TWI780648B - Photosensitive element, and method of forming resist pattern - Google Patents

Abstract

The present invention provides a photosensitive element and a method for forming a resist pattern that can achieve both improvement in resolution and prevention of wrinkles during winding. The photosensitive element of the present invention is characterized in that it has a support film (A), a photosensitive resin composition layer (B) and a protective film (C) in sequence, and the support film (A) specified by JIS B0601-2001 ), the surface roughness Rz _A1 (nm) of the surface of the side that is in contact with the photosensitive resin composition layer (B), and the side of the support film (A) that is in contact with the photosensitive resin composition layer (B) is The surface roughness Rz _A2 (nm) of the surface on the opposite side, the surface roughness Rz _C1 (nm) of the surface of the side of the protective film (C) in contact with the photosensitive resin composition layer, the ratio of the protective film (C) and The surface roughness Rz _C2 (nm) of the side opposite to the photosensitive resin composition layer satisfies the following (1)-(3): (1) 1<Rz _A1 <100 (2)300<Rz _C1 <600 (3)40<Rz _C2 /Rz _A2 .

Description

Photosensitive element and method for forming resist pattern

The invention relates to a photosensitive element and a method for forming a resist pattern.

In electronic devices such as personal computers and mobile phones, printed wiring boards, etc. are used to mount components and semiconductors. As resists for the production of printed wiring boards, etc., conventionally used photosensitive elements in which a photosensitive resin composition layer is laminated on a support film, and a protective film is further laminated on the photosensitive resin composition layer if necessary ( photosensitive resin laminate), so-called dry film resist (for example, refer to Patent Document 1 and Patent Document 2).

In such a photosensitive element, in order to improve the resolution, it is preferable to use a high-quality film with less internal foreign matter that blocks the light of exposure as a support film. [Prior Art Literature] [Patent Document]

[Patent Document 1] Japanese Patent Laid-Open No. 2004-191648 [Patent Document 2] Japanese Patent Laid-Open No. 2019-188612

[Problem to be solved by the invention]

However, since the surface roughness of the high-quality film is small, when the photosensitive resin composition layer and the protective film are laminated and wound up into a roll, the friction force at the interface contacting the protective film becomes too high, causing wrinkles produce.

The present invention has been made in view of such prior circumstances, and an object of the present invention is to provide a photosensitive element and a method for forming a resist pattern that can achieve both improvement in resolution and prevention of wrinkles during winding. [Technical means to solve the problem]

The inventors of the present invention found that the above problems can be solved by the following technical means. [1] A photosensitive element, characterized in that it has a support film (A), a photosensitive resin composition layer (B) and a protective film (C) in this order, and the support specified in JIS B0601-2001 The surface roughness Rz _A1 (nm) of the surface of the film (A) that is in contact with the photosensitive resin composition layer (B), the surface of the support film (A) that is in contact with the photosensitive resin composition layer The surface roughness Rz _A2 (nm) of the surface opposite to the side of (B), the surface roughness Rz _C1 of the surface of the protective film (C) that is in contact with the photosensitive resin composition layer (B) (nm), and the surface roughness Rz _C2 (nm) of the surface of the protective film (C) on the opposite side to the side in contact with the photosensitive resin composition layer (B) satisfies the following (1) to (3) ): (1) 1<Rz _A1 <100 (2) 300<Rz _C1 <600 (3) 40<Rz _C2 /Rz _A2 . [2] The photosensitive element as described in [1], wherein 1<Rz _A2 <200. [3] The photosensitive element described in [1] or [2], wherein 1.1<Rz _A2 /Rz _A1 <7. [4] The photosensitive element according to any one of [1] to [3], wherein 1.1<Rz _C2 /Rz _C1 <10. [5] The photosensitive element according to any one of [1] to [4], wherein 50<Rz _C2 /Rz _A2 <100. [6] The photosensitive element according to any one of [1] to [5], wherein the number of particles with a diameter of 2 μm to 5 μm contained in the support film (A) is 30/30 ^mm2 or less. [7] The photosensitive element according to any one of [1] to [6], wherein the number of particles with a diameter of 2 μm to 5 μm contained in the support film (A) is 15/30 ^mm2 or less. [8] The photosensitive element according to any one of [1] to [7], wherein the number of particles with a diameter of 2 μm to 5 μm contained in the support film (A) is 10/30 ^mm2 or less. [9] The photosensitive element according to any one of [1] to [8], wherein the content of the titanium element contained in the support film (A) is 1 ppm to 20 ppm. [10] The photosensitive element according to any one of [1] to [9], wherein at least one side of the support film (A) is smoothed. [11] The photosensitive element according to any one of [1] to [10], wherein the film thickness of the support film (A) is not less than 5 μm and not more than 16 μm. [12] The photosensitive element according to any one of [1] to [11], wherein the surface of the protective film (C) contains a polypropylene resin. [13] A wound body of a photosensitive element obtained by winding the photosensitive element described in any one of [1] to [12]. [14] A method for forming a resist pattern, comprising: a layering step of laminating the photosensitive element described in any one of [1] to [12] on a substrate; an exposing step of exposing the photosensitive element exposing the photosensitive resin composition layer; and a developing step, which develops and removes the unexposed portion of the photosensitive resin composition layer. [15] The method for forming a resist pattern as described in [14], wherein the exposure step is carried out by a projection exposure method. [Effect of Invention]

According to the present invention, it is possible to provide a photosensitive element and a method for forming a resist pattern that can achieve both improvement in resolution and prevention of wrinkles during winding.

Embodiments for carrying out the present invention will be described in detail below. [Photosensitive element] FIG. 1 is a cross-sectional view schematically showing one configuration example of the photosensitive element of the present invention. The photosensitive element of the present invention is characterized in that it has a support film (A), a photosensitive resin composition layer (B) and a protective film (C) in sequence, and the support film (A) specified by JIS B0601 Surface roughness Rz _A1 (nm) of the side in contact with the photosensitive resin composition layer, surface roughness of the support film (A) on the opposite side to the side in contact with the photosensitive resin composition layer Rz _A2 (nm), the surface roughness Rz _C1 (nm) of the surface of the protective film (C) in contact with the photosensitive resin composition layer, and the protective film (C) in contact with the photosensitive resin composition The surface roughness Rz _C2 (nm) of the surface opposite to the object layer satisfies the following (1)~(3): (1)1<Rz _A1 <100 (2)300<Rz _C1 <600 (3)40 <Rz _C2 /Rz _A2 .

In order to improve the resolution of the photosensitive element, it is preferable to use a high-quality film with less internal foreign matter that blocks exposed light as the support film (A). A high-quality film is characterized by a small surface roughness, especially, a small surface roughness on the side that is in contact with the photosensitive resin composition layer (B). However, when these films are used to manufacture photosensitive element rolls (dry film rolls), the frictional force with the protective film (C) is too high, causing wrinkles when wound up into a roll. Therefore, in order to prevent wrinkles at the time of winding up into a roll, the method of increasing the surface roughness of the side surface which contacts the support film (A) of a protective film (C) is mentioned, for example.

In order to balance the above two issues (improvement of resolution and prevention of wrinkles during winding), it is more important that the surface roughness of the support film (A) is small and that it is in contact with the photosensitive resin composition layer (B) The surface of the side of the protective film (C) is smoother, and the surface of the side contacting the photosensitive resin composition layer (B) of the protective film (C) is relatively smooth, and the other surface is roughened. That is, the inventors of the present invention have thought that a layer configuration in which both the support film (A) and the protective film (C) are smooth to some extent and both have a roughened surface is ideal.

Therefore, the present inventors make the surfaces of the support film (A) and the protective film (C) smoother to some extent, and make the surface roughness of the support film (A) and the protective film (C) different, A photosensitive element that can achieve both improvement in resolution and prevention of wrinkles when wound into a roll.

In the present invention, the above-mentioned configuration is defined using formulas (1) to (3). By satisfying all of the formulas (1) to (3), the photosensitive element of the present invention has good resolution and can well prevent wrinkles when wound up into a roll.

In addition, in this specification, surface roughness is based on the maximum height Rz measured by the method prescribed|regulated by JISB0601-2001. In addition, the value of the surface roughness can be measured using a general surface roughness measuring device such as a laser type, a stylus type, a light cutting type, and an optical interference type.

＜Support film (A)＞ The support film (A) of this embodiment is a layer or film for supporting the photosensitive resin composition layer (B), and is preferably a transparent base film that allows active light to pass through.

As a transparent base film, the film containing synthetic resins, such as polyethylene, a polypropylene, a polycarbonate, polyethylene terephthalate, is mentioned. It is generally preferred to use polyethylene terephthalate (PET), which has moderate flexibility and strength. Among them, it is preferable to use a high-quality film with less internal foreign matter. Specifically, as a high-quality film, it is better to use: a PET film synthesized using a Ti-based catalyst; a PET film with a smaller diameter and less lubricant content; a PET film containing a lubricant on only one side of the film. Film; thin film PET film; PET film with smoothing treatment on at least one side; PET film with roughening treatment such as plasma treatment on at least one side, etc. Thereby, the exposure light can be irradiated to the photosensitive resin composition layer (B) without interrupting the exposure light by internal foreign matter, and the resolution of a photosensitive element can be improved.

The number of particles with a diameter of 2 μm to 5 μm contained in the support film (A) as internal foreign matter is preferably 30 particles/30 mm ² or less, more preferably 15 particles/30 mm ² or less, and still more preferably 10 pieces/30 mm ² or less.

The content of titanium element (Ti) contained in the support film (A) is preferably not less than 1 ppm and not more than 20 ppm, more preferably not less than 2 ppm and not more than 12 ppm. If the content of the titanium element is 20 ppm or less, the number of internal foreign matter originating from the aggregate containing the titanium element can be reduced, and a decrease in resolution can be prevented.

The film thickness of the support film (A) is preferably from 5 μm to 16 μm, more preferably from 6 μm to 12 μm. The thinner the film thickness of the support film, the fewer the number of internal foreign matter, and the better it can prevent the degradation of resolution. However, if the film thickness is less than 5 μm, it will be caused by tension in the manufacturing steps of coating and winding. The resulting elongation deformation or micro damage in the winding direction will cause breakage, or it will cause wrinkles during lamination due to insufficient strength of the film.

It is preferable to perform smoothing treatment using a calender apparatus etc. on at least one side of a support film (A). Thereby, the surface roughness of one side of the support film (A), especially the side in contact with the photosensitive resin composition layer (B) can be reduced, thereby making the effect of the present invention more excellent.

From the perspective of improving the parallelism of the light irradiated to the photosensitive resin composition layer (B) and obtaining higher resolution after exposure and development of the photosensitive element, the haze of the support film (A) is preferably 0.01% to 1.5%, more preferably 0.01% to 1.2%, still more preferably 0.01 to 0.95%.

And, in the photosensitive element of this embodiment, the support film (A) satisfies the following formula (1) about the surface roughness of both surfaces. (1) 1<Rz _A1 <100, where Rz _A1 represents the surface roughness (nm) of the side of the support film (A) that is in contact with the photosensitive resin composition layer (B), and Rz _A2 represents the support Surface roughness (nm) of the surface of the film (A) opposite to the side in contact with the photosensitive resin composition layer (B). Formula (1) stipulates that both sides of the support film (A) are relatively smooth, but one side is roughened. Thereby, the resolution of a photosensitive element becomes excellent.

Rz _A1 and Rz _A2 are not particularly limited as long as they satisfy the above formula (1), but specifically, Rz _A1 is more preferably 10 nm to 70 nm. Regardless of the size of Rz _A1 , Rz _A2 only needs to be a small value. Specifically, Rz _A2 is preferably 1 nm<Rz _A2 <200 nm, more preferably 40 nm˜100 nm, further preferably 50 nm˜90 nm. Also, Rz _A2 /Rz _A1 is preferably 1.1<Rz _A2 /Rz _A1 <7, more preferably 1.2-5.

<Photosensitive resin composition layer (B)> The photosensitive resin composition layer (B) is laminated on the support film (A). As the photosensitive resin composition layer (B) of this embodiment, a well-known photosensitive resin composition layer may be used. Usually, the photosensitive resin composition layer is formed of a photosensitive resin composition comprising (i) an alkali-soluble polymer, (ii) a component containing an ethylenically unsaturated double bond (such as an ethylenically unsaturated addition polymerizable monomer), and (iii) a photopolymerization initiator.

From the viewpoint of alkali solubility, the alkali-soluble polymer as the component (i) preferably has a carboxyl group. Moreover, it is also preferable that an alkali-soluble polymer has an aromatic group in the side chain from the viewpoint of the intensity|strength of a cured film, and the coatability of a photosensitive resin composition.

In terms of the development resistance of the photosensitive resin composition layer, and the development resistance, resolution and adhesion of the resist pattern, the acid equivalent of the alkali-soluble polymer is preferably 100 or more. From the viewpoint of the developability and peelability of the material layer, the acid equivalent weight of the alkali-soluble polymer is preferably 600 or less. The acid equivalent of the alkali-soluble polymer is more preferably from 250 to 550, and still more preferably from 300 to 500.

From the standpoint of keeping the thickness of the dry film resist uniform and obtaining resistance to the developer, the weight average molecular weight of the alkali-soluble polymer is preferably in the range of 5,000-500,000, more preferably 10,000-200,000, More preferably, it is 18,000-100,000. In this specification, the so-called weight average molecular weight refers to the weight average molecular weight measured by gel permeation chromatography (GPC) using a calibration curve of standard polystyrene. The dispersity of the alkali-soluble polymer is preferably 1.0-6.0.

As an alkali-soluble polymer, a carboxylic acid-containing vinyl copolymer, a carboxylic acid-containing cellulose, etc. are mentioned, for example.

Carboxylic acid-containing ethylene-based copolymers are compounds obtained by ethylene-copolymerizing the first monomer and the second monomer. The second monomer system is selected from alkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, (meth)acrylamide and hydrogen on nitrogen replaced by alkyl or alkoxy At least one of compounds, styrene and styrene derivatives, (meth)acrylonitrile, and glycidyl (meth)acrylate.

Examples of the first monomer used in vinyl copolymers containing carboxylic acids include: acrylic acid, methacrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic acid semi- Esters etc. These 1st monomers may be used individually, respectively, and may combine 2 or more types.

The content ratio of the structural unit of the first monomer in the carboxylic acid-containing vinyl copolymer is 15% by mass to 40% by mass, preferably 20% by mass to 35% by mass, based on the mass of the copolymer. If the ratio is less than 15% by mass, it will be difficult to develop with an alkaline aqueous solution. When the ratio exceeds 40% by mass, the first monomer is insoluble in a solvent during polymerization, making it difficult to synthesize a copolymer.

Specific examples of the second monomer used in the carboxylic acid-containing vinyl copolymer include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, ( Cyclohexyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate , 4-Hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, (meth)acrylamide, N-methylolacrylamide , N-butoxymethacrylamide, styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene, (meth)acrylonitrile, glycidyl (meth)acrylate, etc. These second monomers may be used alone, respectively, or may be used in combination of two or more.

The content ratio of the structural unit of the second monomer in the carboxylic acid-containing vinyl copolymer is 60% by mass to 85% by mass, preferably 65% by mass to 80% by mass, based on the mass of the copolymer.

From the viewpoint of introducing an aromatic group into the side chain, it is more preferable to make the carboxylic acid-containing vinyl copolymer contain styrene or α-methylstyrene, p-methylstyrene, p-chlorostyrene, etc. The structural unit of the substance is used as the second monomer. In this case, the content ratio of the structural units of styrene or styrene derivatives in the carboxylic acid-containing vinyl copolymer is based on the mass of the copolymer, preferably 5% by mass or more and 35% by mass or less, more preferably It is not less than 15% by mass and not more than 30% by mass.

The weight average molecular weight of the carboxylic acid-containing vinyl copolymer is in the range of 10,000-200,000, preferably in the range of 18,000-100,000. When this weight average molecular weight is less than 10,000, the intensity|strength of a cured film will become small. When this weight average molecular weight exceeds 200,000, the viscosity of a photosensitive resin composition will become too high, and the applicability will fall.

The vinyl copolymer containing carboxylic acid is preferably synthesized by adding an appropriate amount of benzoyl peroxide, azoisobutyronitrile and other free radical polymerization initiators, and overheated stirring. There is also a case of synthesizing while dropping a part of the mixture into the reaction liquid. There are also cases where after the reaction is completed, a solvent is further added to adjust to a desired concentration. As this synthesis method, in addition to solution polymerization, block polymerization, suspension polymerization, and emulsion polymerization can also be used.

Examples of carboxylic acid-containing cellulose include cellulose acetate phthalate, hydroxyethyl-carboxymethyl cellulose, and the like. The content of the alkali-soluble polymer (A) is based on the total mass of the photosensitive resin composition, preferably in the range of 30% by mass to 80% by mass, more preferably in the range of 40% by mass to 65% by mass . If the content is less than 30% by mass, the dispersibility in an alkaline developing solution will decrease, and the developing time will become significantly longer. When this content exceeds 80 mass %, the photocuring of a photosensitive resin composition layer will become insufficient, and the tolerance as a resist will fall. Alkali-soluble polymers may be used alone or in combination of two or more.

As the ethylenically unsaturated addition-polymerizable monomer as the component (ii), known types of compounds can be used. Examples of ethylenically unsaturated addition polymerizable monomers include: 2-hydroxy-3-phenoxypropyl acrylate, phenoxytetraethylene glycol acrylate, β-hydroxypropyl-phthalic acid β'-(acryloxy)propyl ester, 1,4-tetramethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,4-cyclo Hexylene glycol di(meth)acrylate, heptapropylene glycol di(meth)acrylate, glyceryl (meth)acrylate, 2-di(p-hydroxyphenyl)propane di(meth)acrylate, tri(meth)acrylate Glyceryl acrylate, trimethylolpropane tri(meth)acrylate, compounds containing at least one of ethylene oxide chain, propylene oxide chain, and tetrahydrofuran chain in the molecule; dipentaerythritol penta(meth)acrylate Compounds containing at least one of ethylene oxide chains, propylene oxide chains, and tetrahydrofuran chains in their molecules; compounds containing ethylene oxide chains, propylene oxide chains, and tetrahydrofuran chains in their molecules At least one compound; fr trimethylolpropane triglycidyl ether tri(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, diallyl phthalate, polyethylene glycol Alcohol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 4-n-octylphenoxypentapropylene glycol acrylate, nonapropylene glycol bis(triethylene glycol methacrylate), polypropylene glycol bis( Tetraethylene glycol methacrylate), polypropylene glycol bis(triethylene glycol methacrylate), polypropylene glycol bis(diethylene glycol acrylate), 4-n-nonylphenoxyheptaethylene glycol dipropylene glycol (Meth) acrylate, phenoxy tetrapropylene glycol tetraethylene glycol (meth) acrylate, and bisphenol A (meth) acrylate monomers contain ethylene oxide chains, propylene oxide chains, A compound of at least one kind of tetrahydrofuran chain, etc. Even if the ethylenically unsaturated addition-polymerizable monomer is a compound other than the above-mentioned compounds that preferably contain at least one of an ethylene oxide chain, a propylene oxide chain, and a tetrahydrofuran chain, it is preferable to contain ethylene oxide. chain, propylene oxide chain, tetrahydrofuran chain at least one alkylene oxide chain.

Also, as ethylenically unsaturated addition-polymerizable monomers, polyvalent isocyanate compounds such as hexamethylene diisocyanate and tolyl diisocyanate, 2-hydroxypropyl (meth)acrylate, oligoethylene glycol Urethane compounds of hydroxyacrylate compounds such as mono(meth)acrylate, oligopropylene glycol mono(meth)acrylate, etc. These ethylenically unsaturated addition polymerizable monomers may be used alone or in combination of two or more.

The content of the ethylenically unsaturated addition polymerizable monomer is based on the total mass of the photosensitive resin composition, preferably 20 mass % to 70 mass %, more preferably 30 mass % to 60 mass %. When this content is less than 20 mass %, hardening of a photosensitive resin will be insufficient, and the intensity|strength as a resist will be insufficient. On the other hand, if the content exceeds 70% by mass, when the photosensitive element is stored in roll form, the photosensitive resin composition layer or the photosensitive resin composition will easily overflow from the roll end surface slowly. Phenomenon, that is, edge fusion.

、2,4-二甲基-9-氧硫𠮿

、2,4-二乙基-9-氧硫𠮿

、2-異丙基-9-氧硫𠮿

、4-異丙基-9-氧硫𠮿

、2,4-二異丙基-9-氧硫𠮿

、2-氟-9-氧硫𠮿

、4-氟-9-氧硫𠮿

、2-氯-9-氧硫𠮿

、4-氯-9-氧硫𠮿

、1-氯-4-丙氧基-9-氧硫𠮿

、二苯甲酮、4,4'-雙(二甲胺基)二苯甲酮[米其勒酮]、4,4'-雙(二乙胺基)二苯甲酮、2,2-二甲氧基-2-苯基苯乙酮等芳香族酮類；2-(鄰氯苯基)-4,5-二苯基咪唑基二聚物等聯咪唑化合物；9-苯基吖啶等吖啶類；α,α-二甲氧基-α-嗎啉基-甲硫基苯基苯乙酮、2,4,6-三甲基苯甲醯基二苯基氧化膦等芳香族系起始劑；苯基甘胺酸、N-苯基甘胺酸等N-芳基胺基酸類；1-苯基-1,2-丙二酮-2-鄰苯甲醯肟、2,3-二側氧-3-苯基丙酸乙酯-2-(鄰苯甲醯羰基)-肟等肟酯類；對二甲胺基苯甲酸、對二乙胺基苯甲酸及對二異丙基胺基苯甲酸以及該等與醇之酯化物、對羥基苯甲酸酯等。其中，較佳為2-(鄰氯苯基)-4,5-二苯基咪唑基二聚物與米其勒酮或4,4'-(二乙胺基)二苯甲酮之組合。Regarding the photopolymerization initiator as the component (iii), for example, benzoyl dimethyl ketal, benzoyl diethyl ketal, benzoyl dipropyl ketal, benzoyl diphenyl ketal, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin phenyl ether, 9-oxosulfur𠮿

, 2,4-Dimethyl-9-oxosulfur 𠮿

, 2,4-Diethyl-9-oxothio𠮿

, 2-isopropyl-9-oxothio𠮿

, 4-isopropyl-9-oxothio𠮿

, 2,4-Diisopropyl-9-oxosulfur

, 2-fluoro-9-oxosulfur

, 4-fluoro-9-oxosulfur

, 2-Chloro-9-oxosulfur

, 4-Chloro-9-oxosulfur

, 1-Chloro-4-propoxy-9-oxosulfur

, benzophenone, 4,4'-bis(dimethylamino)benzophenone [Michler's ketone], 4,4'-bis(diethylamino)benzophenone, 2,2- Aromatic ketones such as dimethoxy-2-phenylacetophenone; biimidazole compounds such as 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer; 9-phenylacridine Acridines; α,α-dimethoxy-α-morpholinyl-methylthiophenylacetophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and other aromatics It is an initiator; N-aryl amino acids such as phenylglycine and N-phenylglycine; 1-phenyl-1,2-propanedione-2-phthaloxime, 2, Oxime esters such as 3-dioxy-3-phenylpropionate-2-(o-benzoylcarbonyl)-oxime; p-dimethylaminobenzoic acid, p-diethylaminobenzoic acid and p-diiso Propylaminobenzoic acid and its esterified products with alcohols, parabens, etc. Among them, a combination of 2-(o-chlorophenyl)-4,5-diphenylimidazolyl dimer and Michelerone or 4,4'-(diethylamino)benzophenone is preferred.

The content of the photopolymerization initiator is based on the total mass of the photosensitive resin composition, preferably not less than 0.01% by mass and not more than 20% by mass, more preferably not less than 1% by mass and not more than 10% by mass. If the content is less than 0.01% by mass, the sensitivity will be insufficient. When this content exceeds 20 mass %, ultraviolet absorption rate will become high, and hardening of the part of the bottom part of a photosensitive resin composition layer will become insufficient.

In order to improve the thermal stability and/or storage stability of the photosensitive resin composition layer (B) of this embodiment, it is preferable to make a photosensitive resin composition or a photosensitive resin composition layer contain a radical polymerization inhibitor. As a radical polymerization inhibitor, for example, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxybenzoate radical, 2,2,6,6-tetra TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl , 2,2,6,6-tetramethylpiperidine-1-oxyl radical) derivatives; )-N'-phenyl-p-phenylenediamine, 4,4'-dicumyl-diphenylamine and other amines; 4-tert-butyl catechol (pyrocatechol) and other catechols ; p-benzoquinone, hydroquinone, 2-hydroxy-1,4-naphthoquinone, tertiary butyl hydroquinone, methyl hydroquinone, 2,5-di-tertiary butyl hydroquinone and other quinones; Quinone methides such as tributyl-7-phenylquinone methide; cuproferrin, copper (II) dibutyldithiocarbamate, N-nitroso-N-phenylhydroxylamine aluminum, etc. Chelating compounds; 2-tert-butyl-4,6-dimethylphenol, [ethylenylbis(oxyethylene)]bis[3-(3-tert-butyl-4-hydroxy-5-methanol) phenyl) propionate], 2,2'-methylenebis[6-(1-methylcyclohexyl)-p-cresol, 2,6-di-tert-butyl-p-cresol, 2 ,6-di-tert-butylphenol, octyl-3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid, 2,2-bis[[[3-(3,5-di- tert-butyl-4-hydroxyphenyl)propionyl]oxy]methyl]propane-1,3-diol-1,3-bis[3-(3,5-di-tert-butyl- 4-hydroxyphenyl)propionate], p-methoxyphenol, 4,4'-butylene bis(6-tert-butyl-3-methylphenol) and other phenol derivatives; pyrogallol, Cuprous Chloride etc.

In this embodiment, the photosensitive resin composition layer (B) may contain coloring substances, such as a dye and a pigment. Examples of coloring substances include magenta, phthalocyanine green, auretamine, Calkoxide Green S, Paramagenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green, basic blue 20, diamond Green and so on.

In this embodiment, you may make the photosensitive resin composition layer (B) contain the chromogenic dye which develops a color by light irradiation. As a chromogenic dye, the combination of a leuco dye and a halogen compound is known, for example. Examples of leuco dyes include tris(4-dimethylamino-2-methylphenyl)methane [leuco crystal violet], tris(4-dimethylamino-2-methylphenyl) Methane [leuco malachite green] and so on. Examples of halogen compounds include bromopentane, bromoisopentane, 1,2-dibromo-2-methylpropane, 1,2-dibromoethane, diphenylbromomethane, dibromotoluene, and dibromomethane. , tribromomethyl phenyl sulfide, carbon tetrabromide, tris(2,3-dibromopropyl) phosphate, trichloroacetamide, iodopentane, iodoisobutane, 1,1,1-tri Chloro-2,2-bis(p-chlorophenyl)ethane, hexachloroethane, etc.

In this embodiment, the photosensitive resin composition layer (B) may contain additives, such as a plasticizer, as needed. Examples of additives include: phthalates such as diethyl phthalate, o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, acetylated lemon Triethyl acetate, acetyl tri-n-propyl citrate, acetyl tri-n-butyl citrate, polypropylene glycol, polyethylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, etc.

The thickness of the photosensitive resin composition layer (B) is preferably 3-100 μm, more preferably the upper limit is 50 μm. The closer the thickness of the photosensitive resin layer is to 3 μm, the higher the resolution is, and the closer the thickness of the photosensitive resin layer is to 100 μm, the higher the film strength is, so it can be appropriately selected according to the application.

＜Protective film (C)＞ The protective film (C) is laminated on the photosensitive resin composition layer (B) side of the laminate of the support film (A) and the photosensitive resin composition layer (B), and functions as a protective layer (cover).

Since the adhesive force between the photosensitive resin composition layer (B) and the protective film (C) is sufficiently smaller than the adhesive force between the photosensitive resin composition layer (B) and the support film (A), the protective film (C) can easily The photosensitive resin composition layer (B) peeled off. For example, a polyethylene film, and a polypropylene film, a stretched polypropylene film, etc. can be preferably used as the protective film (C). More preferably, at least the surface of the protective film (C) contains polypropylene resin. The film thickness of the protective film (C) is preferably from 10 to 100 μm, more preferably from 10 to 50 μm. As the protective film (C), for example: EM-501, E-200, E-201F, FG-201, MA-411 manufactured by Oji F-Tex Co., Ltd., KW37 manufactured by Toray Co., Ltd., 2578, 2548, 2500, YM17S, GF-18, GF-818, GF-858 manufactured by Tamapoly Co., Ltd., etc.

And, in the photosensitive element of this embodiment, the protective film (C) satisfies the following formula (2) about the surface roughness of both surfaces. (2) 300<Rz _C1 <600 Here, Rz _C1 represents the surface roughness (nm) of the surface of the side which contacts the photosensitive resin composition layer (B) of a protective film (C). The formula (2) stipulates that the surface roughness of the side of the protective film (C) in contact with the photosensitive resin composition layer (B) is small. Thereby, the resolution of a photosensitive element becomes excellent. Furthermore, it is preferable that 1.1<Rz _C2 /Rz _C1 <10. Here, Rz _C2 represents the surface roughness (nm) of the surface opposite to the side contacting the photosensitive resin composition layer (B) of the protective film (C).

Rz _C1 and Rz _C2 are not particularly limited as long as they satisfy the above formula (2), but specifically, Rz _C1 is preferably 350 nm to 550 nm. Rz _C2 is preferably from 400 nm to 5500 nm, more preferably from 450 nm to 4500 nm. Moreover, Rz _C2 /Rz _C1 is more preferably 1.5 to 9.0.

Furthermore, in the photosensitive element of this embodiment, a support film (A) and a protective film (C) satisfy following formula (3) about the surface roughness of both surfaces. (3) 40<Rz _C2 /Rz _A2 Here, Rz _A2 represents the surface roughness (nm) of the side opposite to the side of the support film (A) that is connected to the photosensitive resin composition layer (B), Rz _C2 shows the surface roughness (nm) of the surface opposite to the side contacting the photosensitive resin composition layer (B) of a protective film (C). Formula (3) stipulates that, in the side opposite to the side that is connected to the photosensitive resin composition layer (B), there is a certain amount of surface roughness between the surface roughness of the support film (A) and the surface roughness of the protective film (C). the above differences. Thereby, generation|occurrence|production of wrinkles at the time of winding up a photosensitive element in roll shape can be prevented favorably.

The upper limit of Rz _C2 /Rz _A2 is preferably less than 100, more preferably 50<Rz _C2 /Rz _A2 <100. Rz _C2 /Rz _A2 is more preferably 40-80.

By satisfying all of the above-mentioned formulas (1) to (3), the photosensitive element of the present invention has good resolution and can well prevent wrinkles when wound up into a roll.

[Photosensitive element volume] A photosensitive element roll obtained by winding the photosensitive element described above is also an aspect of the present invention.

The photosensitive element is wound up on a core in a strip shape, and is used in a roll shape. The winding length is not particularly limited, but is preferably 320 m or less from the viewpoint of the weight of the roll and ease of handling. If there are many substrates that can be laminated by one photosensitive element roll, the efficiency is good. Therefore, from the viewpoint of productivity, the roll length is preferably 100 m or more.

(core) Sometimes the winding core is also called the core. Its shape is not particularly limited, and may be cylindrical or columnar. Since the photosensitive element is used as an etching resist or a plating resist, and a permanent pattern for electronic materials, it is preferably processed without dust generation, and is preferably made of plastic resin. As the material of the plastic resin, it is preferable that it is light, has excellent strength, and does not generate dust. As such plastic resin, for example, polypropylene (PP) resin, acrylonitrile butadiene styrene (ABS) resin, nylon resin, polyvinyl chloride resin, etc. can be used, preferably ABS resin. The diameter of the core is not particularly limited, but it is preferably a diameter of 2 to 5 inches, more preferably a diameter of 3 inches, so that it can be mounted on a device when the photosensitive element roll is mounted on a laminating machine. The length of the core (in the case of using a cylindrical or cylindrical core, its axial length) may be the same as or shorter than the width of the photosensitive element. However, the length of the winding core is preferably longer than the width of the photosensitive element, so as to ensure that there are moderate protrusions on both sides when the photosensitive element is wound up. It is preferable because the ring-shaped sheet is attached to the protruding part in a manner inserted therethrough. Also, by fitting a bearing called a core holder to the protruding portion, the photosensitive element roll can be suspended and stored without moving.

The photosensitive element roll may be arranged such that the roll end surface protection member is in contact with the end surface of the rolled photosensitive element (the width direction end side of the strip-shaped photosensitive element).

In particular, in the photosensitive element roll of the present embodiment, since the surface roughness of both sides of the support film (A) and the protective film (C) are regulated as described above, it is possible to prevent unevenness during winding up well. wrinkled. In addition, by keeping the frictional force between the support film (A) and the protective film (C) in an appropriate range, when the roll is stored vertically to the ground, it is difficult to cause winding misalignment. Furthermore, since it is not easy to generate electrification on the surface of the roll caused by excessive friction during use, it is easy to prevent the adhesion of dust or dirt.

The method for forming a resist pattern using the photosensitive element of this embodiment or its roll preferably includes the following steps in sequence: a lamination step, which laminates photosensitive elements on the substrate; an exposing step of exposing the photosensitive resin composition layer of the photosensitive element; and A development step, which develops and removes the unexposed part of the photosensitive resin composition layer.

In the lamination step, specifically, after the protective film (C) is peeled off from the photosensitive element, the photosensitive resin composition layer is thermally and pressure-bonded to the surface of the support (for example, a substrate) by a laminating machine, and is carried out once. or multiple laminations. As a material of a board|substrate, copper, stainless steel (SUS), glass, indium tin oxide (ITO), etc. are mentioned, for example. The heating temperature during lamination is generally 40°C to 160°C. The thermocompression bonding can be performed by using a two-stage laminating machine equipped with double rollers, or by repeatedly passing the laminate of the substrate and the photosensitive resin composition layer through the rollers several times.

In the exposure step, the photosensitive resin composition layer is exposed to active light using an exposure machine. Exposure can be performed after peeling off a support as needed. In the case of exposing through a photomask, the exposure amount can be determined according to the illuminance of the light source and the exposure time, and can be measured with a light meter. In the exposing step, direct imagewise exposure can be performed. In direct image exposure, exposure is performed on a substrate by a direct writing device without using a mask. As a light source, a semiconductor laser or an ultra-high pressure mercury lamp with a wavelength of 350 nm to 410 nm is used. In the case of computer-controlled pattern drawing, the exposure amount can be determined according to the illuminance of the exposure light source and the moving speed of the substrate.

The light irradiation method used in the exposure step is preferably at least one method selected from projection exposure method, proximity exposure method, contact exposure method, direct imaging exposure method, and electron beam direct drawing method, more preferably by projection exposure method to proceed.

In the developing step, the unexposed part or the exposed part in the exposed photosensitive resin composition layer is removed by using a developing device with a developing solution. After exposure, when a support film exists on a photosensitive resin composition layer, it removes it. Next, the unexposed part or the exposed part is developed and removed using a developer containing an alkaline aqueous solution to obtain a resist image.

The alkaline aqueous solution is preferably an aqueous solution of Na ₂ CO ₃ , K ₂ CO ₃ or the like. The alkaline aqueous solution can be selected according to the characteristics of the photosensitive resin composition layer, and a Na ₂ CO ₃ aqueous solution with a concentration of 0.2% to 2% by mass is usually used. A surfactant, an antifoaming agent, a small amount of organic solvent for promoting development, etc. may also be mixed into the alkaline aqueous solution. The temperature of the developer in the developing step is preferably kept constant within the range of 20°C to 40°C.

A resist pattern can be obtained through the above steps, and a heating step at 60° C. to 300° C. can also be performed if necessary. By performing this heating step, the chemical resistance of the resist pattern can be improved. In the heating step, a heating furnace utilizing hot air, infrared rays, or far infrared rays can be used.

In order to obtain a conductive pattern, a conductive pattern forming step of etching or plating a substrate on which a resist pattern has been formed may be performed after the developing step or the heating step.

The method of manufacturing a conductive pattern can be performed, for example, by using a metal plate or a metal-coated insulating board as a substrate, forming a resist pattern by the above-mentioned resist pattern forming method, and then performing a conductive pattern forming step. In the conductive pattern forming step, a known etching method or plating method is used to form a conductive pattern on the surface of the substrate (such as a copper surface) exposed by development.

Furthermore, after the conductor pattern is produced by the above-mentioned production method of the conductor pattern, a stripping step of stripping the resist pattern from the substrate is performed using an aqueous solution having a stronger alkalinity than the developer, whereby a desired wiring pattern can be obtained. Wiring boards (such as printed wiring boards).

There is no particular limitation on the alkaline aqueous solution for stripping (hereinafter also referred to as "stripping solution"), but usually an aqueous solution of NaOH or KOH at a concentration of 2% to 5% by mass, or an organic amine-based stripping solution is used. A small amount of water-soluble solvent can also be added to the stripping solution. As a water-soluble solvent, alcohol etc. are mentioned, for example. The temperature of the stripping liquid in the stripping step is preferably in the range of 40°C to 70°C.

In this embodiment, the photosensitive element or its roll can be used in: the manufacture of printed wiring boards; the manufacture of IC (Integrated Circuit, integrated circuit) chip mounting lead frame; metal foil precision processing such as metal mask manufacturing; ball grid Manufacture of array (BGA), chip size package (CSP) and other packages; manufacture of chip-on-film (COF), tape automated bonding (TAB) and other tape substrates; manufacture of semiconductor bumps; and ITO electrodes, addressing Manufacturing of partitions between flat panel displays such as electrodes and electromagnetic wave shielding covers. In addition, the value of each said parameter was measured according to the measuring method in the following Example, unless otherwise specified. [Example]

Next, the present embodiment will be described more specifically with examples and comparative examples given. However, this embodiment is not limited to the following examples unless it deviates from the gist. The physical properties in the examples were measured by the following methods.

[Measurement of Surface Roughness] The surface roughness of the support film and the protective film was measured. One drop of water was dropped on a glass plate, and after that, each film was attached with the measurement surface facing up, and the resultant was used as a measurement sample. The measurement of surface roughness is based on the method stipulated in JIS B0601-2001, using the product name "LEXT OLS4100" manufactured by Olympus Co., Ltd. as a laser microscope, Rz measured at any 10 points with a measurement length of 258 μm The average value of the values was set as the maximum height Rz (nm). In addition, the temperature at the time of measurement was made into 23-25 degreeC. Let the surface roughness of the side of the support film that is in contact with the photosensitive resin composition layer be Rz _A1 , and set the surface roughness of the side of the support film that is opposite to the side that is in contact with the photosensitive resin composition layer The surface roughness of the side of the protective film that is in contact with the photosensitive resin composition layer is set as _{Rz C1} , and the side of the protective film that is in contact with the photosensitive resin composition layer is the opposite The surface roughness of the side surface was Rz _C2 .

[Determination of the number of particles with a diameter of 2 μm or more and 5 μm or less] A polarizer (OLS4000-QWP) was inserted into the upper part of the objective lens of the product name "LEXT OLS4100" manufactured by Olympus Co., Ltd. which is a laser microscope. Then, using a porous adsorption plate "65F-HG" manufactured by Universal Giken Co., Ltd. and a vacuum pump, the support film sample cut into 30 mm×30 mm was horizontally sucked and fixed on the stage of the laser microscope. The attracted and immobilized support film was observed through the objective lens with 50 times the laser light intensity 60 (laser wavelength is 405 nm). At this time, the central 2 μm area in the thickness direction of the support film is defined as the measurement interval to ensure that no halo caused by the reflected light from the front and back of the support film will occur. Then, measurement was performed with a measurement area of 260 μm×260 μm and a number of measurement sites of 49 points. Measurements were repeated 9 times at any different locations. Under the conditions of binarization = above threshold, threshold 1 = 10%, small particle removal = 15, hole filling = 20, the measured image was processed to make a histogram. The number of particles whose maximum diameter (μm) in the histogram is between 2 and 5 is accumulated to calculate the number of particles with a diameter of 2 μm to 5 μm.

[Determination of titanium element content] The measurement of the titanium element content in the support film is to use the product name "XRF-1800" manufactured by Shimadzu Corporation as a fluorescent X-ray analysis device, in quantitative molecular TiO ₂ , X-ray tube Target material Rh (4.0 kW), voltage 40 kV, current 95 kA, spectroscopic crystal LiF, detector SC, 2θ=86.14 deg, measurement time 40 seconds.

[How to make samples for evaluation] Samples for evaluation were prepared as follows. ＜Production of photosensitive elements＞ (Examples 1-7, Comparative Examples 1-8) The components shown in Table 1 (wherein, the numbers of each component represent the compounded amount (parts by mass) as solid content) and the methyl ethyl group measured so that the solid content concentration becomes 55% The ketones were sufficiently stirred and mixed to obtain a photosensitive resin composition preparation liquid. Table 2 shows details of the components shown in Table 1. Then, the solution of the photosensitive resin composition preparation solution was coated on the surface of the support film with a width of 500 mm, and it was dried with hot air at 90° C. for 1 minute to form a photosensitive resin composition layer. At this time, the thickness of the photosensitive resin composition layer after heating was 5 micrometers. Furthermore, a protective film was bonded to the surface of the photosensitive resin composition layer on the side where the support film was not laminated to obtain a photosensitive element. Furthermore, the photosensitive element is wound on a cylindrical plastic tube with an outer diameter of 3.5 inches, and a pressure roller arranged parallel to the width direction of the take-up shaft is used to apply pressure to the plastic tube in a linear form, and the coil is wound with a tension of 7 kg. Take 500 m to obtain the roll of photosensitive element. Table 3 shows the types and physical properties of the support films used in Examples and Comparative Examples, and Table 4 shows the types and physical properties of protective films used in Examples and Comparative Examples.

＜Whole surface of substrate＞ As a board for image evaluation, a 0.4 mm thick copper foil laminate laminated with 35 μm rolled copper foil was dipped in Mec Etch Bond CZ-8101 (manufactured by MEC Co., Ltd.) and roughened until the amount of etching reached 1 μm.

＜Laminated＞ While peeling off the protective film of the photosensitive element, the photosensitive element is laminated on the image preheated to 50°C at a roll temperature of 105°C with a heated roll laminating machine (manufactured by Asahi Kasei Co., Ltd., AL-700). The performance evaluation substrate, thereby obtaining the photosensitive element laminated body. The air pressure was set to 0.35 MPa, and the lamination speed was set to 1.5 m/min.

＜Exposure＞ Two hours after the lamination, the surface side of the support film of the photosensitive element laminate was divided into a projection exposure device (manufactured by Ushio Electric Co., Ltd., UX7-Square70) using the width of the exposed part and the unexposed part. 1:1 ratio line pattern exposure mask for exposure. When exposing and developing a line pattern with a width ratio of 1:1 between the exposed portion and the unexposed portion, the exposure is performed at the following exposure amount, that is, the exposed portion of the exposure mask = the unexposed portion = 5 μm The measured width of the exposed part and the non-exposed part of the photosensitive resin composition pattern after the image development of a part was the exposure amount of 5 micrometers.

<Development> After peeling off the support film of the photosensitive element laminate, use an alkaline developer (manufactured by Fuji Kiko Co., Ltd., a developer for dry film) to spray a 1% by mass Na ₂ CO ₃ aqueous solution at 30°C for a specified period of time Develop. The developing spray time is set to be twice the shortest developing time, and the washing spraying time after developing is set to be twice the shortest developing time. At this time, the shortest time required for the complete dissolution of the photosensitive resin composition layer in the unexposed portion was defined as the shortest developing time.

[Evaluation] About the obtained photosensitive element, the wrinkle at the time of winding up, and resolution were evaluated as follows.

＜Wrinkles during coiling＞ The roll of the obtained photosensitive element was observed visually, and it evaluated based on the following reference|standard. Excellent: no wrinkles on the roll Good: There are wrinkles on the roll, but they disappear after 3 days of storage Possible: There are wrinkles on the roll, but they disappear after 7 days of storage Impossible: There are wrinkles on the roll, which have not disappeared after 7 days of storage

＜Resolution＞ In the said exposure process, exposure was performed using the exposure mask which has the line pattern of the ratio of the width of the exposed part and the unexposed part of 1:1. Development was carried out under the above-mentioned development conditions, and the minimum line width normally formed without exposure or collapse of the hardened resist line was evaluated by an optical microscope, and the evaluation was performed according to the following criteria. If it is "possible" or more, it is regarded as a pass. Excellent: below 3 μm Good: more than 3 μm and less than 4 μm Acceptable: more than 4 μm and less than 5 μm Impossible: more than 5 μm

Table 5 shows the evaluation results of the photosensitive elements of the respective examples, and Table 6 shows the evaluation results of the photosensitive elements of the respective comparative examples.

[Table 1] compound Composition 1 Composition 2 Composition 3 Composition 4 Composition 5 A-1 57 57 A-2 57 57 A-3 57 B-1 17 15 20 15 20 B-2 6 8 6 6 6 B-3 11 11 7 14 9 B-4 5 5 5 5 5 C-1 3 3 3 3 3 C-2 0.1 C-3 0.1 C-4 0.1 0.1 0.1 D-1 0.2 0.2 0.2 0.2 0.2 D-2 0.3 0.3 0.3 0.3 0.3 total 99.1 99.1 98.1 100.1 100.1

[Table 2] mark structure A-1 Methacrylic acid/methyl methacrylate/styrene/n-butyl acrylate=25/10/60/5, Mw=28,000 in 54% acetone solution A-2 Methacrylic acid/styrene/benzyl methacrylate=25/60/15, 54% acetone solution of Mw=19,000 A-3 Methacrylic acid/cyclohexyl methacrylate/benzyl acrylate=22/50/28, Mw=30,000 in 54% acetone solution B-1 Tetramethacrylate obtained by adding an average of 15 moles of ethylene oxide to pentaerythritol B-2 Dimethacrylate of polyethylene glycol obtained by adding an average of 2 moles of ethylene oxide to both ends of bisphenol A B-3 Dimethacrylate of polyethylene glycol obtained by adding an average of 1 mole of ethylene oxide to both ends of bisphenol A B-4 Dimethacrylate of polypropylene glycol (the repeating unit of propylene glycol is 12 moles) C-1 2-(O-Chlorophenyl)-4,5-diphenylimidazole dimer C-2 9,10-Diphenylanthracene C-3 9,10-bis(isopropoxycarbonylmethoxy)anthracene (manufactured by Kawasaki Chemical Industry Co., Ltd., Anthracure UVS-107) C-4 4,4'-Bis(diethylamino)benzophenone D-1 diamond green D-2 Leuco Crystal Violet

[table 3] mark Surface roughness/nm The number of particles with a diameter above 2 μm and below 5 μm/piece/30 mm ² Titanium content/ppm Smoothing Thickness/μm The side in contact with the photosensitive resin composition layer Rz _A1 The other side Rz _A2 E-1 36 62 8 0 none 16 E-2 73 92 9 10 none 16 E-3 18 63 11 0 have 12 E-4 twenty three 53 33 0 none 16 E-5 115 115 49 0 none 16

[Table 4] mark Product name manufacturer type Surface roughness/nm The side in contact with the photosensitive resin composition layer Rz _C1 The other side Rz _C2 F-1 Torayfan#25A-KW37 toray co., ltd. OPP 160 160 F-2 MA-411 Oji F-Tex Co., Ltd. OPP 500 4000 F-3 E-200 Oji F-Tex Co., Ltd. OPP 600 600 F-4 GF-818 Tamapoly Co., Ltd. LDPE 490 490

[table 5] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 combination 1 1 1 1 3 4 5 support membrane mark E-1 E-2 E-3 E-4 E-4 E-3 E-2 Rz _A1 36 73 18 twenty three twenty three 18 73 Rz _A2 62 92 63 53 53 63 92 Rz _A2 /Rz _A1 1.7 1.3 3.5 2.3 2.3 3.5 1.3 protective film mark F-2 F-2 F-2 F-2 F-2 F-2 F-2 Rz _C1 500 500 500 500 500 500 500 Rz _C2 4000 4000 4000 4000 4000 4000 4000 Rz _C2 /Rz _C1 8 8 8 8 8 8 8 Rz _C2 /Rz _A2 64.5 43.5 63.5 75.5 75.5 63.5 43.5 Evaluation 1 Wrinkles during winding excellent good excellent excellent excellent excellent good Evaluation 2 Resolution excellent excellent excellent excellent good excellent excellent

[Table 6] Comparative example 1 Comparative example 2 Comparative example 3 Comparative example 4 Comparative Example 5 Comparative example 6 Comparative Example 7 Comparative Example 8 combination 1 1 1 2 1 2 4 5 support membrane mark E-1 E-2 E-3 E-5 E-5 E-1 E-2 E-3 Rz _A1 36 73 18 115 115 36 73 18 Rz _A2 62 92 63 115 115 62 92 63 Rz _A2 /Rz _A1 1.7 1.3 3.5 1.0 1.0 1.7 1.3 3.5 protective film mark F-1 F-1 F-1 F-2 F-2 F-3 F-4 F-4 Rz _C1 160 160 160 500 500 600 700 700 Rz _C2 160 160 160 4000 4000 600 700 700 Rz _C2 /Rz _C1 1 1 1 8 8 1 1 1 Rz _C2 /Rz _A2 2.6 1.7 2.5 34.8 34.8 9.7 7.6 11.1 Evaluation 1 Wrinkles during winding can't can't can't good good can't can't can't Evaluation 2 Resolution excellent excellent excellent can't can't good can't can't

As can be seen from Table 5, in the examples satisfying all the above-mentioned formulas (1) to (3), the resolution is excellent, and the occurrence of wrinkles when wound into a roll can be well prevented.

On the other hand, as shown in Table 6, when the formula (1) is not satisfied, that is, when Rz _A1 is greater than 100, the resolution is lowered. Also, when the formula (2) is not satisfied, that is, when Rz _C1 is 300 or less or 600 or more, the resolution is not sufficient, or wrinkles are observed during winding. Also, when the formula (3) is not satisfied, that is, when Rz _C2 /Rz _A2 is 40 or less, the resolution is insufficient, and wrinkles are also observed during winding.

As mentioned above, although embodiment of this invention was described, this invention is not limited to this, It can change suitably in the range which does not deviate from the summary of invention. [Industrial availability]

By using the photosensitive element of the present invention, both the improvement of resolution and the prevention of wrinkles during winding can be achieved, and it can be widely used as a dry film resist when forming a resist pattern.

Rz _A1 : surface roughness Rz _A2 : surface roughness Rz _C1 : surface roughness Rz _C2 : surface roughness

Fig. 1 is a cross-sectional view schematically showing an example of the configuration of the photosensitive element of the present invention.

Rz _A1 : surface roughness

Rz _A2 : surface roughness

Rz _C1 : surface roughness

Rz _C2 : surface roughness

Claims (15)

A photosensitive element, characterized in that: it has a support film (A), a photosensitive resin composition layer (B) and a protective film (C) in sequence, and the above-mentioned support film (A) specified by JIS B0601-2001 ), the surface roughness Rz _A1 (nm) of the surface of the side that is in contact with the photosensitive resin composition layer (B) above, the The surface roughness Rz _A2 (nm) of the surface on the opposite side, the surface roughness Rz _C1 (nm) of the surface of the protective film (C) that is in contact with the photosensitive resin composition layer (B) , and the surface roughness Rz _C2 (nm) of the surface of the above-mentioned protective film (C) that is opposite to the side that is in contact with the above-mentioned photosensitive resin composition layer (B) satisfies the following (1) ~ (3): ( 1)1<Rz _A1 <100(2)300<Rz _C1 <600(3)40<Rz _C2 /Rz _A2 . The photosensitive element as claimed in item 1, wherein 1<Rz _A2 <200. The photosensitive element as claimed in claim 1 or 2, wherein 1.1<Rz _A2 /Rz _A1 <7. The photosensitive element as claimed in item 1 or 2, wherein 1.1<Rz _C2 /Rz _C1 <10. The photosensitive element according to claim 1 or 2, wherein 50<Rz _C2 /Rz _A2 <100. The photosensitive element according to claim 1 or 2, wherein the number of particles with a diameter of 2 μm to 5 μm contained in the support film (A) is 30 particles/30 mm ² or less. The photosensitive element according to claim 1 or 2, wherein the number of particles with a diameter of 2 μm to 5 μm contained in the support film (A) is 15 particles/30 mm ² or less. The photosensitive element according to claim 1 or 2, wherein the number of particles with a diameter of 2 μm to 5 μm contained in the support film (A) is 10 particles/30 mm ² or less. The photosensitive element according to claim 1 or 2, wherein the content of the titanium element contained in the above-mentioned support film (A) is not less than 1 ppm and not more than 20 ppm. The photosensitive element according to claim 1 or 2, wherein at least one side of the support film (A) is smoothed. The photosensitive element according to claim 1 or 2, wherein the film thickness of the support film (A) is not less than 5 μm and not more than 12 μm. The photosensitive element according to claim 1 or 2, wherein the surface of the protective film (C) contains polypropylene resin. A winding body of a photosensitive element, which is formed by winding the photosensitive element according to any one of Claims 1 to 12. A method for forming a resist pattern, comprising: a layering step of laminating the photosensitive element according to any one of Claims 1 to 12 on a substrate; an exposure step of layering the photosensitive resin composition layer of the photosensitive element performing exposure; and a developing step, which develops and removes the unexposed portion of the photosensitive resin composition layer. The method for forming a resist pattern according to claim 14, which implements the above-mentioned exposure step by a projection exposure method.

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