WO2019225362A1

WO2019225362A1 - Photosensitive transfer material, method for producing resin pattern, method for manufacturing circuit wiring, and method for manufacturing touch panel

Info

Publication number: WO2019225362A1
Application number: PCT/JP2019/018814
Authority: WO
Inventors: 知樹松田; 一真両角; 山田　悟
Original assignee: 富士フイルム株式会社
Priority date: 2018-05-22
Filing date: 2019-05-10
Publication date: 2019-11-28
Also published as: CN112204467B; JP6968273B2; JPWO2019225362A1; TW202003595A; CN112204467A

Abstract

A photosensitive transfer material comprising a temporary support and a photosensitive resin layer, wherein the photosensitive resin layer contains a polymer component which meets at least one of the requirements a1 and a2 and a photo-acid generator, and the polymer component has a glass transition temperature of 90°C or lower; and a method for producing a resin pattern, a method for manufacturing a circuit wiring, and a method for manufacturing a touch panel, each using the photosensitive transfer material. a1: A polymer component which comprises a polymer that has both of a constituent unit having an acid group protected by an acid-degradable group and a constituent unit having a group having a pKaH value of 3 or more; and a2: a polymer component which comprises both of a polymer that has a constituent unit having an acid group protected by an acid-degradable group and a polymer that has a constituent unit having a group having a pKaH value of 3 or more.

Description

Photosensitive transfer material, resin pattern manufacturing method, circuit wiring manufacturing method, and touch panel manufacturing method

The present disclosure relates to a photosensitive transfer material, a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method.

In a display device (such as an organic electroluminescence (EL) display device and a liquid crystal display device) having a touch panel such as a capacitance type input device, an electrode pattern corresponding to a sensor of a visual recognition part, a wiring of a peripheral wiring part, and a lead-out wiring part A conductive layer pattern such as is provided inside the touch panel.
In general, a patterned layer is formed by a photosensitive resin composition layer provided on an arbitrary substrate using a photosensitive transfer material because the number of steps for obtaining a required pattern shape is small. On the other hand, a method of developing after exposure through a mask having a desired pattern is widely used.

Moreover, what was described in patent document 1 or 2 is known as a conventional photosensitive resin composition.
As a conventional method, for example, in Patent Document 1, (A) a polymer component containing a polymer satisfying at least one of the following (1) and (2), (1) (a-1) an acid group is an acid A polymer having a structural unit having a group protected by a decomposable group, and (a-2) a structural unit having a crosslinkable group, and (2) (a-1) the acid group is protected by an acid-decomposable group. (A-2) a polymer having a structural unit having a crosslinkable group, (B) a photoacid generator, (C) a solvent, and (S) a general formula (1) ) And a polymer having a structural unit represented by the general formula (2), the polymer (S) is a general formula in all repeating units of the polymer (S). The molar ratio of the structural unit represented by (2) is represented by the general formula (1) in all repeating units of the polymer (S). 0.3 to 5 times the molar ratio of structural units, the photosensitive resin composition is disclosed.

In formulas (1) and (2), R ¹⁰ and R ¹¹ each independently represent a hydrogen atom or a methyl group, and L ¹ and L ² each independently represent a single bond or a divalent linkage. R ¹ to R 4 each independently represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms, and R ⁵ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or Represents an alkoxy group having 1 to 12 carbon atoms.

Patent Document 2 discloses at least one of repeating unit a having a carboxyl group substituted with an acid labile group and repeating units b1 and b2 having a sulfonium salt represented by the following general formula (1). As described above, a resist material comprising a polymer compound having a repeating unit c having an amino group has been disclosed.

(In the formula, R ¹ , R ³ , R ⁸ and R ¹² each independently represents a hydrogen atom, a methyl group, a fluorine atom or a trifluoromethyl group. R ² represents an acid labile group. X represents a single group. A bond, a phenylene group, or a naphthylene group, or an ester group or a linking group having a lactone ring and having 1 to 12 carbon atoms, R ⁴ is an alkylene group having 1 to 10 carbon atoms, or 6 to 10 carbon atoms An arylene group which may have a fluorine atom, a trifluoromethyl group, an ester group, an ether group or a lactone ring, and R ⁵ , R ⁶ , R ⁷ , R ⁹ , R ¹⁰ and R ¹¹ are the same, or It is a different type of linear, branched or cyclic alkyl group having 1 to 12 carbon atoms and may contain a carbonyl group, an ester group or an ether group, or an aryl group having 6 to 12 carbon atoms, or a carbon number 7 ~ 20 Aralkyl Or a thiophenyl group, which may have an alkyl group having 1 to 10 carbon atoms, an alkoxy group, an alkoxycarbonyl group, a carbonate group, and a halogen atom, a cyano group, a hydroxyl group, or a carboxyl group as a substituent. A single bond, a methylene group, an arylene group substituted with a fluorine atom or a trifluoromethyl group, or —C (═O) —O—R ¹⁷ —, wherein R ¹⁷ is substituted with a fluorine atom or a trifluoromethyl group R ¹³ is a single bond, or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, R ¹⁴ and R ¹⁵ are each independently a hydrogen atom or a linear chain having 1 to 20 carbon atoms. An alkyl group, branched or cyclic alkyl group, t-butoxycarbonyl group, or t-allyloxycarbonyl group, an ether bond, a thioether bond , Hydroxyl group, formyl group, an acetoxy group, a cyano group, may have an aromatic ^group, and ^{R 13} and ^R ^{14, R 13} and ^R ^{15, R 14} and ^{R 15} are respectively bonded to form a ring R ¹⁶ may be bonded to a hydrogen atom or R 15 to form a ring, Z is a single bond, a methylene group, an arylene group, —O—, —C (═O) —O—, or —C (═O) —O—R ¹⁸ —C (═O) —O—, wherein R ¹⁸ is a single bond or a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms. 0 <a <1.0, 0 ≦ b1 ≦ 0.3, 0 ≦ b2 ≦ 0.3, 0 <b1 + b2 ≦ 0.3, and 0 <c ≦ 0.5.)

Further, as a conventional photosensitive transfer material, one described in Patent Document 3 is known.
Patent Document 3 includes a temporary support, a polymer having a structural unit represented by the following general formula A and a structural unit having an acid group, and having a glass transition temperature of 90 ° C. or lower, and a photoacid generator. There is disclosed a photosensitive transfer material having a positive photosensitive resin layer containing.

In general formula A, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group. Alternatively, it represents an aryl group, and R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether. R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or an arylene group.

Patent Document 1: Japanese Patent Laid-Open No. 2015-187634 Patent Document 2: Japanese Patent Laid-Open No. 2011-39266 Patent Document 3: Japanese Patent Laid-Open No. 2017-156735

The problem to be solved by an embodiment of the present invention is to provide a photosensitive transfer material having excellent laminating properties and resolution.
Another problem to be solved by another embodiment of the present invention is to provide a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method using the photosensitive transfer material. .

Means for solving the above problems include the following aspects.
<1> A temporary support and a photosensitive resin layer, wherein the photosensitive resin layer includes a polymer component satisfying at least one of the following a1 and a2, and a photoacid generator, and the polymer component The photosensitive transfer material whose glass transition temperature is 90 degrees C or less.
a1: Polymer component containing a structural unit having an acid group protected by an acid-decomposable group and a polymer having a structural unit having a pKaH group of 3 or more a2: An acid group protected by an acid-decomposable group And a polymer component comprising a polymer having a structural unit having a structural unit having a pKaH group of 3 or more <2> All pKaH groups contained in the photosensitive resin layer are 3 or more groups Among these, the photosensitive transfer material as described in <1> whose ratio of the group whose pKaH is 3 or more contained in the polymer component is 30 mol% or more.
<3> Of all the groups having 3 or more pKaH contained in the photosensitive resin layer, the ratio of the group having 3 or more pKaH contained in the polymer component is 50 mol% or more <1> or The photosensitive transfer material as described in <2>.
<4> The polymer in the polymer component further includes a structural unit other than a structural unit having an acid group protected by an acid-decomposable group and a structural unit having a pKaH of 3 or more. <1> to <3 > The photosensitive transfer material as described in any one of>.
<5> The photosensitive transfer material according to any one of <1> to <4>, wherein the structural unit having the pKaH group of 3 or more is a structural unit represented by the following formula I or formula II.

In Formulas I and II, R ₁ represents a hydrogen atom or a methyl group, and Z is a single bond, a methylene group, an arylene group, —O—, —C (═O) —NH—, or —C (═O) —. Represents O—, and R ₂ may have a single bond or at least one group selected from the group consisting of an ether bond, a urethane bond, a urea bond, an amide bond, an ester bond and a carbonate bond. Represents a linear, branched or cyclic alkylene group of 1 to 10, wherein R ₃ and R ₄ are each independently a hydrogen atom, or an ether bond, a thioether bond, a hydroxy group, a formyl group, an acetoxy group, a cyano group A linear group having 1 to 20 carbon atoms which may have at least one group selected from the group consisting of a group, a urethane bond, a urea bond, an amide bond, an ester bond, a carbonate bond and an aromatic group, Represents a branched or cyclic alkyl group, R ₂ and R ₃ , R ₂ and R ₄ , or R ₃ and R ₄ may be bonded to each other to form a ring, and Q ₁ represents a nitrogen atom Represents an aromatic group or a nitrogen-containing heteroaromatic group.

<6> The photosensitive transfer material according to <5>, wherein the structural unit having the pKaH group of 3 or more is a structural unit represented by the formula I.
<7> The photosensitive transfer material according to any one of <1> to <6>, wherein the structural unit having an acid group protected with an acid-decomposable group is a structural unit represented by the following formula A: .

In formula A, R ³¹ and R ³² each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R ³¹ and R ³² is an alkyl group or an aryl group, and R ³³ is an alkyl group or Represents an aryl group, and R ³¹ or R ³² and R ³³ may combine to form a cyclic ether, R ³⁴ represents a hydrogen atom or a methyl group, and X ⁰ represents a single bond or a divalent linking group. Represents.

<8> A step of bringing the photosensitive resin layer in the photosensitive transfer material according to any one of <1> to <7> into contact with a substrate and bonding the substrate; and a step of pattern exposing the photosensitive resin layer; And a step of developing the exposed photosensitive resin layer to form a pattern, in this order.
<9> A step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of <1> to <7> into contact with a substrate having a conductive layer and bonding the photosensitive resin layer, A circuit wiring including a pattern exposure step, a step of developing the exposed photosensitive resin layer to form a pattern, and a step of etching a conductive layer in a region where the pattern is not disposed. Production method.
<10> The method for manufacturing a circuit wiring according to <9>, wherein the conductive layer is a layer containing copper.
<11> The step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of <1> to <7> into contact with a substrate having a conductive layer and bonding the photosensitive resin layer, Manufacturing of a touch panel that includes a pattern exposure step, a step of developing the exposed photosensitive resin layer to form a pattern, and a step of etching a conductive layer in a region where the pattern is not disposed in this order. Method.

According to one embodiment of the present invention, it is possible to provide a photosensitive transfer material that is excellent in laminating suitability and resolution.
In addition, according to another embodiment of the present invention, a resin pattern manufacturing method, a circuit wiring manufacturing method, and a touch panel manufacturing method using the photosensitive transfer material can be provided.

It is the schematic which shows an example of the laminated constitution of the photosensitive transfer material which concerns on this indication. FIG. 6 is a schematic diagram showing a pattern A. FIG. 6 is a schematic diagram showing a pattern B.

Hereinafter, the contents of the present disclosure will be described. In addition, although it demonstrates referring an accompanying drawing, a code | symbol may be abbreviate | omitted.
In the present specification, a numerical range expressed using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value.
In this specification, “(meth) acryl” represents both and / or acryl and methacryl, and “(meth) acrylate” represents both and / or acrylate and methacrylate.
Further, in the present specification, the amount of each component in the composition is the sum of the plurality of corresponding substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. Means quantity.
In this specification, the term “process” is not limited to an independent process, and is included in this term if the intended purpose of the process is achieved even when it cannot be clearly distinguished from other processes.
In the notation of groups (atomic groups) in this specification, the notation that does not indicate substitution and non-substitution includes those having no substituent and those having a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, “exposure” includes not only exposure using light, but also drawing using particle beams such as an electron beam and an ion beam, unless otherwise specified. In addition, as light used for exposure, in general, an emission ray spectrum of a mercury lamp, an actinic ray (active energy ray) such as a far ultraviolet ray, an extreme ultraviolet ray (EUV light) represented by an excimer laser, an X-ray, and an electron beam is used. Can be mentioned.
In addition, the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
In the present disclosure, “mass%” and “weight%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment.
In addition, the weight average molecular weight (Mw) and number average molecular weight (Mn) in the present disclosure use columns of TSKgel GMHxL, TSKgel G4000HxL, and TSKgel G2000HxL (all trade names manufactured by Tosoh Corporation) unless otherwise specified. The molecular weight was detected by a gel permeation chromatography (GPC) analyzer using a THF (tetrahydrofuran) solvent and a differential refractometer, and converted using polystyrene as a standard substance.

(Photosensitive transfer material)
A photosensitive transfer material according to the present disclosure includes a temporary support and a photosensitive resin layer, and the photosensitive resin layer satisfies at least one of the following a1 and a2, and a photoacid generator The glass transition temperature (Tg) of the polymer component is 90 ° C. or lower.
a1: Polymer component containing a structural unit having an acid group protected by an acid-decomposable group and a polymer having a structural unit having a pKaH group of 3 or more a2: An acid group protected by an acid-decomposable group And a polymer component comprising a polymer having a structural unit having a pKaH group of 3 or more. The photosensitive transfer material according to the present disclosure is a positive photosensitive transfer material. .

Conventional positive photosensitive transfer materials may contain a low molecular weight basic compound (also referred to as “quencher”) for the purpose of capturing the generated acid and stopping the decomposition reaction of the acid-decomposable group. It was. However, in the photosensitive transfer material to which the conventional low molecular weight basic compound is added, the low molecular weight basic compound tends to be unevenly distributed on the transferred substrate side, etc., and the uneven distribution causes tailing at the bottom of the resist pattern during development, The present inventors have found that the resolution may be poor. This problem is specific to a photosensitive transfer material containing an acid-decomposable polymer having a Tg of 90 ° C. or less and a photoacid generator, and has a high Tg of 90 g. This is a problem that cannot be seen in conventional resist compositions using polymers.
As a result of intensive studies, the present inventors have found that by using the photosensitive transfer material having the above-described structure, the laminate suitability and the resolution are excellent.
The detailed expression mechanism of the above effect is unknown, but by containing a polymer having a structural unit having pKaH of 3 or more groups, a group having a basic component of pKaH of 3 or more is fixed to the polymer. It is considered that the structural unit having a base component of pKaH having a group of 3 or more is prevented from being unevenly distributed on the substrate side, and the reduction in resolution resulting from the tailing of the resist pattern during development has been improved. Yes. Therefore, even when using a polymer component having a Tg of 90 ° C. or less, which is considered to easily move the low molecular component, it is possible to improve the decrease in resolution resulting from the tailing of the resist pattern during development. Since it is a polymer component of 90 ° C. or less, the suitability for lamination is also excellent.

In addition, the photosensitive transfer material according to the present disclosure has the above-described configuration, so that excessive diffusion of acid generated from the photoacid generator can be suppressed, and a certain amount of time has elapsed after the photosensitive transfer material is exposed. Even when the development is performed after this, it is possible to suppress the thinning of the line width of the obtained resin pattern (also referred to as “retention time-dependent suppression”).

Hereinafter, the photosensitive transfer material according to the present disclosure will be described in detail.

FIG. 1 schematically illustrates an example of a layer configuration of a photosensitive transfer material according to the present disclosure. In the photosensitive transfer material 100 shown in FIG. 1, a temporary support 10, a photosensitive resin layer 12, and a cover film 14 are laminated in this order.
The photosensitive resin layer 12 includes a polymer component satisfying at least one of the a1 and a2 and a photoacid generator, and the glass transition temperature of the polymer component is 90 ° C. or lower.
Hereinafter, constituent materials and the like of the photosensitive transfer material according to the present disclosure will be described.

<Temporary support>
The temporary support is a support that supports the photosensitive resin layer and can be peeled off.
The temporary support used in the present disclosure preferably has light transparency from the viewpoint that the photosensitive resin layer can be exposed through the temporary support when the photosensitive resin layer is subjected to pattern exposure.
In the present disclosure, having light transmittance means that the transmittance of the main wavelength of light used for pattern exposure is 50% or more, and the transmittance of the main wavelength of light used for pattern exposure is exposure. From the viewpoint of improving sensitivity, 60% or more is preferable, and 70% or more is more preferable. Examples of the method for measuring the transmittance include a method of measuring using MCPD Series manufactured by Otsuka Electronics Co., Ltd.
Examples of the temporary support include a glass substrate, a resin film, paper, and the like, and a resin film is particularly preferable from the viewpoints of strength and flexibility. Examples of the resin film include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among these, a biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of the temporary support is not particularly limited, but is preferably in the range of 5 μm to 200 μm, and more preferably in the range of 10 μm to 150 μm from the viewpoint of ease of handling and versatility.
The thickness of the temporary support is selected according to the material from the viewpoints of strength as a support, flexibility required for bonding with a wiring forming substrate, light transmittance required in the first exposure process, and the like. That's fine.

A preferred embodiment of the temporary support is described, for example, in paragraphs 0017 to 0018 of JP-A-2014-85643, and the contents of this publication are incorporated in this specification.

<Photosensitive resin layer>
The photosensitive transfer material according to the present disclosure has at least a temporary support and a photosensitive resin layer, and the photosensitive resin layer satisfies at least one of the a1 and a2, and a photoacid generator. The glass transition temperature (Tg) of the polymer component is 90 ° C. or less.
The photosensitive resin layer is preferably a chemically amplified positive photosensitive resin layer.
Photoacid generators such as onium salts and oxime sulfonate compounds described below are used to deprotect protected acid groups in binders in which the acid generated in response to actinic rays has acid-decomposable and protected acid groups. The acid produced by the action of one photon contributes to many deprotection reactions, and the quantum yield exceeds 1, for example, a large value such as the power of 10 High sensitivity is obtained as a result of so-called chemical amplification.
On the other hand, when a quinonediazide compound (NQD) is used as a photoacid generator sensitive to actinic rays, a carboxy group is generated by a sequential photochemical reaction, but its quantum yield is always 1 or less. Not applicable.

<< polymer component >>
The polymer component contained in the photosensitive resin layer satisfies at least one of the following a1 and a2. Moreover, the glass transition temperature of the said polymer component is 90 degrees C or less.
a1: Polymer component containing a structural unit having an acid group protected by an acid-decomposable group and a polymer having a structural unit having a pKaH group of 3 or more a2: An acid group protected by an acid-decomposable group And a polymer component comprising a polymer having a structural unit having pKaH and a structural unit having a structural unit having 3 or more groups

The polymer component preferably satisfies the above a1 from the viewpoint of developability, and preferably satisfies the above a2 from the viewpoint of easy physical property adjustment.
Further, all the polymers contained in the polymer component are each at least one structural unit selected from the group consisting of a structural unit having an acid group protected with an acid-decomposable group and a structural unit having an acid group. It is preferable that it is a polymer which has.
Each of the polymers shown in a1 and a2 may contain only one type or two or more types.
Moreover, the polymer component may further contain a polymer other than the polymers shown in the a1 and a2.
Unless otherwise specified, the polymer component in the present disclosure means one including other polymers added as necessary in addition to the above-described aspect of a1 or a2.

The polymer in the polymer component is preferably an addition polymerization type resin, and is derived from a structural unit derived from (meth) acrylic acid and / or an ester thereof, and / or a styrene compound and / or a vinyl naphthalene compound. It is more preferable that the polymer contains a structural unit, and a polymer containing a structural unit derived from (meth) acrylic acid and / or an ester thereof is more preferable. In addition, you may have structural units other than the above, for example, a structural unit derived from a vinyl compound.

-Glass transition temperature (Tg) of polymer component-
The glass transition temperature (Tg) of the polymer component in the present disclosure is 90 ° C. or lower, preferably 60 ° C. or lower, and more preferably 50 ° C. or lower. Within the above range, the photosensitive resin layer has high adhesion and excellent transferability.
The lower limit of Tg is not particularly limited, but is preferably −20 ° C. or higher, more preferably −10 ° C. or higher, still more preferably 10 ° C. or higher, and particularly preferably 25 ° C. or higher. When the Tg of the polymer component is −20 ° C. or higher, good pattern formability is maintained, and when a cover film is used, for example, peeling failure when peeling the cover film is suppressed.
Further, in the present disclosure, a structural unit having an acid group protected with an acid-decomposable group, a polymer having a structural unit having a pKaH group of 3 or more, and a structure having an acid group protected by an acid-decomposable group The glass transition temperature (Tg) of the polymer having a unit or the polymer having a structural unit having a pKaH group of 3 or more is preferably 90 ° C. or less independently from the viewpoint of transferability. It is more preferably 20 ° C. or higher and 70 ° C. or lower, further preferably 10 ° C. or higher and 60 ° C. or lower, and particularly preferably 25 ° C. or higher and 50 ° C. or lower.

The glass transition temperature of the polymer can be measured using differential scanning calorimetry (DSC).
A specific measuring method is performed in accordance with the method described in JIS K 7121 (1987). As the glass transition temperature in this specification, an extrapolated glass transition start temperature (hereinafter sometimes referred to as Tig) is used.
The method for measuring the glass transition temperature will be described more specifically.
When determining the glass transition temperature, after maintaining the apparatus at a temperature about 50 ° C. lower than the expected Tg of the polymer until the apparatus is stabilized, the heating rate is about 20 ° C./min and about 30 times higher than the temperature at which the glass transition is completed. Heat to a higher temperature and draw a DTA or DSC curve.
The extrapolated glass transition start temperature (Tig), that is, the glass transition temperature Tg in the present specification, is a straight line obtained by extending the low-temperature side baseline in the DTA curve or DSC curve to the high-temperature side, and the step-like change portion of the glass transition. Calculated as the temperature of the intersection with the tangent drawn at the point where the slope of the curve is maximum.

As a method for adjusting the Tg of the polymer to the above-described preferable range, for example, from the Tg of the homopolymer of each constituent unit of the target polymer and the mass ratio of each constituent unit, the FOX formula is used as a guideline. It is possible to control the Tg of the target polymer.
Regarding the FOX formula: Tg of the homopolymer of the first structural unit contained in the polymer is Tg1, the mass fraction in the copolymer of the first structural unit is W1, and the Tg of the homopolymer of the second structural unit Is Tg2 and the mass fraction in the copolymer of the second structural unit is W2, the Tg0 (K) of the copolymer containing the first structural unit and the second structural unit is It is possible to estimate according to the equation.
FOX formula: 1 / Tg0 = (W1 / Tg1) + (W2 / Tg2)
A copolymer having a desired Tg can be obtained by adjusting the type and mass fraction of each structural unit contained in the copolymer using the FOX formula described above.
It is also possible to adjust the Tg of the polymer by adjusting the weight average molecular weight of the polymer.

Further, the glass transition temperature of the polymer component in the present disclosure is obtained by measuring or calculating the glass transition temperature of each polymer contained in the polymer component, and the weighted average, that is, the glass transition temperature of each polymer and the entire polymer component. It shall be obtained by adding the product of the mass ratio to.
Tg of polymer component = Tg of polymer 1 × content ratio of polymer 1 + Tg of polymer 2 × content ratio of polymer 2+...

-Weight average molecular weight of polymer (Mw)-
The weight average molecular weight (Mw) of the polymer is preferably 60,000 or less, more preferably 2,000 to 60,000 in terms of polystyrene, from the viewpoint of laminate suitability, More preferably, it is 000 to 50,000, and particularly preferably 15,000 to 50,000.
In addition, the weight average molecular weight and number average molecular weight of the polymer can be measured by GPC (gel permeation chromatography), and various commercially available apparatuses can be used as the measuring apparatus, and the contents of the apparatus, and Measurement techniques are known to those skilled in the art.
For the measurement of the weight average molecular weight by gel permeation chromatography (GPC), HLC (registered trademark) -8220GPC (manufactured by Tosoh Corporation) was used as a measuring device, and TSKgel (registered trademark) Super HZM-M (4 .6 mm ID × 15 cm, manufactured by Tosoh Corporation), Super HZ4000 (4.6 mm ID × 15 cm, manufactured by Tosoh Corporation), Super HZ3000 (4.6 mm ID × 15 cm, manufactured by Tosoh Corporation), Super HZ2000 (4.6 mm ID) × 15 cm, manufactured by Tosoh Corp.), each connected in series, and THF (tetrahydrofuran) can be used as an eluent.
Measurement conditions are 0.2% by mass, flow rate is 0.35 ml / min, sample injection amount is 10 μl, measurement temperature is 40 ° C., and a differential refractive index (RI) detector is used. be able to.
The calibration curve is “Standard sample TSK standard, polystyrene” manufactured by Tosoh Corporation: “F-40”, “F-20”, “F-4”, “F-1”, “A-5000”, “ It can be produced using at least two of any of the seven samples of “A-2500” and “A-1000”.

The ratio (dispersion degree) between the number average molecular weight and the weight average molecular weight of the polymer is preferably 1.0 to 5.0, more preferably 1.05 to 3.5.

-Constitutional unit in which pKaH has 3 or more groups-
The polymer component includes a polymer having at least a structural unit having a pKaH of 3 or more.
Specifically, for example, a polymer having a structural unit having an acid group protected by an acid-decomposable group and a structural unit having a pKaH group of 3 or more, or an acid protected by an acid-decomposable group Examples thereof include a polymer having no structural unit having a group and having a structural unit having a pKaH of 3 or more.
In the present disclosure, pKaH is a pKa of a conjugate acid, and a group having a pKaH of 3 or more represents a group having a pKa of a conjugate acid of the group of 3 or more. For example, the value of pKaH of —NH ₂ is the value of pKa of —NH ₃ ⁺ .
In the present disclosure, pKaH is a calculated value obtained by ACD / ChemSketch (ACD / Labs 8.00 Release Product Version: 8.08).
Specifically, from the chemical structure of the structural unit having a specific functional group, the above-mentioned ACD / ChemSketch is used to calculate the pKaH value of the specific functional group.

The group having a pKaH of 3 or more is preferably a group having a pKaH of 4 or more, more preferably a group having a pKaH of 5 or more, from the viewpoints of resolution and retention time-dependent suppression. A group of 5 or more and 15 or less is more preferable, and a group having a pKaH of 6 or more and 10 or less is particularly preferable.
In other words, the polymer component preferably includes a polymer having at least a constituent unit having a pKaH group of 4 or more, and a pKaH of 5 or more, from the viewpoint of resolution and retention time-dependent suppression. It is more preferable to include a polymer having at least a structural unit having a group, and it is further preferable to include a polymer having at least a structural unit having a pKaH of 5 or more and 15 or less, and a group having a pKaH of 6 to 10 or less. It is particularly preferable to include a polymer having at least a structural unit having.

The group having a pKaH of 3 or more is preferably a group having a nitrogen atom from the viewpoint of resolution and retention time-dependent suppression, and is an aliphatic amino group, an aromatic amino group, or a nitrogen-containing complex. It is more preferably an aromatic ring group, further preferably an aliphatic amino group or a nitrogen-containing heteroaromatic ring group, and particularly preferably an aliphatic amino group.
The aliphatic amino group may be any of a primary amino group, a secondary amino group, or a tertiary amino group, but from the viewpoints of resolution and retention time dependence suppression, It is preferably a secondary amino group or a tertiary amino group.
The aromatic amino group is preferably an anilino group, a monoalkylanilino group, or a dialkylanilino group, and more preferably a monoalkylanilino group or a dialkylanilino group.
The nitrogen-containing heteroaromatic ring in the nitrogen-containing heteroaromatic group is preferably a pyridine ring, an imidazole ring or a triazole ring, more preferably a pyridine ring or an imidazole ring, and a pyridine ring. Is particularly preferred.
The nitrogen-containing heteroaromatic group may further have a substituent on the nitrogen-containing heteroaromatic ring. The substituent is not particularly limited, but is preferably an alkyl group, and more preferably a methyl group.

In addition, the group having a pKaH of 3 or more is particularly preferably a group having an alkylamine structure from the viewpoint of resolution and retention time-dependent suppression.
Examples of the alkylamine structure include dialkylamine and trialkylamine. Specifically, dimethylamino group, diethylamino group, dipropylamino group, diisopropylamino group, 1,2,2,6,6-penta Examples include an alkyl-4-piperidyl group and a 2,2,6,6-tetraalkyl-4-piperidyl group.

The structural unit having a pKaH group of 3 or more is preferably a structural unit represented by the following formula I or formula II from the viewpoints of resolution and retention time-dependent inhibition properties. More preferably, it is a structural unit.

In Formulas I and II, R ₁ represents a hydrogen atom or a methyl group, and Z represents a single bond, a methylene group, an arylene group, —O—, —C (═O) —NH—, or —C (═O) —. Represents O—, and R ₂ may have a single bond or at least one group selected from the group consisting of an ether bond, a urethane bond, a urea bond, an amide bond, an ester bond and a carbonate bond. Represents a linear, branched or cyclic alkylene group of 1 to 10, wherein R ₃ and R ₄ are each independently a hydrogen atom, or an ether bond, a thioether bond, a hydroxy group, a formyl group, an acetoxy group, a cyano group A linear group having 1 to 20 carbon atoms which may have at least one group selected from the group consisting of a group, a urethane bond, a urea bond, an amide bond, an ester bond, a carbonate bond, and an aromatic group Represents a branched or cyclic alkyl group, R ₂ and R ₃ , R ₂ and R ₄ , or R ₃ and R ₄ may be bonded to each other to form a ring, and Q ₁ is a nitrogen atom Represents an aromatic group having nitrogen or a nitrogen-containing heteroaromatic group.

Z in Formula I is a single bond, an arylene group, —C (═O) —NH— or —C (═O) —O— from the viewpoint of resolution, retention time-dependent inhibition, and ease of synthesis. It is preferably an arylene group, more preferably an —C (═O) —NH— or —C (═O) —O—, and —C (═O) —NH— or —C (═O). Particularly preferred is —O—.
Z in Formula II is preferably a single bond, an arylene group, or —C (═O) —O—, and is a single bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. Is more preferable.
R ₂ in Formula I has at least one group selected from the group consisting of an ether bond, a urethane bond, and a urea bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. It is preferably a linear, branched or cyclic alkylene group having 1 to 10 carbon atoms, and has at least one group selected from the group consisting of an ether bond, a urethane bond and a urea bond. It is more preferably a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms, particularly preferably a linear, branched or cyclic alkylene group having 2 to 10 carbon atoms.
R ₂ in Formula II is preferably a single bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis.

R ₃ and R ₄ in formula I are each independently a hydrogen atom or a carbon number of 1 to 20 which may have an ether bond from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis. The linear, branched or cyclic alkyl group is preferably a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms.
Further, in the formula I, from the viewpoints of resolution and retention time dependence suppression, an embodiment in which R ₂ , R ₃ and R ₄ in the formula I are combined to form a nitrogen-containing aliphatic ring is preferable, An embodiment in which a piperidine ring is formed is more preferable.
Q ₁ in Formula II is preferably a nitrogen-containing heteroaromatic group from the viewpoints of resolution, retention time-dependent inhibition, and ease of synthesis, and is pyridyl, methylpyridyl, imidazolyl, methylimidazolyl Group or a triazolyl group is more preferable, a pyridyl group is more preferable, and a 4-pyridyl group is particularly preferable.

Specific examples of the monomer that forms a structural unit having a pKaH group of 3 or more include the following monomers.
1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2- (dimethylamino) ethyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2,2 methacrylate , 6,6-tetramethyl-4-piperidyl, 2,2,6,6-tetramethyl-4-piperidyl acrylate, 2- (diethylamino) ethyl methacrylate, 2- (dimethylamino) ethyl acrylate, acrylic acid 2- (diethylamino) ethyl, N- (3-dimethylamino) propyl methacrylate, N- (3-dimethylamino) propyl acrylate, N- (3-diethylamino) propyl methacrylate, N- (3-diethylamino acrylate) ) Propyl, 2- (diisopropylamino) ethyl methacrylate, 2-morpholinoethyl methacrylate, 2-morpholinoethyl crylate, N- [3- (dimethylamino) propyl] acrylamide, allylamine, 4-aminostyrene, 4-vinylpyridine, 2-vinylpyridine, 3-vinylpyridine, 1-vinylimidazole, 2-methyl -1-vinylimidazole, 1-allylimidazole, 1-vinyl-1,2,4-triazole

In the above monomers, R ¹² represents a hydrogen atom or a methyl group.

In addition, monomers having an amino group or a nitrogen-containing heterocyclic group described in JP-A-2015-187634 or JP-A-2011-39266 are also included.

Resin having at least a structural unit having pKaH having 3 or more groups (for example, a polymer having a structural unit having an acid group protected with an acid-decomposable group, and a structural unit having pKaH having 3 or more groups, Alternatively, the content of the structural unit having pKaH having 3 or more groups in the polymer having a structural unit having pKaH having 3 or more groups is determined from the viewpoint of resolution and retention time dependence suppression. It is preferably 0.01% by mass or more and 30% by mass or less, more preferably 0.05% by mass or more and 20% by mass or less, and more preferably 0.1% by mass or more and 10% by mass or less with respect to the total mass of the coalescence. It is more preferable that it is 0.4 mass% or more and 4 mass% or less, and it is most preferable that it is 0.5 mass% or more and 2 mass% or less.
In addition, the content of the structural unit in which the pKaH has a group of 3 or more in the polymerizable component is 0.01% with respect to the total mass of the polymer component from the viewpoint of resolution and retention time-dependent suppression. It is preferably from 10% by mass to 10% by mass, more preferably from 0.05% by mass to 8% by mass, still more preferably from 0.1% by mass to 5% by mass, The content is particularly preferably from 4% by weight to 4% by weight, and most preferably from 0.5% by weight to 2% by weight.

Further, as will be described later, the photosensitive resin layer may contain a basic compound having a pKaH group of 3 or more in addition to the pKaH group of 3 or more in the polymer.
From the viewpoint of resolution and retention time-dependent suppression, among all the groups having 3 or more pKaH contained in the photosensitive resin layer, the ratio of the groups having 3 or more pKaH contained in the polymer component is 30 mol% or more, preferably 50 mol% or more, more preferably 80 mol% or more, and particularly preferably 90 mol% or more and 100 mol% or less.
The content (content ratio: mass ratio) of the structural unit having a pKaH group of 3 or more in the polymer A can be confirmed by the intensity ratio of the peak intensity calculated by ¹³ C-NMR measurement by a conventional method. .

-Constituent units having acid groups protected with acid-decomposable groups-
The polymer component includes a polymer having at least a structural unit having an acid group protected with an acid-decomposable group.
Specifically, for example, a polymer having a structural unit having an acid group protected with an acid-decomposable group and a structural unit having pKaH having 3 or more groups, or a structure having pKaH having 3 or more groups Examples thereof include a polymer having a constitutional unit having no unit and having an acid group protected with an acid-decomposable group.
When the polymer component contains a polymer having a structural unit having an acid group protected with an acid-decomposable group, a highly sensitive chemically amplified positive photosensitive resin layer can be obtained.
The “acid group protected with an acid-decomposable group” in the present disclosure may be any known acid group and acid-decomposable group, and is not particularly limited. Specific examples of the acid group preferably include a carboxy group and a phenolic hydroxyl group. The acid group protected with an acid-decomposable group is a group that is relatively easily decomposed by an acid (for example, an ester group, a tetrahydropyranyl ester group, or a tetrahydrofuranyl ester protected with a group represented by the formula A). An acetal functional group such as a group) or a group that is relatively difficult to decompose with an acid (for example, a tertiary alkyl group such as a tert-butyl ester group or a tertiary alkyl carbonate group such as a tert-butyl carbonate group). Can do.
Among these, the acid-decomposable group is preferably a group having a structure in which an acid is protected in the form of an acetal from the viewpoints of sensitivity and resolution.

The structural unit having an acid group protected with an acid-decomposable group is preferably a structural unit represented by the following formula A from the viewpoint of sensitivity and resolution.

In the formula A, when R ³¹ or R ³² is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ³¹ or R ³² is an aryl group, a phenyl group is preferable. R ³¹ and R ³² are each preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In Formula A, R ³³ represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
Further, the alkyl group and aryl group in R ³¹ to R ³³ may have a substituent.
In Formula A, R ³¹ or R ³² and R ³³ may be linked to form a cyclic ether, and R ³¹ or R ³² and R ³³ are preferably linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In Formula A, X ⁰ represents a single bond or an arylene group, and a single bond is preferable. The arylene group may have a substituent.
The structural unit represented by the formula A is a structural unit having a carboxy group protected with an acid-decomposable group. When the polymer contains the structural unit represented by the formula A, the sensitivity at the time of pattern formation is excellent and the resolution is superior.

In formula A, R ³⁴ represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint that the Tg of the polymer can be further lowered.
More specifically, the structural unit in which R ³⁴ in Formula A is a hydrogen atom is preferably 20% by mass or more based on the total amount of the structural unit represented by Formula A contained in the polymer.
The content (content ratio: mass ratio) of the structural unit in which R ³⁴ in Formula A is a hydrogen atom in the structural unit having an acid group protected with an acid-decomposable group is ¹³ C-nuclear magnetic resonance. It can be confirmed by the intensity ratio of the peak intensity calculated from the spectrum (NMR) measurement by a conventional method.

Among the structural units represented by the formula A, the structural unit represented by the following formula A2 is more preferable from the viewpoint of further increasing the sensitivity during pattern formation.

In formula A2, R ³⁴ represents a hydrogen atom or a methyl group, and R ³⁵ to R ⁴¹ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In formula A2, R ³⁴ is preferably a hydrogen atom.
In formula A2, R ³⁵ to R ⁴¹ are preferably hydrogen atoms.

Preferable specific examples of the structural unit represented by formula A having a carboxy group protected with an acid-decomposable group include the following structural units. R ³⁴ represents a hydrogen atom or a methyl group.

The structural unit having an acid group protected with an acid-decomposable group is preferably a structural unit represented by the following formula A3 from the viewpoint of suppressing deformation of the pattern shape.

In Formula A3, R ^B1 and R ^B2 each independently represent a hydrogen atom, an alkyl group, or an aryl group, at least one of R ^B1 and R ^B2 is an alkyl group or an aryl group, and R ^B3 is an alkyl group or Represents an aryl group, R ^B1 or R ^B2 and R ^B3 may be linked to form a cyclic ether, R ^B4 represents a hydrogen atom or a methyl group, and X ^B represents a single bond or a divalent linking group; R ^B12 represents a substituent, and n represents an integer of 0 to 4.

In Formula A3, when R ^B1 or R ^B2 is an alkyl group, an alkyl group having 1 to 10 carbon atoms is preferable. When R ^B1 or R ^B2 is an aryl group, a phenyl group is preferable. R ^B1 and R ^B2 are each independently preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
In Formula A3, R ^B3 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group having 1 to 6 carbon atoms.
In addition, the alkyl group and aryl group in R ^B1 to R ^B3 may have a substituent.
In Formula A3, R ^B1 or R ^B2 and R ^B3 may be linked to form a cyclic ether, and R ^B1 or R ^B2 and R ^B3 are preferably linked to form a cyclic ether. The number of ring members of the cyclic ether is not particularly limited, but is preferably 5 or 6, and more preferably 5.
In Formula A3, X ^B represents a single bond or a divalent linking group, and represents a single bond or an alkylene group, —C (═O) O—, —C (═O) NR ^N —, —O—, or a combination thereof. Are preferable, and a single bond is more preferable. The alkylene group may be linear, branched or cyclic, and may have a substituent. The alkylene group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. When X ^B contains —C (═O) O—, an embodiment in which the carbon atom contained in —C (═O) O— and the carbon atom bonded to R ^B4 are directly bonded is preferable. When ^{containing, -C (= O) NR N} - - is ^{X B -C (= O) NR} N and carbon atoms contained in ^a mode in which the carbon atom ^{to which R B4} is bonded is directly bonded is preferable. R ^N represents an alkyl group or a hydrogen atom, preferably an alkyl group or a hydrogen atom having 1 to 4 carbon atoms, more preferably a hydrogen atom.
In formula A3, the group containing R ^B1 to R ^B3 and X ^B are preferably bonded to each other at the para position.
In Formula A3, R ^B12 represents a substituent, and is preferably an alkyl group or a halogen atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
In the formula A3, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

In Formula A3, R ^B4 represents a hydrogen atom or a methyl group, and is preferably a hydrogen atom from the viewpoint of lowering the Tg of the polymer.
More specifically, with respect to the total content of the structural unit having an acid group protected by the acid-decomposable group contained in the polymer, the structural unit in which R ^B4 in formula A3 is a hydrogen atom is 20% by mass or more. It is preferable that
In the structural unit having an acid group protected with an acid-decomposable group, the content (content ratio: mass ratio) of the structural unit in which R ^B4 in formula A3 is a hydrogen atom is ¹³ C-nuclear magnetic resonance. It can be confirmed by the intensity ratio of the peak intensity calculated from the spectrum (NMR) measurement by a conventional method.

Among the structural units represented by the formula A3, the structural unit represented by the following formula A4 is more preferable from the viewpoint of suppressing deformation of the pattern shape.

In Formula A4, R ^B4 represents a hydrogen atom or a methyl group, R ^B5 to R ^B11 each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R ^B12 represents a substituent, and n is 0 Represents an integer of ~ 4.
In formula A4, R ^B4 is preferably a hydrogen atom.
In formula A4, R ^B5 to R ^B11 are preferably hydrogen atoms.
In Formula A4, R ^B12 represents a substituent, and is preferably an alkyl group or a halogen atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
In the formula A4, n represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.

Preferable specific examples of the structural unit A4 represented by the formula A4 include the following structural units. R ^B4 represents a hydrogen atom or a methyl group.

The structural unit having an acid group protected by the acid-decomposable group contained in the polymer may be one type or two or more types.
The content of the structural unit having an acid group protected by the acid-decomposable group in the polymer is preferably 10% by mass or more with respect to the total mass of the polymer, and is 10% by mass to 90% by mass. More preferred is 20% by mass to 70% by mass.
The content (content ratio: mass ratio) of the structural unit having an acid group protected by the acid-decomposable group in the polymer is confirmed by the intensity ratio of the peak intensity calculated by ¹³ C-NMR measurement by a conventional method. be able to.
Moreover, after decomposing all the polymer components into structural units (monomer units), the content ratio of the structural unit having an acid group protected by the acid-decomposable group in the polymer component is the total content of the polymer components. The mass is preferably 5% by mass to 80% by mass, more preferably 10% by mass to 80% by mass, and particularly preferably 20% by mass to 70% by mass.

The mass ratio of the content mass ratio M _B of structural units containing a mass ratio M _A and pKaH constituent units having protected acid groups in the acid-decomposable group in the polymer component having three or more groups (M _A / M _B ) is preferably from 5 to 200, more preferably from 10 to 150, and even more preferably from 20 to 100, from the viewpoints of resolution and retention time-dependent suppression.

From the viewpoint of developability and resolution, the polymer in the polymer component is a structural unit other than a structural unit having an acid group protected with an acid-decomposable group and a structural unit having a pKaH of 3 or more (for example, It is preferable to further include a structural unit having an acid group described below and other structural units).

-Structural unit having an acid group-
The polymers in the polymer component may each independently contain a structural unit having an acid group from the viewpoints of developability and resolution.
The structural unit having an acid group is a structural unit having a protective group, for example, an acid group not protected by an acid-decomposable group, that is, an acid group having no protective group. By including a polymer having a structural unit having an acid group in the polymer component, the sensitivity at the time of pattern formation becomes good, and it becomes easier to dissolve in an alkaline developer in the development process after pattern exposure, thereby shortening the development time. Can be planned.
The acid group in this specification means a proton dissociable group having a pKa of 12 or less. The acid group is usually incorporated into the polymer as a structural unit having an acid group using a monomer capable of forming an acid group. From the viewpoint of improving sensitivity, the pKa of the acid group is preferably 10 or less, and more preferably 6 or less. The pKa of the acid group is preferably −5 or more.

Having at least a constituent unit having an acid group not protected by an acid-decomposable group in any of the polymers in the polymer component, and setting the glass transition temperature of the polymer component to 90 ° C. or less, The positive type photosensitive resin layer to be contained has better resolution and sensitivity at the time of pattern formation while maintaining transferability and peelability from the temporary support at good levels.

Examples of the acid group include a carboxy group, a sulfonamide group, a phosphonic acid group, a sulfonic acid group, a phenolic hydroxyl group, and a sulfonylimide group. Among these, at least one acid group selected from the group consisting of a carboxy group and a phenolic hydroxyl group is preferable.
Introduction of a structural unit having an acid group into the polymer can be carried out by copolymerizing a monomer having an acid group.
The structural unit having an acid group is more preferably a structural unit derived from styrene or a structural unit derived from a vinyl compound, or a structural unit derived from (meth) acrylic acid. preferable.

As the structural unit having an acid group, a structural unit having a carboxy group or a structural unit having a phenolic hydroxyl group is preferable from the viewpoint that sensitivity at the time of pattern formation becomes better.
The monomer having an acid group that can form a structural unit having an acid group is not limited to the examples described above.

The structural unit having an acid group contained in the polymer may be only one type or two or more types.
When the polymer has a structural unit having an acid group, the polymer having a structural unit having an acid group has a structural unit having an acid group in an amount of 0.1% by mass to 20% by mass with respect to the total mass of the polymer. %, Preferably 0.5% to 15% by weight, more preferably 1% to 10% by weight. When it is in the above range, the pattern formability becomes better.
The content (content ratio: mass ratio) of the structural unit having an acid group in the polymer can be confirmed by the intensity ratio of peak intensity calculated by ¹³ C-NMR measurement by a conventional method.
Moreover, after decomposing | disassembling all the polymer components into a structural unit (monomer unit), the content rate of the structural unit which has the said acid group in the said polymer component is 0.1 with respect to the total mass of a polymer component. The mass is preferably 20% by mass to 20% by mass, more preferably 0.5% by mass to 15% by mass, and particularly preferably 1% by mass to 10% by mass.

-Other structural units-
The polymer includes other structural units other than the structural unit having an acid group protected with an acid-decomposable group, the structural unit having a pKaH of 3 or more, and the structural unit having an acid group. The photosensitive transfer material according to the present disclosure may be included within a range that does not impair the effect.
There is no restriction | limiting in particular as a monomer which forms other structural units, For example, styrenes, (meth) acrylic acid alkyl ester, (meth) acrylic acid cyclic alkyl ester, (meth) acrylic acid aryl ester, unsaturated dicarboxylic acid Diester, bicyclounsaturated compound, maleimide compound, unsaturated aromatic compound, conjugated diene compound, unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, unsaturated dicarboxylic acid anhydride, group having aliphatic cyclic skeleton, other Mention may be made of unsaturated compounds.
Various characteristics of the polymer can be adjusted by adjusting at least one of the type and content using other structural units. In particular, the Tg of the polymer component can be easily adjusted to 90 ° C. or lower by appropriately using other structural units.
The polymer may contain only 1 type of other structural units, and may contain 2 or more types.

Other structural units are specifically styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, acetoxystyrene, methoxystyrene, ethoxystyrene, chlorostyrene, methyl vinylbenzoate, ethyl vinylbenzoate, (meta ) Methyl acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meth And a structural unit formed by polymerizing benzyl acrylate, isobornyl (meth) acrylate, acrylonitrile, ethylene glycol monoacetoacetate mono (meth) acrylate, or the like. In addition, the compounds described in paragraphs 0021 to 0024 of JP-A No. 2004-264623 can be given.

As other structural units, structural units having an aromatic ring or structural units having an aliphatic cyclic skeleton are preferable from the viewpoint of improving the electrical properties of the obtained transfer material. Specific examples of monomers that form these structural units include styrene, tert-butoxystyrene, methylstyrene, α-methylstyrene, dicyclopentanyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, And benzyl (meth) acrylate etc. are mentioned. Especially, the structural unit derived from a cyclohexyl (meth) acrylate is mentioned preferably.

In addition, as a monomer that forms other structural unit, for example, (meth) acrylic acid alkyl ester is preferable from the viewpoint of adhesion. Among them, (meth) acrylic acid alkyl ester having an alkyl group having 4 to 12 carbon atoms is more preferable from the viewpoint of adhesion. Specific examples include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate.

The content of other structural units is preferably 70% by mass or less, more preferably 60% by mass or less, and still more preferably 50% by mass or less with respect to the total mass of the polymer. The lower limit may be 0% by mass, but is preferably 1% by mass or more, and more preferably 5% by mass or more. Within the above range, the resolution and adhesion are further improved.

Especially, it is preferable that the polymer contained in the said polymer component contains the structural unit which has a carboxylic ester structure from a laminated suitability and a resolution viewpoint each independently. As the structural unit having a carboxylic acid ester structure, from the viewpoints of laminate suitability and resolution, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, cyclohexyl (meth) acrylate Preferred are structural units derived from 2-ethylhexyl (meth) acrylate or benzyl (meth) acrylate, such as methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate or benzyl (meth) acrylate. The structural unit derived from is more preferable.
Furthermore, the polymer shown in the above a1 or a2 is derived from methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate or benzyl (meth) acrylate from the viewpoint of laminating suitability and resolution. It is preferable to have 2 or more types of structural units derived from methyl (meth) acrylate, ethyl (meth) acrylate, cyclohexyl (meth) acrylate or benzyl (meth) acrylate.

In addition, each of the polymers contained in the polymer component independently contains a structural unit represented by the following formula C as a structural unit having the carboxylic acid ester structure from the viewpoint of laminating suitability and resolution. preferable.

In Formula C, R ^C1 represents a hydrogen atom or a methyl group, and R ^C2 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms. .

R ^C2 in Formula C is preferably a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms or an aralkyl group having 7 to 16 carbon atoms from the viewpoint of laminating suitability and resolution. And more preferably a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a benzyl group, and particularly preferably a methyl group, an ethyl group, a cyclohexyl group, or a benzyl group.

In addition, the polymer shown in a1 or a2 preferably contains 30% by mass or more of a structural unit having a carboxylic acid ester structure with respect to the total mass of the polymer, from the viewpoint of laminating suitability and resolution. More preferably, the content is more preferably 50% by mass to 80% by mass, and particularly preferably 60% by mass to 75% by mass.
Moreover, after decomposing | disassembling all the polymer components into a structural unit (monomer unit), the content rate of the structural unit which has the said carboxylic acid ester structure in the said polymer component is 30 with respect to the total mass of a polymer component. It is preferably at least mass%, more preferably at least 50 mass%, particularly preferably from 50 mass% to 80 mass%.

-Polymer production method-
The polymer production method (synthesis method) is not particularly limited. For example, a polymerizable monomer for forming a structural unit having an acid group protected by an acid-decomposable group, pKaH is 3 or more. A polymerization initiator for forming a structural unit having a group, and, if necessary, a polymerization initiator in an organic solvent containing a polymerizable monomer for forming a structural unit represented by formula C. It can synthesize | combine by superposing | polymerizing using. It can also be synthesized from other polymers by so-called polymer reaction.

The photosensitive resin layer in the present disclosure may contain the polymer component in a proportion of 50% by mass to 99.9% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of developing good adhesion. Preferably, it is contained in a proportion of 70% by mass to 98% by mass.

-Other polymers-
The photosensitive resin layer has, as a polymer component, an acid group protected with an acid-decomposable group, as long as the effect of the photosensitive transfer material according to the present disclosure is not impaired in addition to the polymer shown in a1 or a2. It may further contain a polymer having no structural unit and a structural unit having pKaH having a group of 3 or more (sometimes referred to as "other polymer"). When the photosensitive resin layer contains another polymer, the blending amount of the other polymer is preferably 50% by mass or less, more preferably 30% by mass or less in the total polymer component, More preferably, it is 20 mass% or less.

In addition to the polymer shown to said a1 or a2, the said photosensitive resin layer may contain only 1 type of other polymers, and may contain 2 or more types.
As other polymers, for example, polyhydroxystyrene can be used and are commercially available, such as SMA 1000P, SMA 2000P, SMA 3000P, SMA 1440F, SMA 17352P, SMA 2625P, and SMA 3840F (above, manufactured by Sartomer). , ARUFON UC-3000, ARUFON UC-3510, ARUFON UC-3900, ARUFON UC-3910, ARUFON UC-3920, and ARUFON UC-3080 (above, manufactured by Toagosei Co., Ltd.), and Joncryl 690, Joncryl 6 Joncryl 67, Joncryl 586 (manufactured by BASF) or the like can also be used.

<< Photoacid generator >>
The photosensitive resin layer contains a photoacid generator.
The photoacid generator used in the present disclosure is a compound capable of generating an acid by irradiation with actinic rays such as ultraviolet rays, far ultraviolet rays, X-rays, and charged particle beams.
The photoacid generator used in the present disclosure is preferably a compound that generates an acid in response to an actinic ray having a wavelength of 300 nm or more, preferably 300 nm to 450 nm, but its chemical structure is not limited. Further, a photoacid generator that is not directly sensitive to an actinic ray having a wavelength of 300 nm or more can be used as a sensitizer as long as it is a compound that reacts with an actinic ray having a wavelength of 300 nm or more and generates an acid when used in combination with a sensitizer. It can be preferably used in combination.
The photoacid generator used in the present disclosure is preferably a photoacid generator that generates an acid having a pKa of 4 or less, more preferably a photoacid generator that generates an acid having a pKa of 3 or less, and a pKa of 2 or less. A photoacid generator that generates an acid is particularly preferable. The lower limit value of pKa is not particularly defined, but is preferably −10.0 or more, for example.

Examples of the photoacid generator include an ionic photoacid generator and a nonionic photoacid generator.
The photoacid generator preferably contains at least one compound selected from the group consisting of an onium salt compound described later and an oxime sulfonate compound described later from the viewpoint of sensitivity and resolution, and an oxime sulfonate compound. It is more preferable to contain.

Examples of nonionic photoacid generators include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, the photoacid generator is preferably an oxime sulfonate compound from the viewpoints of sensitivity, resolution, and adhesion. These photoacid generators can be used singly or in combination of two or more. Specific examples of trichloromethyl-s-triazines and diazomethane derivatives include the compounds described in paragraphs 0083 to 0088 of JP 2011-212494A.

As the oxime sulfonate compound, that is, a compound having an oxime sulfonate structure, a compound having an oxime sulfonate structure represented by the following formula (B1) is preferable.

In formula (B1), R ²¹ represents an alkyl group or an aryl group, and * represents a bonding site with another atom or another group.

In the compound having an oxime sulfonate structure represented by the formula (B1), any group may be substituted, and the alkyl group in R ²¹ may be linear or branched. It may have a ring structure. Acceptable substituents are described below.
The alkyl group for R ²¹ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms. The alkyl group of R ²¹ is an aryl group having 6 to 11 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a cycloalkyl group (7,7-dimethyl-2-oxonorbornyl group or other bridged alicyclic group) , Preferably a bicycloalkyl group or the like), or a halogen atom.
The aryl group for R ²¹ is preferably an aryl group having 6 to 18 carbon atoms, and more preferably a phenyl group or a naphthyl group. The aryl group of R ²¹ may be substituted with one or more groups selected from the group consisting of an alkyl group having 1 to 4 carbon atoms, an alkoxy group, and a halogen atom.

The compound having an oxime sulfonate structure represented by the formula (B1) is preferably an oxime sulfonate compound described in paragraphs 0078 to 0111 of JP-A-2014-85643.

Examples of the ionic photoacid generator include onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, quaternary ammonium salts, and the like. Of these, onium salt compounds are preferable, and triarylsulfonium salts and diaryliodonium salts are particularly preferable.

As the ionic photoacid generator, ionic photoacid generators described in paragraphs 0114 to 0133 of JP-A-2014-85643 can also be preferably used.

A photo-acid generator may be used individually by 1 type, and may use 2 or more types together.
The content of the photoacid generator in the photosensitive resin layer is preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of sensitivity and resolution. More preferably, the content is 5% by mass to 5% by mass.

<< basic compound >>
The photosensitive resin layer may further contain a basic compound.
The molecular weight of the basic compound in the present disclosure is less than 2,000, and preferably less than 1,000.
As the basic compound, any basic compound used in a chemically amplified positive resist can be selected and used. Examples thereof include aliphatic amines, aromatic amines, heterocyclic amines, quaternary ammonium hydroxides, and quaternary ammonium salts of carboxylic acids. Specific examples thereof include compounds described in JP-A-2011-212494, paragraphs 0204 to 0207, the contents of which are incorporated herein.

Specific examples of the aliphatic amine include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, di-n-pentylamine, tri-n-pentylamine, diethanolamine, triethanolamine, and the like. Examples include ethanolamine, dicyclohexylamine, and dicyclohexylmethylamine.
Examples of the aromatic amine include aniline, benzylamine, N, N-dimethylaniline, and diphenylamine.
Examples of the heterocyclic amine include pyridine, 2-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 4-dimethylaminopyridine, imidazole, benzimidazole, 4-methylimidazole, 2-phenylbenzimidazole, 2,4,5-triphenylimidazole, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline, pyrazine, Pyrazole, pyridazine, purine, pyrrolidine, piperidine, piperazine, morpholine, 4-methylmorpholine, 1,5-diazabicyclo [4.3.0] -5-nonene, and 1,8-diazabicyclo [5.3.0] -7-Undecene.
Examples of the quaternary ammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-butylammonium hydroxide, and tetra-n-hexylammonium hydroxide.
Examples of the quaternary ammonium salt of carboxylic acid include tetramethylammonium acetate, tetramethylammonium benzoate, tetra-n-butylammonium acetate, and tetra-n-butylammonium benzoate.

The said basic compound may be used individually by 1 type, or may use 2 or more types together.
The photosensitive resin layer does not contain a basic compound, or the content of the basic compound is preferably more than 0% by mass and 2% by mass or less based on the total mass of the photosensitive resin layer. Whether the basic compound is not included, or the content of the basic compound is preferably more than 0% by mass and 2% by mass or less with respect to the total mass of the photosensitive resin layer, and does not include the basic compound More preferably, the content of the basic compound is more than 0% by mass and 1.2% by mass or less, and particularly preferably no basic compound, with respect to the total mass of the photosensitive resin layer.

<< Other additives >>
The said photosensitive resin layer in this indication can contain a well-known additive as needed besides the said component.

-Surfactant-
The photosensitive resin layer preferably contains a surfactant from the viewpoint of film thickness uniformity. As the surfactant, any of anionic, cationic, nonionic (nonionic), or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, higher fatty acid diesters of polyoxyethylene glycol, silicone-based and fluorine-based surfactants. . The following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by JEMCO), MegaFuck (manufactured by DIC Corporation), and Florard (Sumitomo 3M). Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), PolyFox (manufactured by OMNOVA), and SH-8400 (manufactured by Toray Dow Corning Co., Ltd.).
Further, as a surfactant, it contains a structural unit A and a structural unit B represented by the following formula I-1, and is a weight average in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran (THF) as a solvent. A preferable example is a copolymer having a molecular weight (Mw) of 1,000 or more and 10,000 or less.

In formula (I-1), R ⁴⁰¹ and R ⁴⁰³ each independently represent a hydrogen atom or a methyl group, R ⁴⁰² represents a linear alkylene group having 1 to 4 carbon atoms, and R ⁴⁰⁴ represents a hydrogen atom or a carbon group. Represents an alkyl group having 1 to 4 carbon atoms, L represents an alkylene group having 3 to 6 carbon atoms, p and q are mass percentages representing a polymerization ratio, and p is a numerical value of 10 mass% to 80 mass%. Q represents a numerical value of 20% to 90% by mass, r represents an integer of 1 to 18, s represents an integer of 1 to 10, and * represents a bonding site with another structure. Represent.

L is preferably a branched alkylene group represented by the following formula (I-2). R ⁴⁰⁵ in formula (I-2) represents an alkyl group having 1 to 4 carbon atoms, and is preferably an alkyl group having 1 to 3 carbon atoms in terms of compatibility and wettability to the coated surface. Two or three alkyl groups are more preferred. The sum of p and q (p + q) is preferably p + q = 100, that is, 100% by mass.

The weight average molecular weight (Mw) of the copolymer is more preferably from 1,500 to 5,000.

In addition, surfactants described in paragraph 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362 can also be used.

Surfactant may be used individually by 1 type and may use 2 or more types together.
The addition amount of the surfactant is preferably 10% by mass or less, more preferably 0.001% by mass to 10% by mass, and 0.01% by mass with respect to the total mass of the photosensitive resin layer. More preferably, the content is from 3% to 3% by mass.

-Polymerization inhibitor-
The photosensitive resin layer may contain at least one polymerization inhibitor.
As the polymerization inhibitor, for example, the thermal polymerization inhibitor described in paragraph 0018 of Japanese Patent No. 4502784 can be used.
Of these, phenothiazine, phenoxazine or 4-methoxyphenol can be preferably used.

When the photosensitive resin layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 3% by mass, and 0.01% by mass with respect to the total mass of the photosensitive resin layer. % To 1% by mass is more preferable, and 0.01% to 0.8% by mass is even more preferable.

-solvent-
The photosensitive resin layer may contain a solvent.
In addition, the photosensitive resin composition for forming the photosensitive resin layer is a photosensitive resin composition containing a solvent by adjusting the viscosity of the photosensitive resin composition once by adding a solvent in order to easily form the photosensitive resin layer. The photosensitive resin composition can be applied and dried to suitably form the photosensitive resin layer.
As the solvent used in the present disclosure, a known solvent can be used. Solvents include ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, propylene glycol monoalkyl ether acetates, diethylene glycol dialkyl ethers And diethylene glycol monoalkyl ether acetates, dipropylene glycol monoalkyl ethers, dipropylene glycol dialkyl ethers, dipropylene glycol monoalkyl ether acetates, esters, ketones, amides, and lactones. Specific examples of the solvent include the solvents described in paragraphs 0174 to 0178 of JP2011-212494A, the contents of which are incorporated herein.

In addition, benzyl ethyl ether, dihexyl ether, ethylene glycol monophenyl ether acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, isophorone, caproic acid, caprylic acid, 1-octanol, -Solvents such as nonal, benzyl alcohol, anisole, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, ethylene carbonate or propylene carbonate can also be added.
Only 1 type may be used for a solvent and 2 or more types may be used for it.
The solvent which can be used for this indication may be used individually by 1 type, and it is more preferable to use 2 types together. When two or more solvents are used, for example, combined use of propylene glycol monoalkyl ether acetates and dialkyl ethers, combined use of diacetates and diethylene glycol dialkyl ethers, or esters and butylene glycol alkyl ether acetates A combination with the above is preferred.

Further, the solvent is preferably a solvent having a boiling point of 130 ° C. or higher and lower than 160 ° C., a solvent having a boiling point of 160 ° C. or higher, or a mixture thereof.
Solvents having a boiling point of 130 ° C. or higher and lower than 160 ° C. include propylene glycol monomethyl ether acetate (boiling point 146 ° C.), propylene glycol monoethyl ether acetate (boiling point 158 ° C.), propylene glycol methyl-n-butyl ether (boiling point 155 ° C.), and An example is propylene glycol methyl-n-propyl ether (boiling point 131 ° C.).
Solvents having a boiling point of 160 ° C or higher include ethyl 3-ethoxypropionate (boiling point 170 ° C), diethylene glycol methyl ethyl ether (boiling point 176 ° C), propylene glycol monomethyl ether propionate (boiling point 160 ° C), dipropylene glycol methyl ether acetate. (Bp 213 ° C), 3-methoxybutyl ether acetate (bp 171 ° C), diethylene glycol diethyl ether (bp 189 ° C), diethylene glycol dimethyl ether (bp 162 ° C), propylene glycol diacetate (bp 190 ° C), diethylene glycol monoethyl ether acetate (Boiling point 220 ° C), dipropylene glycol dimethyl ether (boiling point 175 ° C), and 1,3-butylene glycol diacetate (boiling point 232 ° C) There can be exemplified.

The content of the solvent in applying the photosensitive resin composition is preferably 50 parts by weight to 1,900 parts by weight, preferably 100 parts by weight to 100 parts by weight of the total solid content in the photosensitive resin composition. More preferably, it is 900 parts by mass.
The content of the solvent in the photosensitive resin layer is preferably 2% by mass or less, more preferably 1% by mass or less, and more preferably 0.5% by mass with respect to the total mass of the photosensitive resin layer. % Or less is more preferable.

-Plasticizer-
The photosensitive resin layer may contain a plasticizer for the purpose of improving plasticity.
The plasticizer preferably has a weight average molecular weight smaller than that of the polymer represented by a1 or a2.
The weight average molecular weight of the plasticizer is preferably from 500 to less than 10,000, more preferably from 700 to less than 5,000, and still more preferably from 800 to less than 4,000, from the viewpoint of imparting plasticity.
The plasticizer is not particularly limited as long as it is a compound that is compatible with the polymer and exhibits plasticity, but from the viewpoint of imparting plasticity, the plasticizer preferably has an alkyleneoxy group in the molecule. The alkyleneoxy group contained in the plasticizer preferably has the following structure.

In the above formula, R represents an alkyl group having 2 to 8 carbon atoms, n represents an integer of 1 to 50, and * represents a bonding site with another atom.

For example, even a compound having an alkyleneoxy group having the above structure (referred to as “compound X”) is obtained by mixing compound X, the above polymer and a photoacid generator, and a chemically amplified positive photosensitive property. When plasticity does not improve compared with the chemically amplified positive photosensitive resin composition formed without containing compound X, the resin composition does not fall under the plasticizer in the present disclosure. For example, the optionally added surfactant is generally not used in an amount that brings plasticity to the photosensitive resin composition, and thus does not correspond to the plasticizer in the present specification.

Examples of the plasticizer include, but are not limited to, compounds having the following structure.

The content of the plasticizer is preferably 1% by mass to 50% by mass and more preferably 2% by mass to 20% by mass with respect to the total mass of the photosensitive resin layer from the viewpoint of adhesion. preferable.
The said photosensitive resin layer may contain only 1 type of plasticizers, and may contain 2 or more types.

-Sensitizer-
The photosensitive resin layer can further contain a sensitizer.
The sensitizer absorbs actinic rays and enters an electronically excited state. The sensitizer in an electronically excited state comes into contact with the photoacid generator, and effects such as electron transfer, energy transfer, and heat generation occur. Thereby, a photo-acid generator raise | generates a chemical change and decomposes | disassembles and produces | generates an acid.
Exposure sensitivity can be improved by containing a sensitizer.

As the sensitizer, a compound selected from the group consisting of an anthracene derivative, an acridone derivative, a thioxanthone derivative, a coumarin derivative, a base styryl derivative, and a distyrylbenzene derivative is preferable, and an anthracene derivative is more preferable.
Anthracene derivatives include anthracene, 9,10-dibutoxyanthracene, 9,10-dichloroanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9-hydroxymethylanthracene, 9-bromoanthracene, 9-chloroanthracene, 9 1,10-dibromoanthracene, 2-ethylanthracene, or 9,10-dimethoxyanthracene is preferred.

Examples of the sensitizer include compounds described in paragraphs 0139 to 0141 of International Publication No. 2015/092731.

The content of the sensitizer is preferably 0% by mass to 10% by mass and more preferably 0.1% by mass to 10% by mass with respect to the total mass of the photosensitive resin layer.

-Heterocyclic compounds-
The photosensitive resin layer in the present disclosure can include a heterocyclic compound.
There is no restriction | limiting in particular in the heterocyclic compound in this indication. For example, the following compounds having an epoxy group or oxetanyl group in the molecule, alkoxymethyl group-containing heterocyclic compounds, other cyclic ethers, oxygen-containing monomers such as cyclic esters (lactones), silicon, sulfur, phosphorus, etc. Heterocyclic monomers having the following d electrons can be added.

The addition amount of the heterocyclic compound in the photosensitive resin layer is preferably 0.01% by mass to 50% by mass with respect to the total mass of the photosensitive resin layer when the heterocyclic compound is added. The content is more preferably 0.1% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass. It is preferable in the said range from a viewpoint of adhesiveness and etching tolerance. Only 1 type may be used for a heterocyclic compound and it can also use 2 or more types together.

Specific examples of the compound having an epoxy group in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, aliphatic epoxy resin and the like.

A compound having an epoxy group in the molecule can be obtained as a commercial product. For example, JER828, JER1007, JER157S70 (manufactured by Mitsubishi Chemical Co., Ltd.), JER157S65 (manufactured by Mitsubishi Chemical Holdings Co., Ltd.), and the like, commercially available products described in paragraph 0189 of JP2011-221494A, and the like can be mentioned.
Other commercially available products include ADEKA RESIN EP-4000S, EP-4003S, EP-4010S, EP-4011S (manufactured by ADEKA Corporation), NC-2000, NC-3000, NC-7300, XD- 1000, EPPN-501, EPPN-502 (above, manufactured by ADEKA Corporation), Denacol EX-611, EX-612, EX-614, EX-614B, EX-622, EX-512, EX-521, EX- 411, EX-421, EX-313, EX-314, EX-321, EX-211, EX-212, EX-810, EX-811, EX-850, EX-851, EX-821, EX-830, EX-832, EX-841, EX-911, EX-941, EX-920, EX-931, EX-212 , EX-214L, EX-216L, EX-321L, EX-850L, DLC-201, DLC-203, DLC-204, DLC-205, DLC-206, DLC-301, DLC-402, EX-111, EX -121, EX-141, EX-145, EX-146, EX-147, EX-171, EX-192 (manufactured by Nagase Chemtech), YH-300, YH-301, YH-302, YH-315, YH-324, YH-325 (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.) Celoxide 2021P, 2081, 2000, 3000, EHPE3150, Epolide GT400, Cellbiners B0134, B0177 (manufactured by Daicel Corporation), and the like.
The compound which has an epoxy group in a molecule | numerator may be used individually by 1 type, and may use 2 or more types together.

Among the compounds having an epoxy group in the molecule, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin and aliphatic epoxy resin are more preferable, and aliphatic epoxy resin is particularly preferable.

Specific examples of compounds having an oxetanyl group in the molecule include Aron Oxetane OXT-201, OXT-211, OXT-212, OXT-213, OXT-121, OXT-221, OX-SQ, PNOX (above, Toagosei Co., Ltd.) Can be used.

In addition, the compound containing an oxetanyl group is preferably used alone or mixed with a compound containing an epoxy group.

In the photosensitive resin layer according to the present disclosure, the heterocyclic compound is preferably a compound having an epoxy group from the viewpoint of etching resistance and line width stability.

-Alkoxysilane compounds-
The photosensitive resin layer may contain an alkoxysilane compound. Preferred examples of the alkoxysilane compound include trialkoxysilane compounds.
Examples of the alkoxysilane compound include γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-glycidoxypropyltriacoxysilane, γ-glycidoxypropylalkyldialkoxysilane, and γ-methacryloxy. Propyltrialkoxysilane, γ-methacryloxypropylalkyldialkoxysilane, γ-chloropropyltrialkoxysilane, γ-mercaptopropyltrialkoxysilane, β- (3,4-epoxycyclohexyl) ethyltrialkoxysilane, vinyltrialkoxysilane Is mentioned. Of these, γ-glycidoxypropyltrialkoxysilane and γ-methacryloxypropyltrialkoxysilane are more preferable, γ-glycidoxypropyltrialkoxysilane is more preferable, and 3-glycidoxypropyltrimethoxysilane is particularly preferable. preferable. These can be used alone or in combination of two or more.

-Other ingredients-
The photosensitive resin layer in the present disclosure includes metal oxide particles, antioxidants, dispersants, acid multipliers, development accelerators, conductive fibers, colorants, thermal radical polymerization initiators, thermal acid generators, and ultraviolet absorption. Known additives such as an agent, a thickener, a crosslinking agent, and an organic or inorganic suspending agent can be further added.
Preferred embodiments of the other components are described in JP-A-2014-85643, paragraphs 0165 to 0184, respectively, and the contents of this publication are incorporated herein.

<< Average film thickness of photosensitive resin layer >>
The average film thickness of the photosensitive resin layer is preferably 1.0 μm or more, and more preferably 2.0 μm or more, from the viewpoint of transferability (laminate). The average film thickness of the photosensitive resin layer is preferably 20 μm or less, more preferably 15 μm or less, from the viewpoint of production suitability.

<< Method for Forming Photosensitive Resin Layer >>
A photosensitive resin composition for forming a photosensitive resin layer can be prepared by mixing each component and a solvent in an arbitrary ratio and by an arbitrary method, and dissolving by stirring. For example, it is possible to prepare a composition by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent. The composition prepared as described above can be used after being filtered using a filter having a pore size of 0.2 μm or the like.

The photosensitive transfer material according to the present disclosure having the photosensitive resin layer on the temporary support can be obtained by applying the photosensitive resin composition on the temporary support or an intermediate layer described later and drying the photosensitive resin composition.
The coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
In addition, the photosensitive resin layer can also be applied after forming other layers described later on the intermediate layer.

<Intermediate layer>
The photosensitive transfer material according to the present disclosure includes the temporary support and the photosensitive resin layer from the viewpoints of resolution, retention time dependency suppression, adhesion between the intermediate layer and the photosensitive resin layer, and pattern formation. It is preferable to have an intermediate layer between them. Moreover, it is preferable that the said intermediate | middle layer contains a binder.

<< Binder >>
The binder is preferably a water-soluble or alkali-soluble binder, and more preferably a water-soluble or alkali-soluble polymer.
In the present disclosure, “water-soluble” means that the solubility in water at pH 7.0 is 0.1% by mass or more at 25 ° C., and “alkali-soluble” means pH 8. It means that the solubility in an alkaline aqueous solution of 5 or more is 0.1% by mass or more.
Further, the above “water-soluble or alkali-soluble” may be either water-soluble or alkali-soluble, or water-soluble and alkali-soluble.

Examples of the binder include phenol formaldehyde resin, m-cresol formaldehyde resin, p-cresol formaldehyde resin, m- / p-mixed cresol formaldehyde resin, phenol / cresol (m-, p-, or m- / p-mixed). Any may be used) novolak resin such as mixed formaldehyde resin, pyrogallol acetone resin, polyhydroxystyrene resin, modified cellulose resin, acrylic resin having a hydroxy group (for example, hydroxyalkyl (meth) acrylate homopolymer or copolymer), Starches, glycogens, chitins, agaroses, carrageenans, pullulans, gum arabic, soya gum, polyamide resin, epoxy resin, polyacetal resin, acrylic resin, polystyrene resin, polyester Urethane resins, polyvinyl alcohol, polyvinyl formal, polyamide resin, polyester resin, polyethyleneimine, polyallylamine, polyalkylene glycol, and the like.

Among these, the binder is at least one selected from the group consisting of a novolak resin, a modified cellulose resin, and an acrylic resin having a hydroxy group from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation. It is preferably a resin, more preferably at least one resin selected from the group consisting of a modified cellulose resin and an acrylic resin having a hydroxy group, and more preferably a modified cellulose resin.
The modified cellulose resin is preferably hydroxyalkylated cellulose from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formation.
Preferred examples of the hydroxyalkylated cellulose include hydroxymethylcellulose, hydroxyethylcellulose, polyhydroxyethylated cellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, glyoxalized hydroxypropylmethylcellulose, hydroxypropylmethylcellulose phthalate and the like.
Among these, from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer and pattern formability, it is preferably at least one resin selected from the group consisting of hydroxypropylcellulose and hydroxypropylmethylcellulose, and is hydroxypropylmethylcellulose. It is more preferable.
In addition, the binder is preferably at least one resin selected from the group consisting of polyvinyl alcohol and polyvinyl formal from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, and is polyvinyl alcohol. Is more preferable.

The weight average molecular weight of the binder is preferably 1,000 or more from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer, pattern formation, solubility in the developer after exposure, and transferability. , Preferably from 100,000 to 100,000, more preferably from 10,000 to 50,000.

The said intermediate | middle layer may contain the binder individually by 1 type, or may contain 2 or more types.
The content of the binder in the intermediate layer is based on the adhesiveness between the intermediate layer and the photosensitive resin layer, pattern formation, solubility in the developer after exposure, and transferability, with respect to the total mass of the intermediate layer, It is preferably 10% by mass or more and 100% by mass or less, more preferably 20% by mass or more and 100% by mass or less, still more preferably 40% by mass or more and 100% by mass or less, and 65% by mass or more and 85% by mass. % Or less is particularly preferable.

<< Other additives >>
The intermediate layer in the present disclosure may contain a known additive as required in addition to the binder.
As other additives, other additives used for the photosensitive resin layer are preferably exemplified.

<< Particles >>
The intermediate layer preferably contains particles from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer.
The above particles are preferably metal oxide particles or organic particles from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer, and oxidation of an element selected from the group consisting of Si, Ti and Zr. More preferably, it is a physical particle or an organic particle.
Note that the metal of the metal oxide particles in the present disclosure includes semimetals such as B, Si, Ge, As, Sb, and Te.
The metal oxide particles include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, Nb, Mo, W, Zn, B , Oxide particles containing atoms such as Al, Si, Ge, Sn, Pb, Sb, Bi, Te, etc. are preferred, silica, titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / tin oxide, or Antimony / tin oxide is more preferable, silica, titanium oxide, titanium composite oxide, or zirconium oxide is more preferable, and silica, titanium oxide, or zirconium oxide is particularly preferable.
As the organic particles, organic resin particles are preferably exemplified.
Examples of the organic resin particles include homopolymers and copolymers of acrylic acid monomers such as acrylic acid, methacrylic acid, acrylic acid esters, and methacrylic acid esters, and cellulose polymers such as nitrocellulose, methylcellulose, ethylcellulose, and cellulose acetate. , Polyethylene, polypropylene, polystyrene, vinyl chloride copolymers, vinyl chloride-vinyl acetate copolymers, polyvinyl pyrrolidone, polyvinyl butyral, vinyl polymers such as polyvinyl alcohol, and copolymers of vinyl compounds, polyesters, polyurethanes, polyamides A condensation polymer such as butadiene-styrene copolymer, a rubber-based thermoplastic polymer such as a butadiene-styrene copolymer, a polymer obtained by polymerizing and crosslinking a photopolymerizable or thermopolymerizable compound such as an epoxy compound, Min compounds and the like.
Among these, acrylic resin particles are preferable as the organic particles, and polymethyl methacrylate particles are more preferable.
Moreover, the surface of these particles can be treated with an organic material or an inorganic material in order to impart dispersion stability. The particles are preferably particles having a hydrophilic surface. For example, the surface of particles having a hydrophobic surface may be subjected to a hydrophilic treatment.

The arithmetic average particle diameter of the particles is preferably 400 nm or less, more preferably 250 nm or less, and further preferably 150 nm or less, from the viewpoint of adhesion between the intermediate layer and the photosensitive resin layer. A thickness of 10 nm to 200 nm is particularly preferable.
The method for measuring the arithmetic average particle diameter of the particles in the present disclosure refers to an arithmetic average obtained by measuring the particle diameter of 200 arbitrary particles with an electron microscope. When the particle shape is not spherical, the maximum diameter is the diameter.

The volume fraction of the particles in the intermediate layer (volume ratio of particles in the intermediate layer) is 5% to 90% with respect to the total volume of the intermediate layer from the viewpoint of adhesion between the intermediate layer and the photosensitive layer. It is preferably 10% to 80%, more preferably 15% to 70%, and particularly preferably 20% to 60%.

<< Average thickness of intermediate layer >>
The average film thickness of the intermediate layer is preferably 0.3 μm to 10 μm, more preferably 0.3 μm to 5 μm, and more preferably 0.3 μm from the viewpoints of adhesion between the intermediate layer and the photosensitive resin layer and pattern formability. ˜2 μm is particularly preferred.
There is no restriction | limiting in particular in the measuring method of the average film thickness of each layer in this indication, A well-known method can be used. The average value is preferably measured and calculated at 10 points or more.
Specific examples include surface shape measurement and cross-sectional optical microscope or electron microscope observation. In addition, Bruker's Dektak series can be suitably used for surface shape measurement. Moreover, a scanning electron microscope (SEM) can be used suitably for cross-sectional observation.
Moreover, it is preferable that the thickness of the said intermediate | middle layer is thinner than the thickness of the said photosensitive resin layer.

<< Method for Forming Intermediate Layer >>
The method for forming the intermediate layer is not particularly limited, but each component and a solvent (preferably an aqueous solvent) are mixed at a predetermined ratio and in an arbitrary method, and stirred to dissolve to form the intermediate layer. An intermediate layer forming composition can be prepared. For example, it is possible to prepare a composition by mixing each component with a predetermined ratio after preparing each solution in advance in a solvent. The composition prepared as described above can be used after being filtered using a filter having a pore diameter of 5 μm.
Examples of the aqueous solvent include water and water-soluble solvents such as alcohols.

The intermediate layer can be easily formed on the temporary support by applying the intermediate layer-forming composition to the temporary support and drying it.
The coating method is not particularly limited, and the coating can be performed by a known method such as slit coating, spin coating, curtain coating, and inkjet coating.
In addition, after forming other layers (for example, a thermoplastic resin layer or the like) described later on the temporary support, an intermediate layer can be applied.

<Other layers>
The photosensitive transfer material according to the present disclosure may have a layer other than the temporary support, the intermediate layer, and the photosensitive resin layer (hereinafter sometimes referred to as “other layers”). Examples of other layers include a contrast enhancement layer, a cover film, and a thermoplastic resin layer.

-Thermoplastic resin layer, cover film, etc.-
The photosensitive transfer material according to the present disclosure preferably further includes a thermoplastic resin layer between the temporary support and the photosensitive resin layer or the intermediate layer from the viewpoint of transferability.
The photosensitive transfer material according to the present disclosure may have a cover film for the purpose of protecting the photosensitive resin layer.
Preferred embodiments of the thermoplastic resin layer are described in paragraphs 0189 to 0193 of JP 2014-85643 A, and preferred embodiments of the other layers are described in paragraphs 0194 to 0196 of JP 2014-85643 A, respectively. The contents of this publication are incorporated herein.
Especially, it is preferable that a thermoplastic resin layer contains the at least 1 sort (s) of thermoplastic resin chosen from the group which consists of an acrylic resin and a styrene / acryl copolymer from a transferable viewpoint.

When the photosensitive transfer material according to the present disclosure has other layers such as a thermoplastic resin layer, the photosensitive transfer material is manufactured according to the method for manufacturing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138. can do.
For example, when preparing a photosensitive transfer material according to the present disclosure having a thermoplastic resin layer, a solution (for thermoplastic resin layer) in which a thermoplastic organic polymer and an additive are dissolved on a temporary support. A coating solution prepared by adding a resin and an additive to a solvent that does not dissolve the thermoplastic resin layer on the obtained thermoplastic resin layer after applying a coating liquid) and drying to provide a thermoplastic resin layer (intermediate) The layer composition) is applied and dried to laminate the intermediate layer. A photosensitive transfer material according to the present disclosure is obtained by further applying a photosensitive resin composition prepared using a solvent that does not dissolve the intermediate layer on the formed intermediate layer, and drying and laminating the photosensitive resin layer. Can be suitably produced.

-Contrast enhancement layer-
The photosensitive transfer material according to the present disclosure can have a contrast enhancement layer in addition to the photosensitive resin layer.
A contrast enhancement layer (CEL) is a material that absorbs light with respect to an exposure wavelength before exposure, but gradually decreases with exposure, that is, a material that increases light transmittance (photodecoloration). It is a layer containing a coloring pigment component). Known photodecolorable dye components include diazonium salts, stilbazolium salts, arylnitroso salts, and the like. A phenolic resin or the like is used as the film forming component.
In addition, as contrast enhancement layers, paragraphs 0004 to 0051 of JP-A-6-97065, paragraphs 0012 to 0055 of JP-A-6-332167, photopolymer handbook, photopolymer social gathering, industrial research group ( 1989), photopolymer technology, Yamaoka, Nagamatsu edition, Nikkan Kogyo Shimbun Co., Ltd. (1988) can be used.

(Resin pattern manufacturing method and circuit wiring manufacturing method)
The method for producing a resin pattern according to the present disclosure is not particularly limited as long as it is a method for producing a resin pattern using the photosensitive transfer material according to the present disclosure, but the photosensitive resin in the photosensitive transfer material according to the present disclosure. A step of bringing the layer into contact with the substrate and bonding, a step of pattern exposing the photosensitive resin layer, and a step of developing the exposed photosensitive resin layer to form a pattern, in this order, It is preferable to include the process of peeling the said temporary support body after the process of bonding together and before the process of forming the said pattern.
The circuit wiring manufacturing method according to the present disclosure is not particularly limited as long as it is a circuit wiring manufacturing method using the photosensitive transfer material according to the present disclosure. A step of bringing the photosensitive resin layer into contact with a substrate having a conductive layer, a step of pattern-exposing the photosensitive resin layer, a step of developing the exposed photosensitive resin layer to form a pattern, Etching the conductive layer in the region where the pattern is not disposed in this order, and after the step of bonding to the substrate and before the step of forming the pattern, the temporary support is peeled off It is preferable to include a process.
The substrate is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface.

Conventionally, photosensitive resin compositions are classified into a negative type in which a portion irradiated with actinic rays is left as an image and a positive type in which a portion not irradiated with actinic rays is left as an image due to differences in photosensitive systems. In the positive type, by irradiating actinic rays, for example, to improve the solubility of the exposed portion using a photosensitive agent that generates acid upon irradiation with actinic rays, both the exposed and unexposed portions are exposed at the time of pattern exposure. If the pattern shape obtained is not cured and the substrate is defective, the substrate can be reused (reworked) by full exposure or the like. Therefore, the positive type is preferable from the viewpoint of excellent so-called reworkability. Further, since the technique of reexposing the remaining photosensitive resin layer to produce a different pattern can be realized only by the photosensitive resin layer, the resin pattern manufacturing method according to the present disclosure or the circuit according to the present disclosure In the method for producing a wiring, an embodiment in which exposure is performed twice or more is preferable.

<Lamination process>
A method for manufacturing a resin pattern according to the present disclosure or a method for manufacturing a circuit wiring according to the present disclosure is provided by contacting the photosensitive resin layer in the photosensitive transfer material according to the present disclosure with a substrate, preferably a substrate having a conductive layer. It is preferable to include the process of bonding together (bonding process).
Moreover, in the said bonding process, it is preferable to make it pressure-bond so that the said conductive layer and the said photosensitive resin layer may contact. In the above embodiment, the patterned photosensitive resin layer after exposure and development can be suitably used as an etching resist when the conductive layer is etched.
There is no restriction | limiting in particular as a method of crimping | bonding the said board | substrate and the said photosensitive transfer material, A well-known transfer method and a lamination method can be used.
Specifically, for example, the photosensitive resin layer side of the photosensitive transfer material is preferably overlapped on a substrate and pressed by a roll or the like, or pressed and heated. For laminating, known laminators such as a laminator, a vacuum laminator, and an auto-cut laminator that can further increase productivity can be used.
There are no particular limitations on the pressure and temperature of the bonding in the bonding step, and it depends on the surface material of the substrates to be bonded, for example, the material of the conductive layer, the material of the photosensitive resin layer, the conveyance speed, and the pressure bonding machine used. Can be set as appropriate. Moreover, what is necessary is just to crimp | bond, after removing a cover film from the photosensitive resin layer, when having a cover film on the photosensitive resin layer of a photosensitive transfer material.
When the base material is a resin film, a roll-to-roll pressure bonding may be performed.

The substrate used in the present disclosure is preferably a substrate having a conductive layer, and more preferably a substrate having a conductive layer on the surface of a base material. A wiring is formed by patterning the conductive layer. Moreover, in this indication, it is preferable that several electroconductive layers, such as a metal oxide and a metal, were provided in film base materials, such as a polyethylene terephthalate.
Moreover, it is preferable that the board | substrate used for this indication is a board | substrate containing copper from a viewpoint which exhibits the effect in this indication more. Moreover, it is preferable that the said conductive layer is a layer containing copper from a viewpoint which exhibits the effect in this indication more.

The substrate is preferably a substrate in which a plurality of conductive layers are stacked on a support.
As for the board | substrate with which the some electroconductive layer was laminated | stacked on the support body, it is preferable that a support body is a glass base material or a film base material, and it is more preferable that it is a film base material. When the circuit wiring manufacturing method according to the present disclosure is a touch panel circuit wiring, the support is particularly preferably a sheet-shaped resin composition.
The support is preferably transparent.
The refractive index of the support is preferably 1.50 to 1.52.
The support may be composed of a translucent substrate such as a glass substrate, and tempered glass represented by Corning's gorilla glass can be used. In addition, as the above-described transparent substrate, materials used in JP 2010-86684 A, JP 2010-152809 A, and JP 2010-257492 A can be preferably used.
When a film substrate is used as the substrate, it is more preferable to use a substrate that is not optically distorted and a substrate having high transparency. Specific examples of the material include polyethylene terephthalate (PET), Examples thereof include polyethylene naphthalate, polycarbonate, triacetyl cellulose, and cycloolefin polymer.

Examples of the conductive layer include any conductive layer used for general wiring or touch panel wiring.
Examples of the material for the conductive layer include metals and metal oxides.
Examples of the metal oxide include ITO (Indium Tin Oxide), IZO (Indium Zinc Oxide), and SiO ₂ . Examples of the metal include Al, Zn, Cu, Fe, Ni, Cr, and Mo.

In the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure, it is preferable that at least one of the plurality of conductive layers includes a metal oxide.
The conductive layer is preferably an electrode pattern corresponding to a sensor for a visual recognition part used in a capacitive touch panel or a wiring for a peripheral extraction part.

<Exposure process>
It is preferable that the manufacturing method of the resin pattern which concerns on this indication, or the manufacturing method of the circuit wiring which concerns on this indication includes the process (exposure process) of carrying out pattern exposure of the said photosensitive resin layer after the said bonding process.
In the exposure step, the photosensitive resin layer is preferably irradiated with actinic rays through a mask having a predetermined pattern. In this step, the photoacid generator is decomposed to generate an acid. By the catalytic action of the generated acid, the acid-decomposable group contained in the coating film component is hydrolyzed to produce an acid group, for example, a carboxy group or a phenolic hydroxyl group.
In the present disclosure, the detailed arrangement and specific size of the pattern are not particularly limited. Since it is desired to improve the display quality of a display device (for example, a touch panel) including an input device having a circuit board manufactured in the present disclosure and to minimize the area occupied by the extraction wiring, at least a part of the pattern (particularly the touch panel) The electrode pattern and the part of the lead-out wiring) are preferably fine wires of 100 μm or less, and more preferably 70 μm or less.
The exposure in the exposure step may be exposure through a mask or digital exposure using a laser or the like, but is preferably exposure through an exposure mask.
The method for producing a resin pattern according to the present disclosure or the method for producing a circuit wiring according to the present disclosure includes a step of bringing the photosensitive transfer material and an exposure mask into contact between the bonding step and the exposure step. It is preferable to contain. It is excellent in the resolution of the pattern obtained as it is the said aspect.

Visible light, ultraviolet light, and an electron beam are mentioned as actinic light, However, Visible light or ultraviolet light is preferable and an ultraviolet-ray is especially preferable.
As an exposure light source using actinic light, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a chemical lamp, a light emitting diode (LED) light source, an excimer laser generator, etc. can be used. Actinic rays having a wavelength of 300 nm to 450 nm, such as h-line (405 nm), can be preferably used. Moreover, irradiation light can also be adjusted through spectral filters, such as a long wavelength cut filter, a short wavelength cut filter, and a band pass filter, as needed.
As the exposure apparatus, various types of exposure machines such as a mirror projection aligner, a stepper, a scanner, a proximity, a contact, a microlens array, and a laser exposure can be used.
Exposure dose, depending on the photosensitive resin layer to be used may be appropriately ^selected, but is preferably from 5mJ / cm 2 ~ 200mJ / cm 2, more preferably 10mJ / cm 2 ~ 100mJ / cm 2 .
It is also preferable to perform heat treatment before development for the purpose of improving the rectangularity and linearity of the pattern after exposure. By a process called PEB (Post Exposure Bake), pattern edge roughness due to standing waves generated in the photosensitive resin layer during exposure can be reduced.

In addition, even if pattern exposure performs after peeling a temporary support body from the photosensitive resin layer, before peeling a temporary support body, it exposes through a temporary support body, and peels a temporary support body after that. Also good. The pattern exposure may be exposure through a mask or digital exposure using a laser or the like.

<Development process>
The resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure includes a step of developing the exposed photosensitive resin layer to form a pattern after the exposing step (developing step). It is preferable to contain.
When the photosensitive transfer material has an intermediate layer, the exposed intermediate layer is also removed together with the exposed photosensitive resin layer in the development step.
Furthermore, in the development step, the intermediate layer in the unexposed area may also be removed in a form of being dissolved or dispersed in the developer.
Development of the exposed photosensitive resin layer in the development step can be performed using a developer.
The developer is not particularly limited as long as the exposed portion of the photosensitive resin layer can be removed. For example, a known developer such as the developer described in JP-A No. 5-72724 can be used. . The developer is preferably a developer in which the exposed portion of the photosensitive resin layer exhibits a dissolution type development behavior. The developer is preferably an alkaline aqueous solution, and more preferably, for example, an alkaline aqueous solution containing a compound having a pKa of 7 to 13 at a concentration of 0.05 mol / L (liter) to 5 mol / L. The developer may further contain an organic solvent miscible with water, a surfactant, and the like. Examples of the developer suitably used in the present disclosure include the developer described in Paragraph 0194 of International Publication No. 2015/092731.

The development method is not particularly limited, and any of paddle development, shower development, shower and spin development, dip development, and the like may be used. Here, the shower development will be described. The exposed portion can be removed by spraying the developer onto the exposed photosensitive resin layer by shower. Further, after the development, it is preferable to remove the development residue while spraying a cleaning agent or the like with a shower and rubbing with a brush or the like. The liquid temperature of the developer is preferably 20 ° C. to 40 ° C.
Moreover, the effect which suppresses the deformation | transformation of the pattern shape in this indication is more exhibited in the aspect with long time from exposure to image development. Although development may be performed immediately after exposure, in a mode in which development is performed after the time from exposure to development is preferably 0.5 hours or more, more preferably 1 hour or more, and further preferably 6 hours or more after exposure. The effect of suppressing the deformation of the pattern shape in the present disclosure is further exhibited.
In addition, a method for manufacturing a resin pattern according to the present disclosure or a method for manufacturing a circuit wiring according to the present disclosure includes a step of washing with water after development, a step of drying a substrate having the obtained pattern, and the like. These steps may be included.

Furthermore, you may have the post-baking process which heat-processes the pattern obtained by image development.
The post-baking is preferably performed in an environment of 8.1 kPa to 121.6 kPa, and more preferably in an environment of 50.66 kPa or more. On the other hand, it is more preferable to carry out in an environment of 111.46 kPa or less, and it is particularly preferable to carry out in an environment of 101.3 kPa or less.
The post-baking temperature is preferably 80 ° C. to 250 ° C., more preferably 110 ° C. to 170 ° C., and particularly preferably 130 ° C. to 150 ° C.
The post-baking time is preferably 1 minute to 30 minutes, more preferably 2 minutes to 10 minutes, and particularly preferably 2 minutes to 4 minutes.
The post-bake may be performed in an air environment or a nitrogen substitution environment.

The transport speed of the support in each step of the resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure is not particularly limited. It is preferably from min to 10 m / min, and more preferably from 2.0 m / min to 8.0 m / min except during exposure.

<Peeling process>
The method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure peels off the temporary support after the step of bonding to the substrate and before the step of forming the pattern. It is preferable to include a process (peeling process).
The resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure uses the photosensitive transfer material. Therefore, after the photosensitive transfer material is bonded to each other and at any timing before development, Even if the support is peeled off, the adhesiveness with the photosensitive resin layer is excellent, so that the cause of defects such as partial peeling is suppressed, and the pattern can be formed satisfactorily.
In addition, the method for manufacturing a resin pattern according to the present disclosure or the method for manufacturing a circuit wiring according to the present disclosure includes a step of bonding the substrate to the substrate and the photosensitive resin layer from the viewpoint of pattern formability and resolution. It is more preferable that a step of peeling the temporary support is included before the pattern exposure step. Further, in the case of the above-described aspect, when pattern exposure is performed with a mask in contact, the photosensitive resin layer and the mask are not in direct contact with each other, so that the pattern formability and resolution are excellent.
There is no restriction | limiting in particular in the method of peeling the temporary support body in the said peeling process, What is necessary is just to peel by a well-known method.

<Etching process>
The circuit wiring manufacturing method according to the present disclosure preferably includes a step (etching step) of etching the conductive layer in a region where the pattern is not disposed.
In the etching step, the conductive layer is etched using the pattern formed from the photosensitive resin layer in the developing step as an etching resist.
Etching of the conductive layer can be performed by a known method such as a method described in paragraphs 0048 to 0054 of JP 2010-152155 A or a dry etching method such as a known plasma etching.
For example, as an etching method, a commonly performed wet etching method in which the substrate is immersed in an etching solution can be used. As an etchant used for wet etching, an acid type or alkaline type etchant may be appropriately selected in accordance with an object to be etched.
Acidic etchants include hydrochloric acid, sulfuric acid, nitric acid, acetic acid, hydrofluoric acid, oxalic acid, aqueous solutions of acidic components such as phosphoric acid, acidic components and ferric chloride, ammonium fluoride, or permanganese Examples thereof include a mixed aqueous solution of a salt such as potassium acid. As the acidic component, a component obtained by combining a plurality of acidic components may be used.
Alkali type etching solutions include sodium hydroxide, potassium hydroxide, ammonia, organic amines, or aqueous solutions of alkali components such as organic amine salts such as tetramethylammonium hydroxide, alkaline components and potassium permanganate. A mixed aqueous solution of a salt such as As the alkali component, a component obtained by combining a plurality of alkali components may be used.

The temperature of the etching solution is not particularly limited, but is preferably 45 ° C. or lower. In the present disclosure, the pattern used as an etching mask (etching pattern) preferably exhibits particularly excellent resistance to acidic and alkaline etching solutions in a temperature range of 45 ° C. or lower. Therefore, the pattern is prevented from peeling off during the etching process, and a portion where the pattern does not exist is selectively etched.

After the etching process, in order to prevent contamination of the process line, a process of cleaning the etched substrate (cleaning process) and a process of drying the etched substrate (drying process) are performed as necessary. Also good. As for the cleaning step, for example, the substrate may be cleaned with pure water for 10 seconds to 300 seconds at room temperature (10 ° C. to 35 ° C.). Regarding the drying step, for example, air blow may be used, and the air blow pressure (about 0.1 kg / cm ² to about 5 kg / cm ² ) may be appropriately adjusted for drying.

<Etching resist stripping process>
It is preferable that the manufacturing method of the circuit wiring which concerns on this indication includes the process (etching resist peeling process) which peels the said photosensitive resin layer using peeling liquid after the said etching process.
After the etching process is finished, the patterned photosensitive resin layer remains. If the photosensitive resin layer is unnecessary, all the remaining photosensitive resin layers may be removed.
As a method of peeling using a peeling solution, for example, a substrate having the above-mentioned photosensitive resin layer or the like in the peeling solution preferably stirred at 30 ° C. to 80 ° C., more preferably 50 ° C. to 80 ° C. for 5 minutes. Examples include a method of immersing for ˜30 minutes.
As the stripping solution, for example, an inorganic alkali component such as sodium hydroxide or potassium hydroxide, or an organic alkali component such as a tertiary amine or quaternary ammonium salt, water, dimethyl sulfoxide, N-methylpyrrolidone, or And a stripping solution dissolved in a mixed solution thereof. A stripping solution may be used and stripped by a spray method, a shower method, a paddle method, or the like.

Moreover, the manufacturing method of the circuit wiring which concerns on this indication may repeat an exposure process, a image development process, and an etching process twice or more as needed.
As examples of the exposure step, the development step, and other steps in the present disclosure, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present disclosure.

The resin pattern manufacturing method according to the present disclosure or the circuit wiring manufacturing method according to the present disclosure may include other optional steps. For example, although the following processes are mentioned, it is not limited to these processes.

<Step of reducing visible light reflectance>
The manufacturing method of the circuit wiring according to the present disclosure may include a process of reducing the visible light reflectivity of the surface of the conductive layer, for example, a part or all of the surface of the conductive layer on the substrate. .
Examples of the treatment for reducing the visible light reflectance include an oxidation treatment. For example, the visible light reflectance can be reduced by blackening the copper by oxidizing copper.
Regarding preferred embodiments of the treatment for reducing the visible light reflectance, paragraphs 0017 to 0025 of JP2014-150118A, and paragraphs 0041, 0042, 0048 and 0058 of JP2013-206315A are described. The contents of this publication are incorporated herein.

<Process for forming an insulating film on the etched substrate and process for forming a new conductive layer on the insulating film>
A method of manufacturing a circuit wiring according to the present disclosure includes a step of forming an insulating film on the substrate, for example, a formed wiring (etched conductive layer), and a step of forming a new conductive layer on the insulating film. It is also preferable to contain.
There is no restriction | limiting in particular about the process of forming an insulating film, The method of forming a well-known permanent film can be mentioned. Alternatively, an insulating film having a desired pattern may be formed by photolithography using a photosensitive material having insulating properties.
There is no particular limitation on the process of forming a new conductive layer on the insulating film. A new conductive layer having a desired pattern may be formed by photolithography using a photosensitive material having conductivity.

Further, in the method for manufacturing a circuit wiring according to the present disclosure, the new conductive layer may be etched by forming an etching resist by a method similar to the above, or may be separately etched by a known method. .
The substrate having the circuit wiring obtained by the circuit wiring manufacturing method according to the present disclosure may have only one layer of wiring on the substrate, or may have two or more layers of wiring.

Further, in the method for manufacturing circuit wiring according to the present disclosure, the substrate may have a plurality of conductive layers on both surfaces, and the circuit may be sequentially or simultaneously formed on the conductive layers formed on both surfaces of the substrate. preferable. With such a configuration, a wiring in which a first conductive pattern (first wiring) is formed on one surface of the substrate and a second conductive pattern (second wiring) is formed on the other surface, preferably a touch panel wiring. Can be formed.

(Circuit wiring and substrate having circuit wiring)
The circuit wiring according to the present disclosure is a circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure.
The board | substrate which has the circuit wiring which concerns on this indication is a board | substrate which has the circuit wiring manufactured by the manufacturing method of the circuit wiring which concerns on this indication.
Although the use of the board | substrate which has the circuit wiring which concerns on this indication is not limited, For example, it is preferable that it is a circuit wiring board for touchscreens.

(Input device and display device)
An input device is mentioned as an apparatus provided with the circuit wiring manufactured by the manufacturing method of the circuit wiring concerning this indication.
The input device according to the present disclosure may be an input device having at least a circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure, and is preferably a capacitive touch panel.
The display device according to the present disclosure preferably includes the input device according to the present disclosure. The display device according to the present disclosure is preferably an organic EL display device and an image display device such as a liquid crystal display device.

(Touch panel and touch panel display device)
The touch panel according to the present disclosure is a touch panel having at least circuit wiring manufactured by the method for manufacturing circuit wiring according to the present disclosure. In addition, the touch panel according to the present disclosure preferably includes at least a transparent substrate, an electrode, and an insulating layer or a protective layer.
The touch panel display device according to the present disclosure is a touch panel display device having at least circuit wiring manufactured by the circuit wiring manufacturing method according to the present disclosure, and is preferably a touch panel display device including the touch panel according to the present disclosure.
Further, the touch panel manufacturing method according to the present disclosure is not particularly limited as long as it is a touch panel manufacturing method using the photosensitive transfer material according to the present disclosure, but the photosensitive resin of the photosensitive transfer material according to the present disclosure. A step of bringing a layer into contact with a substrate having a conductive layer, a step of pattern-exposing the photosensitive resin layer, a step of developing the exposed photosensitive resin layer to form a pattern, and the pattern It is preferable to include a step of etching the conductive layer in a region where no is disposed.
As a detection method in the touch panel according to the present disclosure and the touch panel display device according to the present disclosure, any of known methods such as a resistive film method, a capacitance method, an ultrasonic method, an electromagnetic induction method, and an optical method may be used. Among these, the electrostatic capacity method is preferable.

As the touch panel type, a so-called in-cell type (for example, those described in FIGS. 5, 6, 7, and 8 of JP-T-2012-517051), a so-called on-cell type (for example, JP 2013-168125 A). 19 of the gazette, those described in FIGS. 1 and 5 of JP 2012-89102 A, OGS (One Glass Solution) type, TOL (Touch-on-Lens) type (for example, JP No. 2013-54727 shown in FIG. 2), other configurations (for example, those shown in FIG. 6 of JP2013-164671A), various out-cell types (so-called GG, G1, G2, GFF, GF2, GF1, G1F, etc.).

As the touch panel according to the present disclosure and the touch panel display device according to the present disclosure, “latest touch panel technology” (issued July 6, 2009, published by Techno Times Co., Ltd.), supervised by Yuji Mitani, “touch panel technology and development” ( The configurations disclosed in FPD International 2009 Forum T-11 lecture textbook, Cypress Semiconductor Corporation application note AN2292, etc. can be applied.

Hereinafter, embodiments of the present invention will be described more specifically with reference to examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the embodiment of the present invention. Therefore, the scope of the embodiment of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

<Polymer component>
In the following synthesis examples, the following abbreviations represent the following compounds, respectively.
ATHF: 2-tetrahydrofuranyl acrylate (synthetic product)
MATHF: 2-tetrahydrofuranyl methacrylate (synthetic product)
TBA: tert-butyl acrylate (Fuji Film Wako Pure Chemical Industries, Ltd.)
AA: Acrylic acid (Fuji Film Wako Pure Chemical Industries, Ltd.)
EA: ethyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
MMA: Methyl methacrylate (Fuji Film Wako Pure Chemical Industries, Ltd.)
CHA: cyclohexyl acrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
BMA: benzyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
PMPMA: 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
DMAPAA: N- [3- (dimethylamino) propyl] acrylamide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
DMAEMA: 2- (dimethylamino) ethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
DEAEMA: 2- (diethylamino) ethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
DPAEMA: 2- (diisopropylamino) ethyl methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
MEMA: 2-morpholinoethyl methacrylate (manufactured by Tokyo Chemical Industry Co., Ltd.)
VP: Vinylpyridine (Fuji Film Wako Pure Chemical Industries, Ltd.)
VI: 1-vinylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
VT: 1-vinyl-1,2,4-triazole (manufactured by Sigma-Aldrich)
NVP: N-vinylpyrrolidone (Fuji Film Wako Pure Chemical Industries, Ltd.)
DMAA: Dimethylacrylamide (Fujifilm Wako Pure Chemical Industries, Ltd.)
MANa: sodium methacrylate (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)
PGMEA: Propylene glycol monomethyl ether acetate (manufactured by Showa Denko KK)
V-601: Dimethyl 2,2′-azobis (2-methylpropionate) (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.)

<Synthesis of ATHF>
Acrylic acid (72.1 parts by mass, 1.0 molar equivalent) and hexane (72.1 parts by mass) were added to a three-necked flask and cooled to 20 ° C. After adding camphor sulfonic acid (0.0070 parts by mass, 0.03 mmol equivalent) and 2-dihydrofuran (77.9 parts by mass, 1.0 mol equivalent), 1. within a range of 20 ° C. ± 2 ° C. After stirring for 5 hours, it heated up to 35 degreeC and stirred for 2 hours. After spreading Kyoward 200 (filter material, aluminum hydroxide powder, manufactured by Kyowa Chemical Industry Co., Ltd.) and Kyoward 1000 (filter material, hydrotalcite-based powder, manufactured by Kyowa Chemical Industry Co., Ltd.) The reaction solution was filtered to obtain a filtrate. Hydroquinone monomethyl ether (MEHQ, 0.0012 parts by mass) was added to the obtained filtrate, followed by concentration under reduced pressure at 40 ° C., whereby 140.8 parts by mass of tetrahydrofuran-2-yl acrylate (ATHF) was a colorless oil. (Yield 99.0%).

<Synthesis of MATHF>
The synthesis was carried out with the same equivalent ratio as the synthesis of ATHF except that acrylic acid was changed to methacrylic acid.

<Synthesis Example of Polymer A-1>
PGMEA (75.0 parts by mass) was placed in a three-necked flask and heated to 90 ° C. in a nitrogen atmosphere. ATHF (30.0 parts by mass), PMPMA (1.0 parts by mass), ethyl acrylate (EA, 35.0 parts by mass), methyl methacrylate (MMA, 34.0 parts by mass), V-601 (4. 0 parts by mass) and PGMEA (75.0 parts by mass) were added dropwise to the three-necked flask solution maintained at 90 ° C. ± 2 ° C. over 2 hours. After completion of the dropwise addition, the mixture was stirred at 90 ° C. ± 2 ° C. for 2 hours to obtain a polymer A-1 (solid content concentration 40.0%).

<Synthesis Example of Polymer A-2 to Polymer A-23>
The monomer type and the like were changed as shown in Table 1 below, and the other conditions were synthesized in the same manner as for Polymer A-1. The solid content concentration of the polymer was 40% by mass. The unit of the amount of each monomer used in Table 1 is mass%.

<Photo acid generator>
B-1: Compound having the structure shown below (Compound described in paragraph 0227 of JP 2013-47765 A, synthesized according to the method described in paragraph 0227)

B-2: PAG-103 (trade name, manufactured by BASF, the following compound)

B-3: Compound having the structure shown below (synthesized according to the method described in paragraph 0210 of JP-A-2014-197155)

In the above compounds, Ts represents a tosyl group.

B-4: GSID-26-1, triarylsulfonium salt (manufactured by BASF, the following compound)

<Surfactant>
C-1: Compound having the structure shown below

<Basic compound>
D-1: Compound having the structure shown below

D-2: 2-Phenylimidazole (manufactured by Tokyo Chemical Industry Co., Ltd.)
D-3: Trioctylamine (manufactured by Tokyo Chemical Industry Co., Ltd.)

<Production of photosensitive transfer material>
In Examples 1 to 17 and Comparative Examples 1 to 5, the polymer component, the photoacid generator, the basic compound, and the surfactant were added to PGMEA so that the solid content ratio (mass ratio) shown in Table 2 below was obtained. The solution was dissolved and mixed so as to have a solid content concentration of 10% by mass and filtered through a polytetrafluoroethylene filter having a pore diameter of 0.2 μm to obtain a photosensitive resin composition.
In each Example and Comparative Example, the obtained photosensitive resin composition was used on a 30 μm-thick polyethylene terephthalate film (hereinafter also referred to as PET (A)) serving as a temporary support, using a slit nozzle. The coating was applied so that the dry film thickness was 3.0 μm and the coating width was 1.0 m. Thereafter, the film is passed through a drying zone at 80 ° C. for 40 seconds, a polyethylene film (OSM-N, manufactured by Tredegar) is pressure-bonded as a cover film to produce a photosensitive transfer material, and the photosensitive transfer material is taken up and rolled. Formed.

<Performance evaluation>
A PET substrate with a copper layer in which copper was deposited to a thickness of 200 nm on a PET film having a thickness of 100 μm by a vacuum deposition method was used.

-Evaluation of suitability for lamination-
The produced photosensitive transfer material was cut into a 50 cm square, the cover film was peeled off, and the roll temperature was 90 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 4.0 m / min. It laminated on the said PET board | substrate with a copper layer on the following lamination conditions. The part where the intermediate layer and the photosensitive resin layer adhere to the copper layer is visually discriminated, and the oily magic is used from above the temporary support of the part where the intermediate layer and the photosensitive resin layer adhere to the copper layer. And image the entire PET substrate, and with image analysis software (ImageJ (manufactured by National Institute of Health, USA)), the area where the intermediate layer and the photosensitive resin layer adhere to the copper layer and the area of the entire sample piece Was calculated respectively. And area ratio was calculated | required from the following formula and evaluated according to the following evaluation criteria.
Area ratio (%) = area where the intermediate layer and the photosensitive resin layer adhere / area of the entire sample piece × 100
5: 95% or more 4: 90% or more and less than 95% 3: 85% or more and less than 90% 2: 80% or more and less than 85% 1: less than 80%

-Sensitivity evaluation-
After unwinding the produced photosensitive transfer material, a lamiroll temperature of 120 ° C., a linear pressure of 1.0 MPa, and a linear velocity of 0.5 m / min. Lamination was performed on a PET substrate with a copper layer under the laminating conditions. Without peeling off the temporary support, after exposure with an ultra-high pressure mercury lamp through a line-and-space pattern mask (duty ratio 1: 1) with a line width of 10 μm, after leaving it at 25 ° C. for 3 hours, the temporary support was peeled off. Developed. Development was performed by shower development for 30 seconds using a 1.0% aqueous sodium carbonate solution at 25 ° C.
When a 10 μm line and space pattern was formed by the above method, the residue in the space was observed and evaluated with a scanning electron microscope (SEM), and the exposure amount at which the residue was completely eliminated was determined. The exposure amount is preferably less than 200 mJ / cm ² .
5: 80mJ / cm ² less than 4: 80mJ / cm ² or more 150 mJ / cm ² less than 3: 150mJ / cm ² or more 200 mJ / cm ² less than ^2: 200mJ / cm 2 or more 300 mJ / cm ² less than 1: 300mJ / cm ² or more

-Evaluation of restraint time dependence inhibition
After unwinding the produced photosensitive transfer material, the roll temperature was 120 ° C., the linear pressure was 1.0 MPa, and the linear velocity was 0.5 m / min. Lamination was performed on a PET substrate with a copper layer under the laminating conditions. Without exposing the temporary support, it was left at 25 ° C. for 12 hours after exposure with the exposure amount with no residue in the sensitivity evaluation through a line and space pattern mask (Duty ratio 1: 1) having a line width of 10 μm. Thereafter, the temporary support was peeled off and developed. Development was performed by shower development for 30 seconds using a 1.0% aqueous sodium carbonate solution at 25 ° C.
The line width of the obtained line and space pattern was observed with a scanning electron microscope (SEM), and the fluctuation of the line width from 10 μm was evaluated. The line width variation from 10 μm is preferably less than 1.5 μm.
5: Less than 0.5 μm 4: 0.5 μm or more and less than 1.0 μm 3: 1.0 μm or more and less than 1.5 μm 2: 1.5 μm or more and less than 3 μm 1: 3 μm or more

-Resolution evaluation-
The produced photosensitive transfer material was subjected to a roll temperature of 120 ° C., a linear pressure of 0.8 MPa, and a linear velocity of 1.0 m / min. It laminated on the PET board | substrate with a copper layer on the lamination conditions of these.
Without peeling off the temporary support, it was exposed with an ultra-high pressure mercury lamp through a line-and-space pattern mask (duty ratio 1: 1) with a line width of 3 μm to 20 μm, and after leaving for 3 hours, the temporary support was peeled off. Developed. Development was performed by shower development for 30 seconds using a 1.0% aqueous sodium carbonate solution at 25 ° C. Next, the copper layer was etched by a dipping method for 60 seconds using a copper etching solution at 25 ° C. (Cu-02 manufactured by Kanto Chemical Co., Inc.). The remaining photosensitive resin layer was peeled off with a shower using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.) at 50 ° C. to form a copper wiring having a conductive pattern with a line and space of 10 μm. The copper wiring LWR (Line Width Roughness, 3σ of a value obtained by measuring the width of the copper wiring at 250 points) was obtained, and the linearity was evaluated using the following criteria as an index. Three or more are practical levels.
5: LWR is 200 nm or less.
4: LWR is 230 nm or less and more than 200 nm.
3: LWR is a value of 250 nm or less and exceeding 230 nm.
2: LWR is a value of 300 nm or less and exceeding 250 nm.
1: LWR was larger than 300 nm or a conductive pattern could not be formed.

Table 2 summarizes the evaluation results in each example and each comparative example.

From Table 2 above, it can be seen that the photosensitive transfer materials of Examples 1 to 17 are superior in laminate suitability and resolution as compared with the photosensitive transfer materials of Comparative Examples 1 to 5.
Further, from the above Table 2, the photosensitive transfer materials of Examples 1 to 17 are excellent in sensitivity and retention time dependence suppression.

(Example 101)
On the 100 μm-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer at a thickness of 200 nm by vacuum evaporation. Thus, a circuit forming substrate was obtained.
The photosensitive transfer material obtained in Example 1 was laminated on the copper layer (Lamiroll temperature 120 ° C., linear pressure 0.8 MPa, linear velocity 1.0 m / min.). A photomask provided with a pattern (hereinafter also referred to as “pattern A”) shown in FIG. 2 having a structure in which conductive layer pads are connected in one direction without peeling off the temporary support from the laminated support is used. The contact pattern was exposed.
In the pattern A shown in FIG. 2, the solid line portion SL and the gray portion G are light shielding portions, and the dotted line portion DL virtually shows an alignment alignment frame.
Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A. Next, after etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), A substrate on which both copper and ITO were drawn in pattern A was obtained.
Next, pattern alignment was performed using a photomask provided with openings of a pattern shown in FIG. 3 (hereinafter also referred to as “pattern B”) in the aligned state, and development and washing were performed.
In the pattern B shown in FIG. 3, the gray portion G is a light shielding portion, and the dotted line portion DL is a virtual alignment alignment frame.
Thereafter, the copper layer was etched using Cu-02, and the remaining photosensitive resin layer was peeled off using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
When the obtained circuit wiring board was observed with a microscope, it was a clean pattern with no peeling or chipping.

(Example 102)
On the 100 μm-thick PET substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer at a thickness of 200 nm by vacuum evaporation. Thus, a circuit forming substrate was obtained.
The photosensitive transfer material obtained in Example 1 was unwound and laminated on the copper layer (roll temperature 120 ° C., linear pressure 0.8 MPa, linear velocity 1.0 m / min.). The laminated support was subjected to pattern exposure using a photomask provided with a pattern A having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a pattern A. Next, after etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), A substrate on which both copper and ITO were drawn in pattern A was obtained.
Next, PET (A) was laminated as a protective layer on the remaining resist. In this state, pattern exposure was performed using a photomask provided with an opening of pattern B in the aligned state, and after developing PET (A), development and washing were performed. Thereafter, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was stripped using a stripping solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board.
When the obtained circuit wiring board was observed with a microscope, it was a clean pattern with no peeling or chipping.

(Example 103)
On the 100 μm-thick cycloolefin polymer (COP) substrate, ITO was deposited as a second conductive layer by sputtering to a thickness of 150 nm, and copper was deposited thereon as a first conductive layer by a thickness of 200 nm by vacuum evaporation. To form a substrate for forming a conductive pattern.
The photosensitive transfer material obtained in Example 1 was bonded to a substrate on a copper layer (roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.) To obtain a laminate. The laminate was subjected to pattern exposure using a photomask provided with a pattern A having a configuration in which conductive layer pads were connected in one direction without peeling off the temporary support. Thereafter, the temporary support was peeled off, developed and washed with water to obtain a resin pattern drawn with pattern A. Next, after etching the copper layer using a copper etching solution (Cu-02 manufactured by Kanto Chemical Co., Ltd.), the ITO layer is etched using an ITO etching solution (ITO-02 manufactured by Kanto Chemical Co., Ltd.), and a peeling solution. By peeling using (KP-301, manufactured by Kanto Chemical Co., Inc.), a substrate on which both copper and ITO were drawn with the pattern A was obtained.
Next, the photosensitive transfer material obtained in Example 1 was bonded onto the remaining resist (roll temperature 100 ° C., linear pressure 0.8 MPa, linear velocity 3.0 m / min.). In this state, pattern exposure was performed using a photomask provided with openings of pattern B in the aligned state, and the temporary support of the photosensitive transfer material was peeled off, followed by development and washing with water. Thereafter, the copper wiring was etched using Cu-02, and the remaining photosensitive resin layer was peeled using a peeling solution (KP-301 manufactured by Kanto Chemical Co., Inc.) to obtain a circuit wiring board having a conductive pattern. .
When the obtained circuit wiring board was observed with a microscope, it was a clean pattern with no peeling or chipping.

The disclosure of Japanese Patent Application No. 2018-098331 filed on May 22, 2018 is incorporated herein by reference in its entirety.
All documents, patent applications, and technical standards described in this specification are the same as if each document, patent application, and technical standard were specifically and individually stated to be incorporated by reference. Which is incorporated herein by reference.

10: Temporary support, 12: Photosensitive resin layer, 14: Cover film, 100: Photosensitive transfer material, SL: Solid line part, G: Gray part, DL: Dotted line part

Claims

A temporary support;
A photosensitive resin layer,
The photosensitive resin layer contains a polymer component that satisfies at least one of the following a1 and a2, and a photoacid generator,
The photosensitive transfer material whose glass transition temperature of the said polymer component is 90 degrees C or less.
a1: Polymer component containing a structural unit having an acid group protected by an acid-decomposable group and a polymer having a structural unit having a pKaH group of 3 or more a2: An acid group protected by an acid-decomposable group And a polymer component comprising a polymer having a structural unit having a structural unit having a pKaH group of 3 or more
2. The photosensitive composition according to claim 1, wherein among all the groups having 3 or more pKaH contained in the photosensitive resin layer, the proportion of the group having 3 or more pKaH contained in the polymer component is 30 mol% or more. Transfer material.
The ratio of the group having 3 or more pKaH contained in the polymer component among all the groups having 3 or more pKaH contained in the photosensitive resin layer is 50 mol% or more. The photosensitive transfer material described in 1.
The polymer in the polymer component further has a structural unit other than a structural unit having an acid group protected with an acid-decomposable group and a structural unit having a pKaH group of 3 or more. 2. The photosensitive transfer material according to item 1.
The photosensitive transfer material according to any one of claims 1 to 4, wherein the structural unit having a pKaH group of 3 or more is a structural unit represented by the following formula I or formula II.

In Formulas I and II, R 1 represents a hydrogen atom or a methyl group, and Z is a single bond, a methylene group, an arylene group, —O—, —C (═O) —NH—, or —C (═O) —. Represents O—, and R 2 may have a single bond or at least one group selected from the group consisting of an ether bond, a urethane bond, a urea bond, an amide bond, an ester bond and a carbonate bond. Represents a linear, branched or cyclic alkylene group of 1 to 10, wherein R 3 and R 4 are each independently a hydrogen atom, or an ether bond, a thioether bond, a hydroxy group, a formyl group, an acetoxy group, a cyano group A linear group having 1 to 20 carbon atoms which may have at least one group selected from the group consisting of a group, a urethane bond, a urea bond, an amide bond, an ester bond, a carbonate bond and an aromatic group, Represents a branched or cyclic alkyl group, R 2 and R 3 , R 2 and R 4 , or R 3 and R 4 may be bonded to each other to form a ring, and Q 1 represents a nitrogen atom Represents an aromatic group or a nitrogen-containing heteroaromatic group.
6. The photosensitive transfer material according to claim 5, wherein the structural unit in which the pKaH has a group of 3 or more is a structural unit represented by the formula I.
7. The photosensitive transfer material according to claim 1, wherein the structural unit having an acid group protected by an acid-decomposable group is a structural unit represented by the following formula A.

In formula A, R 31 and R 32 each independently represent a hydrogen atom, an alkyl group or an aryl group, at least one of R 31 and R 32 is an alkyl group or an aryl group, and R 33 is an alkyl group or Represents an aryl group, R 31 or R 32 and R 33 may combine to form a cyclic ether, R 34 represents a hydrogen atom or a methyl group, and X 0 represents a single bond or a divalent linking group. Represents.
A step of bringing the photosensitive resin layer in the photosensitive transfer material according to any one of claims 1 to 7 into contact with a substrate and bonding the substrate;
Pattern exposing the photosensitive resin layer;
And developing the exposed photosensitive resin layer to form a pattern, in this order.
A step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of claims 1 to 7 into contact with a substrate having a conductive layer;
Pattern exposing the photosensitive resin layer;
Developing the exposed photosensitive resin layer to form a pattern; and
And a step of etching the conductive layer in a region where the pattern is not disposed, in this order.
The circuit wiring manufacturing method according to claim 9, wherein the conductive layer is a layer containing copper.
A step of bringing the photosensitive resin layer of the photosensitive transfer material according to any one of claims 1 to 7 into contact with a substrate having a conductive layer;
Pattern exposing the photosensitive resin layer;
Developing the exposed photosensitive resin layer to form a pattern;
And a step of etching the conductive layer in a region where the pattern is not disposed, in this order.