensitive transfer material according to claim 5, wherein the alicyclic structure is a cyclohexane ring. 7. The photosensitive transfer material according to claim 5, wherein the surface layer contains copolymerized polyethylene terephthalate containing isophthalic acid as a copolymerization component. A method for producing a resin pattern using the photosensitive transfer material according to any one of claims 1 to 7, comprising:
a step of preparing a substrate;
bringing the photosensitive transfer material into contact with the substrate and arranging a photosensitive resin layer and a temporary support in this order on the substrate;
pattern-exposing the photosensitive resin layer;
Developing the exposed photosensitive resin layer to form a resin pattern;
A method for manufacturing a resin pattern, including: The method for manufacturing a resin pattern according to claim 8, wherein the resin pattern has a line width of 10 μm or less. A method for producing a conductive pattern using the photosensitive transfer material according to any one of claims 1 to 7, comprising:
preparing a substrate including a conductive layer;
bringing the photosensitive transfer material into contact with the substrate and arranging a photosensitive resin layer and a temporary support in this order on the substrate;
pattern-exposing the photosensitive resin layer;
Developing the exposed photosensitive resin layer to form a resin pattern;
etching the conductive layer not covered by the resin pattern to form a conductive pattern;
A method of manufacturing a conductive pattern, including: