Photosensitive resin laminate and method for forming resist pattern

Abstract

To provide a photosensitive resin laminate which is excellent in at least one of minimum development time, resolution, a side edge (SE) amount, a contrast and bleeding property.SOLUTION: A photosensitive resin laminate has a support, and a photosensitive resin composition layer formed on the support using a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a compound whose absorbency at a light wavelength of 550-700 nm increases, and (E) an organic developer, in which film thickness of the photosensitive resin composition layer exceeds 0 and 10 μm or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive resin laminate and a method for forming a resist pattern. [Background technology]

[0002] Conventionally, photolithography has been used for the manufacture of printed wiring boards, precision processing of metals, etc. Photosensitive resin compositions used in photolithography are classified into negative-type compositions that dissolve and remove unexposed areas, and positive-type compositions that dissolve and remove exposed areas.

[0003] When applying a photosensitive resin composition to a substrate in a photolithography method, (1) A method of applying a photoresist solution to a substrate and drying it; (2) A method of laminating a photosensitive resin layer on a substrate using a photosensitive resin laminate in which a support, a layer containing a photosensitive resin composition (hereinafter also referred to as a "photosensitive resin layer"), and, if necessary, a protective layer are laminated in this order. In the manufacture of printed wiring boards, the latter method is often used.

[0004] A method for forming a pattern using the above-mentioned photosensitive resin laminate is briefly described below. First, the protective layer is peeled off from the photosensitive resin laminate. Next, using a laminator, the photosensitive resin layer and the support are laminated on a substrate such as a copper-clad laminate or a copper-sputtered thin film in the order of the substrate, photosensitive resin layer, and support. Next, the photosensitive resin layer is exposed to light through a photomask bearing the desired wiring pattern. Next, the support is peeled off from the exposed laminate, and the non-patterned portions are dissolved or dispersed and removed using a developer to form a resist pattern on the substrate.

[0005] Furthermore, a wiring pattern can be obtained by subjecting a substrate provided with a resist pattern to an etching process or a plating process such as copper plating or solder plating.

[0006] Various photosensitive resin compositions have been investigated for forming resist patterns or wiring patterns. For example, Patent Document 1 discloses a photosensitive film having a photosensitive resin layer containing a binder polymer, a photopolymerizable compound, a leuco dye, and a compound that generates an acid when exposed to light or heat. In this photosensitive film, the photosensitive resin layer before color development can be sufficiently cured in a desired shape by exposure to light, and a colored pattern having a desired optical density can be formed by subsequent irradiation with light and / or application of heat.

[0007] Furthermore, Patent Document 2 describes a photosensitive resin composition using a radically polymerizable polymer containing structural units made of an unsaturated double bond-containing compound having a bond that can be decomposed by the action of acid and / or heat at 130 to 250° C. In this photosensitive resin composition, the bond is cleaved by acid and / or heat at 130 to 250° C. before or during peeling after photocuring and development, thereby generating phenolic hydroxyl groups and / or carboxylic acids, thereby improving the peelability against alkaline stripping solutions. Recently, the spread of smartphones (registered trademarks) and the like has led to an increasing demand for touch panel displays. Photosensitive resin laminates are often used to manufacture the wiring portions of sensors in these touch panels. In the case of touch panel sensors, various properties such as high definition and high density are often required for the wiring manufactured through an etching process. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] International Publication No. 2020 / 031379 [Patent Document 2] Japanese Patent Application Laid-Open No. 2009-3000 Summary of the Invention [Problem to be solved by the invention]

[0009] However, the minimum development time, resolution, side edge (SE) amount, contrast, and bleeding characteristics were not satisfactory. Furthermore, since some of these characteristics were considered difficult to achieve in combination, it was desired to achieve a balance between various characteristics.

[0010] The present invention has been proposed in view of the above-described conventional circumstances, and an object of the present invention is to provide a photosensitive resin laminate and a method for forming a resist pattern that are excellent in at least one of minimum development time, resolution, side edge (SE) amount, contrast, and bleeding properties. [Means for solving the problem]

[0011] [1] A support; Ingredients: (A) an alkali-soluble resin, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a compound that increases absorbance at light wavelengths of 550 to 700 nm, and (E) an organic color developer; a photosensitive resin composition layer formed on the support using a photosensitive resin composition comprising: A photosensitive resin laminate, wherein the thickness of the photosensitive resin composition layer is more than 0 μm and 10 μm or less. [2] A support; Ingredients: (A) an alkali-soluble resin, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a compound that increases absorbance at light wavelengths of 550 to 700 nm, and (E) an organic color developer; a photosensitive resin composition layer formed on the support using a photosensitive resin composition comprising: A photosensitive resin laminate, characterized in that the product of the film thickness (μm) of the photosensitive resin composition layer formed on the support and the content (mass%) of the component (E) relative to the total amount of the photosensitive resin composition is more than 0 and 5.0 or less. [3] The photosensitive resin laminate according to [1] or [2], wherein a 0.01 mg / ml acetonitrile solution of the component (E) has an absorbance at 330 nm or 405 nm of 0.1 or more and less than 1.0. [4] The photosensitive resin laminate according to any one of [1] to [3], which contains a nonionic organic color developer as the component (E). [5] The photosensitive resin laminate according to any one of [1] to [4], which contains a lophine dimer as the component (C). [6] The photosensitive resin laminate according to any one of [1] to [5], which contains a compound having a triarylmethane skeleton as the component (D). [7] The photosensitive resin laminate according to any one of [1] to [6], wherein the weight average molecular weight of the component (A) is 5,000 or more and less than 55,000. [8] The photosensitive resin laminate according to any one of [1] to [7], wherein the content of the component (A) relative to the total amount of the photosensitive resin composition is 10% by mass to 90% by mass. [9] The photosensitive resin laminate according to any one of [1] to [8], wherein the content of the component (B) relative to the total amount of the photosensitive resin composition is 5% by mass to 70% by mass.

[10] The photosensitive resin laminate according to any one of [1] to [9], wherein the content of the component (C) relative to the total amount of the photosensitive resin composition is 0.01% by mass to 20% by mass.

[11] The photosensitive resin laminate according to any one of [1] to

[10] , wherein the content of the component (D) relative to the total amount of the photosensitive resin composition is 0.001% by mass to 3% by mass.

[12] The photosensitive resin laminate according to any one of [1] to

[11] , wherein the content of the component (E) relative to the total amount of the photosensitive resin composition is more than 0% by mass and 3.5% by mass or less.

[13] The photosensitive resin laminate according to any one of [1] to

[12] , wherein the content of the component (E) relative to the total amount of the component (A) is more than 0 and 2.5 mass % or less.

[14] The photosensitive resin laminate according to any one of [1] to

[13] , wherein the component (A) contains an aromatic monomer component.

[15] The photosensitive resin laminate according to any one of [1] to

[14] , which is capable of forming a resist pattern in which ΔE / T is 3.5 or more, where ΔE is the color difference before and after exposure of a resist pattern produced using the photosensitive resin laminate, and T [μm] is the thickness of the photosensitive resin composition layer.

[16] The photosensitive resin laminate according to any one of [1] to

[15] , wherein the thickness of the photosensitive resin composition layer is more than 0 μm and less than 10 μm.

[17] a laminating step of laminating the photosensitive resin laminate according to any one of [1] to

[16] onto a substrate; an exposure step of exposing the laminated photosensitive resin laminate to light; a developing step of developing the exposed photosensitive resin laminate; A method for forming a resist pattern, comprising: A method for forming a resist pattern, wherein ΔE is the color difference before and after exposure of a resist pattern prepared using the photosensitive resin laminate, and T [μm] is the thickness of the photosensitive resin composition layer, and ΔE / T is 3.5 or more.

[18] The method for forming a resist pattern according to

[17] , wherein the exposure step is performed by an exposure method in which a pattern is directly drawn without peeling off the support, or by an exposure method in which an image of a photomask is projected through a lens.

[19] The method for forming a resist pattern according to

[17] or

[18] , wherein the exposure step is performed using a light source of 300 to 500 nm.

[20] The method for forming a resist pattern according to any one of

[17] to

[19] , wherein after the exposure step, the support is peeled off and development is performed with an aqueous inorganic alkaline solution. [twenty one] The method for forming a resist pattern according to any one of

[17] to

[20] , further comprising the step of etching the substrate in an area where no pattern is disposed, after the developing step. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a photosensitive resin laminate and a method for forming a resist pattern that are excellent in at least one of minimum development time, resolution, side edge (SE) amount, contrast, and bleeding properties. DETAILED DESCRIPTION OF THE INVENTION

[0013] Hereinafter, a mode for carrying out the present invention (hereinafter abbreviated as "embodiment") will be described in detail. Note that the present invention is not limited to the following embodiment, and various modifications can be made within the scope of the gist of the present invention.

[0014] Also, in this specification, "(meth)acrylic" means acrylic or methacrylic, "(meth)acryloyl" means acryloyl or methacryloyl, and "(meth)acrylate" means acrylate or methacrylate.

[0015] The photosensitive resin laminate of the present invention comprises: A support; Ingredients: (A) an alkali-soluble resin, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a compound that increases absorbance at light wavelengths of 550 to 700 nm, and (E) an organic color developer; a photosensitive resin composition layer formed on a support using a photosensitive resin composition comprising the following: The photosensitive resin composition layer has a thickness of more than 0 μm and 10 μm or less.

[0016] In the photosensitive resin laminate of the present invention, by including the component (D), a photosensitive resin composition having high resolution and excellent visibility of exposed areas can be obtained. By including the component (E), a photosensitive resin composition having high sensitivity and excellent visibility of exposed areas can be obtained. Furthermore, by having the film thickness of the photosensitive resin composition layer be greater than 0 and not greater than 10 μm, a photosensitive resin composition having high resolution and excellent release properties can be obtained. As a result, the present invention can provide a photosensitive resin laminate that is excellent in at least one of minimum development time, resolution, side edge (SE) amount, contrast, and bleeding properties. Each component will be described in detail below.

[0017] <(A) Alkali-soluble resin> The alkali-soluble resin (A) is a polymer that can be dissolved in an alkaline solution. The alkali-soluble resin (A) preferably has a carboxyl group, more preferably has an acid equivalent of 100 to 600, and is even more preferably a copolymer containing a carboxyl group-containing monomer as a copolymerization component. Furthermore, the alkali-soluble resin (A) may be thermoplastic.

[0018] The acid value (mgKOH / g) of the alkali-soluble resin (A) is preferably greater than 0, and is preferably 200 or less from the viewpoints of the development resistance of the photosensitive resin layer, the resolution and adhesion of the resist pattern, and further the developability and releasability of the photosensitive resin layer.

[0019] The acid value (acid equivalent) of the alkali-soluble resin (A) is more preferably more than 0 and not more than 78.0, and even more preferably more than 0 and not more than 76.0.

[0020] An acid value in the above range corresponds to a so-called "low acid value" compared with the prior art. In one embodiment of the present invention, while there has been a particular demand in recent years for thinner photosensitive resin layers, the "thinner photosensitive resin layer" and the "low acid value" have been realized. In the past, one method known to achieve high resolution (low SE) was to improve the hydrophobicity of the resist. However, improving the hydrophobicity of the resist reduces its solubility in the developer, which tends to lengthen the development time. In this regard, lowering the molecular weight of the resin to shorten the development time can sometimes lead to a decrease in Cu deficiency (film strength).

[0021] (A) The alkali-soluble resin is represented by the following formula (I):

number

[0022] Glass transition temperature Tg iWhen calculating the glass transition temperature of a homopolymer consisting of comonomers that form the corresponding alkali-soluble resin, the value shown in "Polymer Handbook, Third Edition, John Wiley & Sons, 1989, p. 209, Chapter VI 'Glass transition temperatures of polymers'" edited by Brandrup, J. and Immergut, EH, should be used.

[0023] Tg of representative comonomers i are as follows (all literature values): Methacrylic acid: Tg=501K Benzyl methacrylate: Tg=327K Methyl methacrylate: Tg=378K Styrene: Tg=373K 2-Ethylhexyl acrylate: Tg=223K Cyclohexyl methacrylate: Tg=365K Butyl acrylate: Tg=219K The glass transition temperature (Tg total The alkali-soluble resin exhibiting the formula (I) is preferably a copolymer of an acid monomer and another monomer.

[0024] The glass transition temperature (Tg total There is no particular limitation on the lower limit of the glass transition temperature (Tg total ) may be 10°C or higher, 30°C or higher, 50°C or higher, or 70°C or higher.

[0025] The weight-average molecular weight (Mw) of the (A) alkali-soluble resin is preferably 5,000 or more and less than 55,000. From the viewpoints of maintaining a uniform thickness of a photosensitive resin laminate such as a dry film resist and obtaining resistance to a developer, the weight-average molecular weight of the (A) alkali-soluble resin is preferably 5,000 or more, while from the viewpoint of maintaining the developability of a photosensitive resin laminate such as a dry film resist, the weight-average molecular weight is preferably less than 55,000. The weight-average molecular weight (Mw) of the (A) alkali-soluble resin is more preferably 10,000 to 50,000, and even more preferably 23,000 to 50,000. Furthermore, the dispersity (Mw / Mn) of the (A) alkali-soluble resin, which is the ratio of the Mw to the number-average molecular weight (Mn) of the (A) alkali-soluble resin, is preferably 1.0 to 6.0.

[0026] The alkali-soluble resin (A) is preferably obtained by polymerizing at least one type of first monomer described below. The alkali-soluble resin (A) preferably contains an aromatic monomer component contained in the second monomer described below. Furthermore, the alkali-soluble resin (A) is more preferably obtained by copolymerizing at least one type of first monomer with at least one type of second monomer described below.

[0027] The first monomer is a monomer containing a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, β-carboxyethyl (meth)acrylate, and maleic acid half ester. Among these, (meth)acrylic acid is particularly preferred.

[0028] Examples of the second monomer include unsaturated aromatic compounds (sometimes referred to as "aromatic monomers"), (meth)acrylic acid alkyl esters, (meth)acrylic acid aralkyl esters, conjugated diene compounds, polar monomers, and crosslinkable monomers. Among these, unsaturated aromatic compounds are preferred from the viewpoint of improving the resolution of the resist pattern. When using a second monomer containing an unsaturated aromatic compound, the proportion of the unsaturated aromatic compound relative to the total amount of the alkali-soluble resin (A) is preferably 5% by mass or more, more preferably 10% by mass or more.

[0029] Examples of unsaturated aromatic compounds include benzyl (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, styrene, cinnamic acid, polymerizable styrene derivatives (e.g., methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, styrene trimer, etc.), etc. Among these, benzyl (meth)acrylate and styrene are preferred, and benzyl (meth)acrylate is more preferred.

[0030] The (meth)acrylic acid alkyl ester is a concept that encompasses both chain alkyl esters and cyclic alkyl esters, and specific examples thereof include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, t-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, heptyl (meth)acrylate, octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, lauryl (meth)acrylate, n-tetradecyl (meth)acrylate, stearyl (meth)acrylate, and cyclohexyl (meth)acrylate.

[0031] Examples of (meth)acrylic acid aralkyl esters include benzyl (meth)acrylate, and examples of conjugated diene compounds include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5-diethyl-1,3-octadiene, and 3-butyl-1,3-octadiene. Examples of polar monomers include hydroxy group-containing monomers such as hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, and penteneol; amino group-containing monomers such as 2-aminoethyl methacrylate; amide group-containing monomers such as (meth)acrylamide and N-methylol (meth)acrylamide; cyano group-containing monomers such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, and α-cyanoethyl acrylate; and epoxy group-containing monomers such as glycidyl (meth)acrylate and 3,4-epoxycyclohexyl (meth)acrylate.

[0032] Examples of the crosslinkable monomer include trimethylolpropane triacrylate and divinylbenzene.

[0033] The alkali-soluble resin (A) can be prepared by subjecting the first monomer and / or the second monomer to a known polymerization method, preferably addition polymerization, more preferably radical polymerization.

[0034] The content of (A) alkali-soluble resin in the photosensitive resin composition (based on the total solid content of the photosensitive resin composition; hereinafter, the same applies to each component unless otherwise specified) is preferably in the range of 10% to 90% by mass, more preferably in the range of 20% to 80% by mass, and even more preferably in the range of 30% to 60% by mass. The content of (A) alkali-soluble resin is preferably 10% by mass or more from the viewpoint of maintaining the alkaline developability of the photosensitive resin layer, while being preferably 90% by mass or less from the viewpoint of ensuring that the resist pattern formed by exposure fully exhibits the performance of the resist material.

[0035] <(B) Photopolymerizable Compound Having an Ethylenically Unsaturated Bond> (B) The photopolymerizable compound having an ethylenically unsaturated bond is a compound that has polymerizability due to the presence of an ethylenically unsaturated bond, specifically an ethylenically unsaturated group, in its structure. The photosensitive resin composition may have at least one ethylenic double bond as component (B), and it is preferable to use a compound having two or more ethylenic double bonds.

[0036] Specific examples of the component (B) include di(meth)acrylates of polyalkylene glycols in which an average of 2 to 15 moles of alkylene oxide are added to both ends of bisphenol A, tri(meth)acrylates of polyalkylene triols in which an average of 3 to 25 moles of alkylene oxide are added to trimethylolpropane, glycerin, trimethylolpropane, pentaerythritol, diglycerin, ditrimethylolpropane, and polyalkylene oxide groups are added to isocyanurate rings, and ε-carboxylates. Examples of suitable polyols include compounds obtained by converting alcohols obtained by modifying them with prolactone or the like into (meth)acrylates, compounds obtained by directly reacting these with (meth)acrylic acid without modifying them with an alkylene oxide group or ε-caprolactone, tetra(meth)acrylates of polyols in which an average of 4 to 35 moles of alkylene oxide are added to pentaerythritol, and hexa(meth)acrylates of polyols in which an average of 4 to 30 moles of alkylene oxide are added to dipentaerythritol. These may be used alone or in combination of two or more.

[0037] The content of the (B) photopolymerizable compound having an ethylenically unsaturated group in the photosensitive resin composition is preferably 5% by mass to 70% by mass, more preferably 20% by mass to 60% by mass, and even more preferably 30% by mass to 50% by mass. The content of the (B) compound having an ethylenically unsaturated group is preferably 5% by mass or more from the viewpoint of suppressing poor curing of the photosensitive resin layer and delay in development time, while it is preferably 70% by mass or less from the viewpoint of suppressing delay in peeling of the cured resist.

[0038] <(C) Photopolymerization initiator> The (C) photopolymerization initiator is a compound that generates radicals when exposed to actinic rays and can polymerize the (B) photopolymerizable compound having an ethylenically unsaturated group, etc. The photosensitive resin composition may contain (C) a photopolymerization initiator that is generally known in the art.

[0039] Examples of the (C) photopolymerization initiator include hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinone compounds, aromatic ketone compounds, acetophenone compounds, acylphosphine oxide compounds, benzoin compounds, benzoin ether compounds, dialkyl ketal compounds, thioxanthone compounds, dialkylaminobenzoic acid ester compounds, oxime ester compounds, acridine compounds, pyrazoline derivatives, N-arylamino acid ester compounds, and halogen compounds.

[0040] Examples of the hexaarylbiimidazole compound include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole (also known as 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole), 2,2',5-tris-(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis-(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, and 2,4,5-tris-(o-chlorophenyl)-diphenyl Biimidazole, 2-(o-chlorophenyl)-bis-4,5-(3,4-dimethoxyphenyl)-biimidazole, 2,2'-bis-(2-fluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3-difluoromethylphenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,5- difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,6-difluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3 ,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,5-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,4,6-trifluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,Examples include 2'-bis-(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, 2,2'-bis-(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis-(3-methoxyphenyl)-biimidazole, and lophine (2,4,5-triarylimidazole) dimer.

[0041] Examples of lophine dimers include 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-bis-(m-methoxyphenyl)imidazole dimer, and 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer. From the viewpoints of high sensitivity, resolution, and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is particularly preferred.

[0042] Examples of N-aryl-α-amino acid compounds include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine, etc. N-phenylglycine is particularly preferred because of its high sensitizing effect.

[0043] Examples of quinone compounds include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 2,3-dimethylanthraquinone, and 3-chloro-2-methylanthraquinone.

[0044] Examples of aromatic ketone compounds include benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone. Examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 4-(2-hydroxyethoxy)-phenyl(2-hydroxy-2-propyl)ketone, 1-hydroxycyclohexylphenyl ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butanone-1, and 2-methyl-1-[4-(methylthio)phenyl]-2-morpholino-propanone-1. Commercially available acetophenone compounds include Irgacure-907, Irgacure-369, and Irgacure-379 manufactured by Ciba Specialty Chemicals. From the viewpoint of use as a sensitizer and adhesion, 4,4'-bis(diethylamino)benzophenone is preferred.

[0045] Examples of acylphosphine oxide compounds include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, etc. Commercially available acylphosphine oxide compounds include Lucirin TPO manufactured by BASF and Irgacure-819 manufactured by Ciba Specialty Chemicals.

[0046] Examples of the benzoin compounds and benzoin ether compounds include benzoin, benzoin ethyl ether, benzoin phenyl ether, methylbenzoin, and ethylbenzoin. Examples of the dialkyl ketal compound include benzyl dimethyl ketal and benzyl diethyl ketal. Examples of thioxanthone compounds include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, and 2-chlorothioxanthone. Examples of dialkylaminobenzoate compounds include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, and 2-ethylhexyl-4-(dimethylamino)benzoate.

[0047] Examples of oxime ester compounds include 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2-(O-ethoxycarbonyl)oxime, etc. Commercially available oxime ester compounds include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 manufactured by Ciba Specialty Chemicals.

[0048] As the acridine compound, 1,7-bis(9,9'-acridinyl)heptane or 9-phenylacridine is preferred in terms of sensitivity, resolution, availability, etc.

[0049] From the viewpoints of adhesion and rectangularity of the resist pattern, the pyrazoline derivatives are preferably 1-phenyl-3-(4-tert-butyl-styryl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(4-biphenyl)-5-(4-tert-butyl-phenyl)-pyrazoline, and 1-phenyl-3-(4-biphenyl)-5-(4-tert-octyl-phenyl)-pyrazoline.

[0050] Examples of the ester compound of N-arylamino acid include methyl ester of N-phenylglycine, ethyl ester of N-phenylglycine, n-propyl ester of N-phenylglycine, isopropyl ester of N-phenylglycine, 1-butyl ester of N-phenylglycine, 2-butyl ester of N-phenylglycine, tert-butyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, hexyl ester of N-phenylglycine, pentyl ester of N-phenylglycine, and octyl ester of N-phenylglycine.

[0051] Examples of halogen compounds include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenylsulfone, carbon tetrabromide, tris(2,3-dibromopropyl)phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis(p-chlorophenyl)ethane, chlorinated triazine compounds, and diaryliodonium compounds, with tribromomethylphenylsulfone being particularly preferred.

[0052] The content of the (C) photopolymerization initiator in the photosensitive resin composition is preferably 0.01% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass. By adjusting the content of the (C) photopolymerization initiator within the above range, it is possible to obtain a photosensitive resin composition that has sufficient sensitivity, allows light to be sufficiently transmitted to the bottom of the resist, provides high resolution, and is well-balanced with the amount of side etching in the conductor pattern.

[0053] From the viewpoints of high sensitivity, resolution, and adhesion, it is preferable that the (C) photopolymerization initiator contains a lophine dimer. In this case, the content of the lophine dimer in the photosensitive resin composition is preferably 0.1 to 10% by mass, more preferably 0.5 to 5% by mass.

[0054] <(D) Compounds that increase absorbance at light wavelengths of 550 to 700 nm> Component (D) is a compound whose structure changes when irradiated with light having a wavelength of 300 to 500 nm, and whose absorbance at a wavelength of 550 to 700 nm increases. By including component (D), a photosensitive resin composition can be obtained that has high resolution and excellent visibility in exposed areas.

[0055] Examples of such component (D) include triarylmethane compounds, spiropyran compounds, fluoran compounds, diarylmethane compounds, rhodamine lactam compounds, indolylphthalide compounds, leucoauramine compounds, phenothiazine compounds, xanthene compounds, and oxazine compounds.

[0056] From the viewpoint of visibility of exposed areas, it is preferable that the component (D) contains a compound having a triarylmethane skeleton. Examples of compounds having a triarylmethane skeleton include tris(4-dimethylaminophenyl)methane [leucocrystal violet], Green DCF, methyl blue, thymol blue, bromothymol blue, bromophenol blue, water blue, solvent blue 5, basic blue 7, xylene cyanol, Coomassie brilliant blue G250, Coomassie brilliant blue R250, brilliant blue FCF, green S, malachite green, fast green FCF, basic violet 3, basic violet 4, methyl violet 2B, methyl violet 6B, methyl violet 10B, crystal violet lactone, phenolphthalein, phenol red, cresol red, magenta O, and phloxine. Among these, malachite green or basic violet 3 is preferred.

[0057] The content of component (D) in the photosensitive resin composition is preferably 0.001% by mass to 3% by mass, more preferably 0.002% by mass to 2% by mass. By adjusting the content of component (D) within the above range, it is possible to obtain a photosensitive resin composition that has sufficient sensitivity, allows sufficient light transmission to the bottom of the resist, and provides high resolution while being well balanced with the amount of side etching in the conductor pattern.

[0058] <(E) Organic color developer> The (E) organic color developer is a compound capable of generating an acid when irradiated with radiation such as ultraviolet light, far ultraviolet light, X-rays, or charged particle beams. By including such an (E) organic color developer, the photosensitive resin composition can have high resolution, high sensitivity, and excellent visibility in exposed areas.

[0059] Examples of the (E) organic color developer include photoacid generators that decompose upon irradiation with light to generate an acid, such as trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, oxime sulfonate compounds, onium salt compounds such as diaryliodonium salts and triarylsulfonium salts, and quaternary ammonium salts. Among these, oxime sulfonate compounds and imide sulfonate compounds are preferred from the viewpoints of absorption wavelength and the strength of the acid generated.

[0060] Specific examples of (E) organic color developers include (5-propylsulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, (5-p-toluenesulfonyloxyimino-5H-thiophen-2-ylidene)-(2-methylphenyl)acetonitrile, naphthalimide trifluoromethylsulfonate, naphthalimide methanesulfonate, and naphthalimide camphorsulfonate.

[0061] The absorbance of a 0.01 mg / ml acetonitrile solution of (E) the organic color developer at 330 nm or 405 nm is preferably 0.1 or more. The absorbance is preferably less than 1.0, more preferably 0.15 or more and less than 0.9. This allows for the production of a photosensitive resin composition with high sensitivity and excellent visibility in exposed areas.

[0062] From the viewpoint of the storage stability and color development stability of the photosensitive resin laminate, it is preferable that the (E) organic color developer contains a nonionic organic color developer, which makes it possible to form a photosensitive resin laminate and maintain the visibility of the exposed area stably even after long-term storage without reducing the resolution. Examples of nonionic organic color developers include trichloromethyl-s-triazines, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. Among these, oxime sulfonate compounds and imide sulfonate compounds are preferred from the viewpoints of absorption wavelength and the strength of the acid generated.

[0063] The content of the (E) organic color developer in the photosensitive resin composition is more than 0 to 3.5% by mass or less, preferably 0.0005% to 3% by mass, more preferably 0.001% to 2% by mass, and even more preferably 0.5% to 0.9% by mass. By adjusting the content of the (E) organic color developer within the above range, a photosensitive resin composition can be obtained that has excellent compatibility with the composition, sufficient sensitivity, allows sufficient light transmission to the bottom of the resist, achieves high resolution, and is well-balanced with the amount of side etching in the conductor pattern. In particular, for the same reasons as above, it is preferable that the content of the (E) organic color developer relative to the total amount of the (A) alkali-soluble resin is more than 0 and 2.5% by mass or less.

[0064] <Other ingredients> The photosensitive resin composition preferably contains, as desired, additives such as a base dye, an antioxidant, a stabilizer, a sensitizer, a plasticizer, etc. The other components are components other than the above (A) to (E).

[0065] A base dye can be blended into the photosensitive resin composition of this embodiment to impart color development to unexposed areas and excellent peelability. Examples include Basic Green 1 [CAS Number (hereinafter the same): 633-03-4] (e.g., Aizen Diamond Green GH, product name, manufactured by Hodogaya Chemical Co., Ltd.), Fuchsin [632-99-5], Methyl Violet [603-47-4], Methyl Green [82-94-0], Victoria Blue B [2580-56-5], Basic Blue 7 [2390-60-5] (e.g., Aizen Victoria Pure Blue BOH, product name, manufactured by Hodogaya Chemical Co., Ltd.), Rhodamine B [81-88-9], Rhodamine 6G [989-38-8], and Basic Yellow 2 [2465-27-2]. Among these, Basic Green 1 is preferred from the viewpoint of improving colorability, hue stability, and exposure contrast. These may be used alone or in combination of two or more.

[0066] The content of the base dye in the photosensitive resin composition is preferably in the range of 0.001% by mass to 3% by mass, more preferably in the range of 0.01% by mass to 2% by mass, and even more preferably in the range of 0.04% by mass to 1% by mass. The content of the dye is preferably 0.001% by mass or more from the viewpoint of obtaining good colorability, and is preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

[0067] Examples of antioxidants include triphenyl phosphite (e.g., manufactured by Asahi Denka Kogyo Co., Ltd., trade name: TPP), tris(2,4-di-tert-butylphenyl) phosphite (e.g., manufactured by Asahi Denka Kogyo Co., Ltd., trade name: 2112), tris(mononylphenyl) phosphite (e.g., manufactured by Asahi Denka Kogyo Co., Ltd., trade name: 1178), and bis(mononylphenyl)-dinonylphenyl phosphite (e.g., manufactured by Asahi Denka Kogyo Co., Ltd., trade name: 329K). These may be used alone or in combination of two or more.

[0068] The content of the antioxidant in the photosensitive resin composition is preferably in the range of 0.01 to 0.8% by mass, more preferably in the range of 0.01 to 0.3% by mass. The content of the antioxidant is preferably 0.01% by mass or more from the viewpoint of achieving good hue stability of the resist pattern and improving the sensitivity of the photosensitive resin layer, and on the other hand, from the viewpoint of achieving good hue stability while suppressing color development of the resist pattern and improving adhesion, the content is preferably 0.8% by mass or less.

[0069] The stabilizer is preferably used from the viewpoint of improving the thermal stability and / or storage stability of the photosensitive resin composition. Examples of the stabilizer include at least one compound selected from the group consisting of a radical polymerization inhibitor and an alkylene oxide compound having a glycidyl group. These may be used alone or in combination of two or more.

[0070] Examples of radical polymerization inhibitors include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, tert-butylcatechol, cuprous chloride, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], nitrosophenylhydroxyamine aluminum salt (e.g., aluminum salt with 3 moles of nitrosophenylhydroxylamine added), and diphenylnitrosamine. Among these, triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] or aluminum salt with 3 moles of nitrosophenylhydroxylamine added is preferred. These can be used alone or in combination of two or more.

[0071] Examples of alkylene oxide compounds having a glycidyl group include neopentyl glycol diglycidyl ether (e.g., Epolite 1500NP manufactured by Kyoeisha Chemical Co., Ltd.), nonaethylene glycol diglycidyl ether (e.g., Epolite 400E manufactured by Kyoeisha Chemical Co., Ltd.), bisphenol A-propylene oxide 2-mol adduct diglycidyl ether (e.g., Epolite 3002 manufactured by Kyoeisha Chemical Co., Ltd.), and 1,6-hexanediol diglycidyl ether (e.g., Epolite 1600 manufactured by Kyoeisha Chemical Co., Ltd.). These compounds may be used alone or in combination of two or more.

[0072] The total content of the radical polymerization inhibitor and the alkylene oxide compound having a glycidyl group in the photosensitive resin composition is preferably in the range of 0.001% by mass to 3% by mass, more preferably 0.05% by mass to 1% by mass. This total content is preferably 0.001% by mass or more from the viewpoint of imparting good storage stability to the photosensitive resin composition, and is preferably 3% by mass or less from the viewpoint of maintaining the sensitivity of the photosensitive resin layer.

[0073] <Photosensitive resin composition mixture> In one embodiment, a photosensitive resin composition preparation can be prepared by adding a solvent to the photosensitive resin composition. Suitable solvents include, for example, ketones such as acetone and methyl ethyl ketone (MEK), and alcohols such as methanol, ethanol, and isopropyl alcohol. The solvent is preferably added to the photosensitive resin composition so that the viscosity of the photosensitive resin composition preparation is 500 mPa·sec to 4000 mPa·sec at 25°C.

[0074] <Photosensitive resin laminate, dry film resist and transfer film> A photosensitive resin laminate can be provided using the photosensitive resin composition or photosensitive resin composition preparation of the present disclosure. The photosensitive resin laminate has a support film (support) and a layer containing the photosensitive resin composition formed on the support film. The photosensitive resin laminate may have a protective layer on the surface opposite to the support film side, as necessary. From the viewpoint of significantly achieving the effects of the present invention, the photosensitive resin laminate is preferably a dry film resist or a transfer film, and more preferably a dry film resist.

[0075] The support film is preferably transparent and transmits light emitted from the exposure light source. Examples of such support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, polystyrene film, polyacrylonitrile film, styrene copolymer film, polyamide film, and cellulose derivative film. These films can also be stretched as needed.

[0076] The haze of the support film is preferably not more than 5. A thinner support film is advantageous in terms of image formation and economy, but taking into consideration the function of maintaining strength, the thickness is preferably 10 μm to 30 μm.

[0077] The layer of the photosensitive resin composition described above (hereinafter also referred to as "photosensitive resin layer") may contain or consist of a photosensitive resin composition. The film thickness of the layer of the photosensitive resin composition in the photosensitive resin laminate is preferably 0.5 μm to 25 μm, more preferably 1 μm to 20 μm, from the viewpoints of the resolution of the resist pattern, the amount of side etching, the piercing strength, and the peelability. From the same viewpoint, the upper limit of the film thickness is more preferably 16 μm or less, particularly preferably 10 μm or less, and most preferably less than 10 μm.

[0078] An important characteristic of the protective layer used in the photosensitive resin laminate is that it has an appropriate adhesive strength. In other words, it is preferable that the adhesive strength of the protective layer to the photosensitive resin layer is sufficiently smaller than the adhesive strength of the support film to the photosensitive resin layer, so that the protective layer can be easily peeled off from the photosensitive resin laminate. For example, a polyethylene film, a polypropylene film, a polyethylene terephthalate film, a polyester film, etc. can be used as the protective layer. In addition, a release layer that can be suitably used to peel the protective film from the photoresist layer may be provided on one side of the protective layer film. Release layers are generally classified into silicone compounds and non-silicone compounds. Silicone compounds include condensation-type silicone resins obtained by reacting a silanol-terminated polydimethylsiloxane with a polymethylhydrogensiloxane or a polymethylmethoxysiloxane; addition-type silicone resins obtained by reacting a dimethylsiloxane-methylvinylsiloxane copolymer or a dimethylsiloxane-methylhexenylsiloxane copolymer with a polymethylhydrogensiloxane; UV-curable or electron-beam-curable silicone resins obtained by curing an acrylic silicone or an epoxy-containing silicone with UV or an electron beam; and modified silicone resins such as epoxy-modified silicone resins (silicone epoxy), polyester-modified silicone resins (silicone polyester), acrylic-modified silicone resins (silicone acrylic), phenol-modified silicone resins (silicone phenol), alkyd-modified silicone resins (silicone alkyd), and melamine-modified silicone resins (silicone melamine). Non-silicone compounds include alkyd (also called alkyd) resins, long-chain alkyl resins, acrylic resins, and polyolefin resins. The thickness of the release layer is preferably in the range of 0.001 to 2 μm, more preferably 0.005 to 1 μm, and even more preferably 0.01 to 0.5 μm. If the thickness exceeds 2 μm, the appearance of the coating film may deteriorate and the coating film may not be sufficiently cured, while if the thickness is less than 0.001 μm, sufficient release properties may not be obtained. The thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.

[0079] <Method for producing photosensitive resin laminate> The photosensitive resin laminate can be produced by sequentially laminating a photosensitive resin layer and, if necessary, a protective layer on a support film (support). Known methods can be used for this purpose. For example, the photosensitive resin composition used in the photosensitive resin layer is mixed with a solvent that dissolves it to form a uniform solution-like photosensitive resin composition preparation (coating liquid). The coating liquid is then applied to the support film using a bar coater or roll coater, and then dried, thereby laminating the photosensitive resin layer on the support film. If necessary, a protective layer can be laminated on the photosensitive resin layer to produce a photosensitive resin laminate.

[0080] In the photosensitive resin laminate of this embodiment, the product of the film thickness (μm) of the photosensitive resin layer formed on the support film (support) and the content (mass %) of the (E) organic color developer relative to the total amount of the photosensitive resin composition is more than 0 and 5.0 or less. In this embodiment, the focus is on making the photosensitive resin layer a thin film and adjusting the content of the (E) organic color developer to a specific small amount range. By limiting the product of the film thickness (μm) of the photosensitive resin layer and the content of the (E) organic color developer to a specific range, it is possible to obtain a photosensitive resin laminate that has sufficient sensitivity, allows light to be sufficiently transmitted to the bottom of the resist, obtains higher resolution, and is particularly well-balanced with the amount of side etching in the conductor pattern.

[0081] Furthermore, the photosensitive resin laminate of this embodiment can form a resist pattern in which ΔE / T is 3.5 or more, where ΔE is the color difference before and after exposure of a resist pattern prepared using the photosensitive resin laminate and T [μm] is the thickness of the photosensitive resin composition layer.

[0082] <Method for forming a resist pattern> Another aspect of the present invention is a method for producing a method for manufacturing a semiconductor device comprising the steps of: a step of laminating the photosensitive resin laminate of the present disclosure onto a substrate (lamination step); A step of exposing the laminated photosensitive resin laminate to light (exposure step), and A step of developing the exposed photosensitive resin laminate (developing step) The present invention provides a method for forming a resist pattern, comprising the steps of:

[0083] In particular, in this embodiment, when the color difference before and after exposure of a resist pattern prepared using the photosensitive resin laminate is ΔE and the thickness of the photosensitive resin composition layer is T [μm], from the viewpoint of improving the visibility of exposed and unexposed areas, ΔE / T is 3.5 or more, and preferably 4.0 or more.

[0084] In the method for forming a resist pattern of this embodiment, the color difference ΔE between before and after exposure of the resist pattern produced using the photosensitive resin laminate may be 8.0 or more. From the viewpoint of improving contrast, the color difference ΔE is preferably 10 or more, and more preferably 11 or more. In this specification, the color difference ΔE between before and after exposure of a resist pattern is measured by the method described in the examples below.

[0085] <Wiring pattern formation method> Yet another aspect of the present disclosure is a method for producing a pharmaceutical composition comprising the steps of: A step of etching or plating the substrate on which the resist pattern has been formed by the above-mentioned resist pattern forming method (etching or plating step). The present invention provides a method for forming a wiring pattern, comprising the steps of:

[0086] An example of a method for forming a resist and a wiring pattern using a photosensitive resin laminate and a substrate will be described below.

[0087] (Lamination process) In the case where the photosensitive resin laminate has a protective layer, the lamination step can be carried out by peeling off the protective layer from the laminate, and then laminating the photosensitive resin layer onto the surface of the substrate by heat and pressure using a laminator, for example.

[0088] Examples of materials for the substrate include copper (Cu), stainless steel (SUS), glass, indium tin oxide (ITO), and flexible substrates laminated with a conductive thin film. Examples of conductive thin films include ITO, copper, copper-nickel alloy, and silver. Examples of materials constituting the flexible substrate include polyethylene terephthalate (PET).

[0089] The substrate may be in the form of a copper-clad laminate with copper wiring formed thereon, a substrate made of glass alone, or a transparent resin substrate with a transparent electrode (e.g., ITO, Ag nanowire substrate, etc.) or a metal electrode (e.g., Cu, Al, Ag, Ni, Mo, and alloys of at least two of these, etc.) formed thereon. The substrate may also have through-holes to accommodate multilayer substrates.

[0090] From the viewpoint of significantly achieving the effects of the present invention, the substrate used is preferably a copper-clad laminate, more preferably a copper-clad laminate having a thickness of 1.6 mm and a through-hole with a diameter of 6 mm, laminated with a copper foil having a thickness of 35 μm.

[0091] The photosensitive resin layer may be laminated on only one surface of the substrate, or may be laminated on both surfaces of the substrate as necessary. The heating temperature during lamination is preferably 40°C to 160°C, more preferably 80°C to 120°C. The thermocompression bonding may be performed two or more times to improve the adhesion of the resulting resist pattern to the substrate. When performing the thermocompression bonding two or more times, a two-stage laminator equipped with two rolls may be used, or the laminate of the substrate and the photosensitive resin layer may be repeatedly passed through the rolls to be compressed.

[0092] (Exposure process) In the exposure step, the photosensitive resin layer is exposed using an exposure machine. From the viewpoints of mask contamination and dimensional stability, this exposure is preferably performed by an exposure method in which a pattern is directly drawn without peeling off the support, or an exposure method in which an image of a photomask is projected through a lens. By carrying out this patternwise exposure, a resist film having a desired pattern (resist pattern) can be obtained after a development step described later. The patternwise exposure may be carried out by either a method of exposure through a photomask or a method of maskless exposure.

[0093] When exposure is performed through a photomask, the exposure dose is determined by the illuminance of the light source and the exposure time. The exposure dose may be measured using an actinometer. In maskless exposure, a photomask is not used, and exposure is performed directly on the substrate using a drawing device. As the light source, a semiconductor laser with a wavelength of 300 to 500 nm, an ultra-high pressure mercury lamp, etc. are used. In maskless exposure, the drawing pattern is controlled by a computer, and the exposure dose can be determined by the illuminance of the exposure light source and the moving speed of the substrate.

[0094] From the viewpoints of improving the resolution of the resist pattern, reducing the amount of side etching, and improving the yield of the resist or wiring pattern, it is preferable to carry out exposure through a photomask.

[0095] (Development process) In the development step, the non-patterned portions of the photosensitive resin layer are removed with a developer. In the development step, the support is peeled off, and a developer consisting of an inorganic alkaline aqueous solution is used to dissolve and remove the unexposed portions to obtain a resist pattern when a negative-tone photosensitive resin composition is used. In the development step, the exposed portions are dissolved and removed to obtain a resist pattern when a positive-tone photosensitive resin composition is used.

[0096] As the alkaline aqueous solution, it is preferable to use an inorganic alkaline aqueous solution such as Na2CO3 or K2CO3. The alkaline aqueous solution is selected according to the properties of the photosensitive resin composition layer, but it is preferable to use an aqueous Na2CO3 solution with a concentration of 0.2% by mass to 2% by mass. The alkaline aqueous solution may contain a surfactant, an antifoaming agent, a small amount of an organic solvent to promote development, etc. The temperature of the developer in the development step is preferably kept constant in the range of 18°C ​​to 40°C.

[0097] If desired, after the development step, a heating step may be carried out in which the obtained resist pattern is heated at 100°C to 300°C. By carrying out this heating step, the chemical resistance and resolution of the resist pattern may be improved. For heating, a heating furnace using an appropriate method such as hot air, infrared, or far infrared can be used.

[0098] (etching or plating process) After forming a resist pattern by the above-described resist pattern forming method, a wiring pattern can be formed on the substrate by etching or plating the substrate in the area where the resist pattern is not arranged. From the viewpoint of significantly achieving the effects of the present invention, it is preferable to perform at least an etching step.

[0099] The etching step can be carried out according to a known etching method, for example, by spraying an etching solution onto the resist pattern to etch the substrate surface not covered by the resist pattern. Examples of etching methods include acid etching and alkaline etching, and the etching is carried out by a method appropriate for the photosensitive resin laminate used. The etching solution can be, for example, an aqueous hydrochloric acid solution, an aqueous ferric chloride solution, or a mixture thereof. The etching solution can also be sprayed.

[0100] The plating step can be carried out by plating the substrate surface exposed by development with metal (for example, with a copper sulfate plating solution) or solder according to known plating methods.

[0101] After the etching step and / or plating step, the photosensitive resin laminate may be treated with an aqueous solution having a stronger alkalinity than the developer to strip the resist pattern from the substrate. The stripping solution may be, for example, an aqueous solution of NaOH or KOH with a concentration of about 2% by mass to 5% by mass and a temperature of about 40°C to 70°C.

[0102] Unless otherwise specified, the evaluation values ​​of the various parameters described above are measured values ​​in accordance with the measurement methods in the examples described below.

[0103] Although the embodiment of the present invention has been described above, the present invention is not limited to this and can be modified as appropriate within the scope of the invention. [Example]

[0104] Next, the present embodiment will be described in more detail with reference to examples and comparative examples. However, the present embodiment is not limited to the following examples as long as they do not deviate from the gist of the present invention.

[0105] <1. Preparation of photosensitive resin composition> Photosensitive resin compositions were prepared by mixing the compounds shown in Tables 1 and 2. The values ​​in Tables 1 and 2 are solid content amounts. The names of the components represented by abbreviations in Tables 1 and 2, the solvents used, etc. are shown in Tables 3 and 4.

[0106] <2. Production of photosensitive resin laminate> Acetone solvent was added to the photosensitive resin composition until the solid content reached 58% by mass, and the mixture was thoroughly stirred and mixed to prepare a solution of the photosensitive resin composition. The solution of the photosensitive resin composition was uniformly applied to a 25 μm-thick polyethylene terephthalate film (Toray FB-40; 16 μm polyethylene terephthalate film) using a bar coater and dried in a dryer at 95 ° C for 5 minutes to form a 3 μm-thick photosensitive resin layer (dry film). Next, a 33 μm-thick polyethylene film (Tamapoly GF-858) was laminated onto the surface of the photosensitive resin layer to obtain a photosensitive resin laminate. The film thickness of the photosensitive resin layer was measured using a film thickness meter (ID-C112B, Mitutoyo).

[0107] <3. Preparation of evaluation board> (laminate) While peeling off the polyethylene film from the photosensitive resin laminate, the laminate was laminated onto a PET substrate with a copper layer using a hot roll laminator (AL-700, manufactured by Asahi Kasei Electronics Corporation) at a roll temperature of 105°C. The air pressure was 0.35 MPa, and the lamination speed was 1.5 m / min.

[0108] (exposure) The support film was peeled off, and the evaluation substrate was exposed to light using a chrome glass photomask with an exposure machine (parallel light exposure machine (HMW-801, manufactured by Oak Manufacturing Co., Ltd.)) equipped with an ultra-high pressure mercury lamp.

[0109] (developing) Using a developing device manufactured by Fuji Kiko Co., Ltd., the unexposed portions of the photosensitive resin layer were dissolved and removed by spraying a 1% by mass Na2CO3 aqueous solution at 23°C for 30 seconds using a full cone type nozzle at a spray pressure of 0.15 MPa. The water washing step was carried out using a flat type nozzle at a water washing spray pressure of 0.15 MPa for the same time as the development step.

[0110] (etching) Using an etching device manufactured by Fuji Kiko Co., Ltd., etching was carried out with a full cone type nozzle at a spray pressure of 0.15 MPa, a temperature of 30°C, a hydrochloric acid concentration of 2 mass %, and ferric chloride of 2 mass % for 60 seconds.

[0111] (peeling) Using a Fuji Kiko Co., Ltd. peeling device, the coating was treated with a full cone type nozzle at a spray pressure of 0.15 MPa and a temperature of 50°C for 30 seconds using a 3% by mass aqueous solution of NaOH to remove the coating.

[0112] <4. Evaluation Method> (Image quality) A photosensitive resin laminate with a photosensitive layer thickness of 3 μm was laminated by the method described above (Lamination), and the evaluation substrate was left for 15 minutes, after which it was exposed through a chrome glass mask having a line pattern with a width ratio of 1:1 between exposed and unexposed areas.Then, it was developed by the method described above (Development) to produce a resist pattern.

[0113] The minimum mask width at which the produced cured resist lines were normally formed was taken as the resolution value, and the resolution was ranked as follows: The minimum mask width at which the cured resist patterns were normally formed without collapse or adhesion between the cured resists was evaluated. ◎ (Good): The resolution value is 2 μm or less. ○ (Acceptable): The resolution value is greater than 2 μm and less than or equal to 3 μm. × (bad): Resolution value exceeds 3 μm.

[0114] (Side etch (SE) amount) To evaluate the side etching amount, a photosensitive resin laminate having a photosensitive resin layer thickness of 3 μm was laminated onto a PET substrate with a copper layer by the method described above (Lamination), and then an evaluation substrate was used after 15 minutes had passed. The laminate evaluation substrate was exposed to light in a pattern with a line / space of 10 μm / 10 μm, and then developed by the method described above in (Development). The resist top width Wr (μm) of the pattern thus formed was measured using an optical microscope.

[0115] Next, the substrate having this line / space pattern was etched using a dip method in an aqueous solution containing 2% by mass of hydrochloric acid and 2% by mass of ferric chloride at a temperature of 30° C. for 1.5 times the minimum etching time. Here, the minimum etching time refers to the minimum time required for the copper foil on the substrate to be completely dissolved and removed under the above conditions. After the etching, the cured film on the substrate was peeled off at 50°C using a 3% by mass aqueous NaOH solution as a stripping solution, and the top width Wc (μm) of the resulting copper line pattern was measured using an optical microscope.

[0116] And the following formula: Side etch (μm) = (Wr-Wc) ÷ 2 The side etch amount was calculated by the above method, and the side etch amount was ranked as follows: ⊚ (very good): The amount of side etching is 2.5 μm or less. ◯ (Good): The amount of side etching is more than 2.5 μm and 3.0 μm or less. △ (Acceptable): The amount of side etching is more than 3.0 μm and 3.5 μm or less. × (bad): The amount of side etching exceeds 3.5 μm.

[0117] (minimum development time) A photosensitive resin laminate having a photosensitive layer thickness of 3 μm was laminated onto a 0.4 mm copper-clad laminate substrate having a copper foil thickness of 18 μm by the method described above (Lamination) to obtain a laminate. After removing the support film laminated on the photosensitive layer, the laminate was spray-developed using a 1.0 mass % sodium carbonate aqueous solution at 23°C for a predetermined time.

[0118] The surface of the substrate after development was observed, and the time until no development residue remained was taken as the minimum development time, and was evaluated according to the following criteria. ◎ (Excellent): The minimum development time is within 10 seconds. ◯ (Good): The minimum development time is within 15 seconds. × (bad): The minimum development time exceeds 15 seconds.

[0119] (contrast) A photosensitive resin laminate having a photosensitive layer thickness of 3 to 10 μm was laminated onto Nikaflex F-30VC1 25C1 1 / 2 (manufactured by Nikkan Industries) by the method described above (Lamination) to obtain a laminate. Before exposure, the ΔE value was measured using a color difference meter (NF333 manufactured by Nippon Denshoku Industries Co., Ltd.) and set to 0. After setting to 0, the sample was exposed to 140 mJ / cm 2 using an exposure machine (parallel light exposure machine (HMW-801 manufactured by Oak Manufacturing Co., Ltd.)) equipped with an ultra-high pressure mercury lamp. 2 The evaluation substrate was exposed to light. The ΔE value of the substrate was measured with a color difference meter 3 minutes after exposure, and the obtained ΔE value was evaluated according to the following criteria. ◎ (Very good): Color difference (ΔE) value is 15 or more. ◯ (Good): Color difference (ΔE) value is 13 or more. △ (Acceptable A): Color difference (ΔE) value is 10 or more. △△ (Acceptable B): Color difference (ΔE) value is 8.0 or more. × (bad): The color difference (ΔE) value is less than 8.0.

[0120] (bleedability) The photosensitive resin laminate (30 cm x 30 cm) obtained in <2. Production of photosensitive resin laminate> was stored in an environment of 25°C and 55% humidity for 7 days, and then the surface was observed and evaluated according to the following criteria. 〇 (Good): No abnormalities on the surface. △ (Acceptable): Precipitated components present in several places on the surface. × (bad): Precipitation components found over the entire surface.

[0121] For each example and comparative example, the composition of the photosensitive resin composition and the evaluation results of the laminate are shown in Tables 1 and 2. In addition, the names of the components represented by abbreviations in Tables 1 and 2, the solvents used, etc. are shown in Tables 3 and 4.

[0122] [Table 1]

[0123] [Table 2]

[0124] [Table 3]

[0125] [Table 4]

[0126] As is clear from the table, in Comparative Examples 1 and 2, which did not contain the component (E), the contrast was insufficient. Furthermore, in Comparative Example 3, in which the thickness of the photosensitive resin composition layer was greater than 10 μm, the minimum development time and resolution were insufficient. Furthermore, at a film thickness of 15 μm, the resolution was not good with a development time of 30 seconds or more, and therefore the side edge amount could not be evaluated. In contrast, in Examples containing component (E) and having a photosensitive resin composition layer with a thickness of 10 μm or less, sufficiently good results were obtained in terms of minimum development time, resolution, side edge (SE) amount, contrast, and bleeding properties. [Industrial Applicability]

[0127] The use of the photosensitive resin laminate of the present invention results in excellent minimum development time, resolution, side edge (SE) amount, contrast, and bleeding properties, and the photosensitive resin laminate can be widely used as a photosensitive resin laminate for forming resist patterns or wiring patterns. Therefore, the present invention can be suitably used when forming lead wiring in the frame region of a touch sensor panel, which particularly requires the above-mentioned minimum development time, resolution, side edge (SE) amount, contrast, and bleeding properties.

Claims

1. A support; Ingredients: (A) an alkali-soluble resin, (B) a photopolymerizable compound having an ethylenically unsaturated bond, (C) a photopolymerization initiator, (D) a compound whose structure changes when irradiated with light having a wavelength of 300 to 500 nm, and whose absorbance at a wavelength of 550 to 700 nm increases; and (E) an organic color developer which is a photoacid generator capable of generating an acid upon irradiation with light and which contains at least one compound selected from the group consisting of an oxime sulfonate compound and a triarylsulfonium salt; a photosensitive resin composition layer formed on the support using a photosensitive resin composition comprising: A photosensitive resin laminate, wherein the thickness of the photosensitive resin composition layer is more than 0 μm and 10 μm or less.

2. 2. The photosensitive resin laminate according to claim 1, wherein a 0.01 mg / ml acetonitrile solution of the component (E) has an absorbance at 330 nm or 405 nm of 0.1 or more and less than 1.

0.

3. 3. The photosensitive resin laminate according to claim 1, wherein the component (E) comprises a nonionic organic color developer.

4. The photosensitive resin laminate according to any one of claims 1 to 3, wherein the component (C) comprises a lophine dimer.

5. The photosensitive resin laminate according to any one of claims 1 to 4, wherein the component (D) comprises a compound having a triarylmethane skeleton.

6. 6. The photosensitive resin laminate according to claim 1, wherein the weight average molecular weight of the component (A) is 5,000 or more and less than 55,000.

7. 7. The photosensitive resin laminate according to claim 1, wherein the content of the component (A) relative to the total amount of the photosensitive resin composition is 10% by mass to 90% by mass.

8. 8. The photosensitive resin laminate according to claim 1, wherein the content of the component (B) relative to the total amount of the photosensitive resin composition is 5% by mass to 70% by mass.

9. 9. The photosensitive resin laminate according to claim 1, wherein the content of the component (C) relative to the total amount of the photosensitive resin composition is 0.01% by mass to 20% by mass.

10. 10. The photosensitive resin laminate according to claim 1, wherein the content of the component (D) relative to the total amount of the photosensitive resin composition is 0.001% by mass to 3% by mass.

11. The photosensitive resin laminate according to any one of claims 1 to 10, wherein the content of the component (E) relative to the total amount of the photosensitive resin composition is more than 0 and 3.5 mass% or less.

12. 12. The photosensitive resin laminate according to claim 1, wherein the content of the component (E) relative to the total amount of the component (A) is more than 0 and 2.5 mass% or less.

13. The photosensitive resin laminate according to any one of claims 1 to 12, wherein the component (A) comprises an aromatic monomer component.

14. The photosensitive resin laminate according to any one of claims 1 to 13, wherein a resist pattern can be formed in which ΔE / T is 3.5 or more, where ΔE is the color difference before and after exposure of a resist pattern produced using the photosensitive resin laminate, and T [μm] is the thickness of the photosensitive resin composition layer.

15. The photosensitive resin laminate according to any one of claims 1 to 14, wherein the photosensitive resin composition layer has a thickness of more than 0 and less than 10 µm.

16. a laminating step of laminating the photosensitive resin laminate according to any one of claims 1 to 15 onto a substrate; an exposure step of exposing the laminated photosensitive resin laminate to light; a developing step of developing the exposed photosensitive resin laminate; A method for forming a resist pattern, comprising: The method for forming a resist pattern, wherein ΔE is the color difference before and after exposure of a resist pattern prepared using the photosensitive resin laminate, and T [μm] is the thickness of the photosensitive resin composition layer, and ΔE / T is 3.5 or more.

17. 17. The method for forming a resist pattern according to claim 16, wherein the exposure step is performed by an exposure method in which a pattern is directly drawn without peeling off the support, or an exposure method in which an image of a photomask is projected through a lens.

18. 18. The method for forming a resist pattern according to claim 16, wherein the exposure step is performed using a light source of 300 to 500 nm.

19. The method for forming a resist pattern according to any one of claims 16 to 18, wherein after the exposure step, the support is peeled off and development is carried out with an inorganic alkaline aqueous solution.

20. 20. The method for forming a resist pattern according to claim 16, further comprising the step of etching the substrate in an area where no pattern is disposed, after the developing step.

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