Method for forming photosensitive resin composition and resist pattern

Abstract

Provided is a photosensitive resin composition suitable for heating after exposure to achieve higher resolution. A photosensitive resin composition is used for heating after exposure and then developing to obtain a cured resin, and comprises the following components based on the total solid content of the photosensitive resin composition: (A) 10% to 90% by mass of an alkali-soluble polymer; (B) 5% to 70% by mass of a compound having an ethylenically unsaturated double bond; and (C) 0.01% to 20% by mass of a photopolymerization initiator, wherein the structural unit of styrene and / or a styrene derivative in the alkali-soluble polymer as a whole (A) is 15% by mass or more.

Description

Technical Field

[0001] The present invention relates to a photosensitive resin composition, a method for forming a resist pattern, and the like. Background Art

[0002] Printed circuit boards are used in electronic devices such as personal computers and mobile phones to mount components, semiconductors, etc. As resists for manufacturing printed circuit boards, photosensitive resin layers are laminated on support films, and a protective film is laminated on the photosensitive resin layer as needed, so-called dry film photoresists (hereinafter sometimes referred to as DF) are used. As photosensitive resin layers, alkali-developable resin layers using weak alkaline aqueous solutions as developer are generally used at present.

[0003] When using DF to make a printed circuit board, for example, the following steps are performed. When DF has a protective film, first, the protective film is peeled off. Thereafter, DF is laminated on a substrate for permanent circuit production such as a copper-clad laminate or a flexible substrate using a laminator, and exposure is performed through a wiring pattern mask film. Next, the support film is peeled off as needed, and the photosensitive resin layer of the uncured portion (for example, the unexposed portion in the case of a negative type) is dissolved or dispersed and removed using a developer, thereby forming a cured resist pattern (hereinafter sometimes referred to as a resist pattern) on the substrate.

[0004] After forming the resist pattern, the process of forming the circuit can be roughly divided into two methods. The first method is to etch away the substrate surface not covered by the resist pattern (e.g., the copper surface of a copper-clad laminate), and then use an alkaline aqueous solution stronger than the developer to remove the resist pattern portion (etching method).

[0005] The second method is to plate the substrate surface with copper, solder, nickel, tin, etc., remove the resist pattern portion in the same manner as the first method, and then etch the exposed substrate surface (e.g., the copper surface of a copper-clad laminate) (plating method). Etching uses copper chloride, ferric chloride, copper ammonia complex solution, etc.

[0006] In recent years, with the miniaturization and lightness of electronic devices, the miniaturization and high density of printed circuit boards have been developed, and in the above-mentioned manufacturing process, high-performance DF with high resolution and high adhesion is required. As a material for achieving such high resolution, Patent Document 1 describes a photosensitive resin composition that improves resolution by using a specific thermoplastic resin, a monomer and a photopolymerization initiator.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Publication No. 2010-249884 Summary of the invention

[0010] Problem that the invention aims to solve

[0011] After the exposure process, depending on the situation, the photosensitive resin layer is sometimes subjected to a heating process, followed by development. By implementing this heating process, further improvement in high resolution and high adhesion can be achieved. However, even if a heating process is applied after exposure, conventional photosensitive resin compositions still have the following problems: the improvement in adhesion becomes insufficient, or good adhesion cannot be obtained when the time after exposure becomes longer.

[0012] The present invention is proposed in view of this existing actual situation, and the purpose of the present invention is to:

[0013] Provided is a photosensitive resin composition which can significantly improve the adhesiveness when developing after heating after exposure, and which can achieve good adhesiveness even when the time after exposure becomes long.

[0014] Solutions for solving problems

[0015] As a result of intensive studies, the present inventors have found that the above-mentioned object can be achieved by using a monomer component having a specific structural unit in a specific amount in an alkali-soluble polymer constituting a photosensitive resin composition, thereby completing the present invention.

[0016] Furthermore, as a result of intensive studies, the present inventors have found that the above-mentioned object can be achieved by using a specific photopolymerization initiator in an alkali-soluble polymer constituting a photosensitive resin composition, thereby completing the present invention.

[0017] That is, the present invention is as follows.

[0018] [1] A photosensitive resin composition for obtaining a cured resin by heating after exposure and then developing, wherein the photosensitive resin composition comprises the following components based on the total solid content of the photosensitive resin composition:

[0019] (A) alkali-soluble polymer: 10% to 90% by mass;

[0020] (B) compounds having an ethylenically unsaturated double bond: 5% to 70% by mass; and

[0021] (C) Photopolymerization initiator: 0.01% to 20% by mass,

[0022] The structural unit of styrene and / or a styrene derivative in the entire (A) alkali-soluble polymer is 15% by mass or more.

[0023] [2] The photosensitive resin composition according to [1], wherein the content of the compound (B-1) having a bisphenol A skeleton concentration of 0.18 mol / 100 g or more as the compound (B) having an ethylenically unsaturated double bond is 0% to 18% by mass based on the solid content of the photosensitive resin composition.

[0024] [3] The photosensitive resin composition according to [1] or [2], further comprising (D) an inhibitor.

[0025] [4] The photosensitive resin composition according to any one of [1] to [3], further comprising (E) a benzotriazole derivative.

[0026] [5] The photosensitive resin composition according to any one of [1] to [4], wherein the (B) compound having an ethylenically unsaturated double bond comprises a (meth)acrylate compound having three or more ethylenically unsaturated double bonds.

[0027] [6] The photosensitive resin composition according to [5], wherein the (B) compound having an ethylenically unsaturated double bond comprises a (meth)acrylate compound having four or more ethylenically unsaturated double bonds.

[0028] [7] The photosensitive resin composition according to [6], wherein the (B) compound having an ethylenically unsaturated double bond comprises a (meth)acrylate compound having 6 or more ethylenically unsaturated double bonds.

[0029] [8] The photosensitive resin composition according to any one of [1] to [7], wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 0.94 or more.

[0030] [9] The photosensitive resin composition according to [8], wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 1.04 or more.

[0031]

[10] The photosensitive resin composition according to [9], wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 1.11 or more.

[0032]

[11] The photosensitive resin composition according to

[10] , wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 1.21 or more.

[0033]

[12] The photosensitive resin composition according to

[11] , wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 1.30 or more.

[0034]

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

[12] , wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 5 or less.

[0035]

[14] The photosensitive resin composition according to

[13] , wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 4 or less.

[0036]

[15] The photosensitive resin composition according to

[14] , wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 3 or less.

[0037]

[16] The photosensitive resin composition according to

[15] , wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 2 or less.

[0038]

[17] The photosensitive resin composition according to

[16] , wherein the value of [(A) content of the alkali-soluble polymer] / [(B) content of the compound having an ethylenically unsaturated double bond] is 1.5 or less.

[0039]

[18] A photosensitive resin composition that is used to obtain a cured resin by heating after exposure and then developing, wherein the photosensitive resin composition comprises the following components based on the total solid content of the photosensitive resin composition:

[0040] (A) alkali-soluble polymer: 10% to 90% by mass;

[0041] (B) compounds having an ethylenically unsaturated double bond: 5% to 70% by mass; and

[0042] (C) Photopolymerization initiator: 0.01% to 20% by mass,

[0043] The (C) photopolymerization initiator contains anthracene and / or anthracene derivative.

[0044]

[19] The photosensitive resin composition according to

[18] , wherein the anthracene derivative has an alkoxy group having 1 to 40 carbon atoms which may have a substituent and / or an aryl group having 6 to 40 carbon atoms which may have a substituent at the 9-position and / or the 10-position.

[0045]

[20] The photosensitive resin composition according to

[18] or

[19] , wherein the anthracene derivative has an alkoxy group having 1 to 40 carbon atoms which may have a substituent and / or an aryl group having 6 to 40 carbon atoms which may have a substituent at the 9- and 10-positions.

[0046]

[21] The photosensitive resin composition according to

[20] , wherein the (C) photopolymerization initiator contains 9,10-diphenylanthracene.

[0047]

[22] The photosensitive resin composition according to

[20] , wherein the (C) photopolymerization initiator contains 9,10-dialkoxyanthracene.

[0048]

[23] The photosensitive resin composition according to any one of

[18] to

[22] , wherein the (C) photopolymerization initiator contains an anthracene derivative having a halogen atom.

[0049]

[24] The photosensitive resin composition according to

[23] , wherein the (C) photopolymerization initiator comprises a halogenated 9,10-dialkoxyanthracene.

[0050]

[25] The photosensitive resin composition according to

[24] , wherein the photopolymerization initiator (C) comprises a compound in which the alkoxy group at the 9-position and / or 10-position of 9,10-dialkoxyanthracene is modified with one or more halogen atoms.

[0051]

[26] The photosensitive resin composition according to any one of

[18] to

[25] , wherein the (C) photopolymerization initiator contains a compound having a halogen atom directly bonded to an anthracene skeleton.

[0052]

[27] The photosensitive resin composition according to any one of

[18] to

[26] , wherein the structural unit of styrene and / or a styrene derivative in the alkali-soluble polymer (A) accounts for 15% by mass or more.

[0053]

[28] The photosensitive resin composition according to any one of [1] to

[27] , wherein the structural unit of styrene and / or a styrene derivative in the alkali-soluble polymer (A) accounts for 25% by mass or more.

[0054]

[29] The photosensitive resin composition according to

[28] , wherein the structural unit of styrene and / or a styrene derivative in the alkali-soluble polymer (A) accounts for 30% by mass or more.

[0055]

[30] The photosensitive resin composition according to

[29] , wherein the structural unit of styrene and / or a styrene derivative in the alkali-soluble polymer (A) accounts for 35% by mass or more.

[0056]

[31] The photosensitive resin composition according to

[30] , wherein the structural unit of styrene and / or a styrene derivative in the alkali-soluble polymer (A) is 40% by mass or more.

[0057]

[32] The photosensitive resin composition according to any one of [1] to

[31] , wherein the structural unit of styrene and / or a styrene derivative in the alkali-soluble polymer (A) accounts for 90% by mass or less.

[0058]

[33] The photosensitive resin composition according to any one of [1] to

[32] , wherein the (A) alkali-soluble polymer further contains benzyl (meth)acrylate as a monomer component.

[0059]

[34] A method for forming a resist pattern, comprising the following steps:

[0060] A step of exposing the photosensitive resin composition according to any one of [1] to

[33] ; a heating step of heating the exposed photosensitive resin composition; and a developing step of developing the heated photosensitive resin composition.

[0061]

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

[34] , wherein the heating temperature in the heating step is in the range of 30°C to 150°C.

[0062]

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

[34] or

[35] , wherein the exposure step is performed by an exposure method based on direct drawing of a drawing pattern or an exposure method in which an image of a photomask is projected through a lens.

[0063]

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

[34] or

[35] , wherein the exposure step is performed by an exposure method based on direct drawing of a drawing pattern.

[0064]

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

[34] to

[37] , wherein the heating step is performed within 15 minutes after the exposure.

[0065]

[39] A method for forming an anti-etching pattern according to any one of

[34] to

[38] , wherein the exposure step is carried out by exposing a first laser having a central wavelength less than 390 nm and a second laser having a central wavelength greater than 390 nm.

[0066]

[40] The method for forming an anti-etching pattern according to

[39] , wherein the central wavelength of the first laser is greater than 350 nm and less than 380 nm, and the central wavelength of the second laser is greater than 400 nm and less than 410 nm.

[0067]

[41] A method for producing a circuit board, comprising etching or plating a substrate having a resist pattern produced by the method according to any one of

[34] to

[40] , thereby forming the circuit board.

[0068]

[42] The photosensitive resin composition according to any one of [1] to

[33] , which is a photosensitive resin composition for obtaining a resin cured product by exposure using a first laser having a central wavelength of less than 390 nm and a second laser having a central wavelength of 390 nm or more.

[0069]

[43] The photosensitive resin composition according to

[42] , wherein the central wavelength of the first laser is from 350 nm to 380 nm, and the central wavelength of the second laser is from 400 nm to 410 nm.

[0070] Effects of the Invention

[0071] According to the present invention, it is possible to provide a photosensitive resin composition which can significantly improve the adhesiveness when developing after heating after exposure, and which can achieve good adhesiveness even when the elapsed time after exposure is long. DETAILED DESCRIPTION

[0072] Hereinafter, the illustrative modes (hereinafter abbreviated as "embodiment") for implementing the present invention are described in detail. In addition, the present invention is not limited to the following embodiments, and various modifications can be carried out within the scope of its main purpose to implement. In addition, for the various measured values ​​in this specification, as long as there is no special record, the method recorded in [Examples] of the application or the method equivalent thereto is considered by those skilled in the art to be measured.

[0073] [Photosensitive resin composition]

[0074] The photosensitive resin composition of the present invention is a photosensitive resin composition for obtaining a resin cured product by heating after exposure and then developing. The photosensitive resin composition, calculated based on the total solid content of the photosensitive resin composition, comprises the following components: (A) 10% to 90% by mass of an alkali-soluble polymer; (B) 5% to 70% by mass of a compound having an ethylenically unsaturated double bond; and (C) 0.01% to 20% by mass of a photopolymerization initiator.

[0075] Furthermore, in particular, the photosensitive resin composition of the present embodiment is characterized in that, when the (A) alkali-soluble polymer includes a plurality of alkali-soluble polymers, the structural unit of styrene and / or a styrene derivative in the entire (A) alkali-soluble polymer accounts for 15% by mass or more.

[0076] The dry film resist obtained from the photosensitive resin composition generally does not have the effect of improving adhesion unless it is heated immediately after exposure, but the dry film resist obtained from the photosensitive resin composition of the present invention can show good adhesion (in other words, fine resist) even when the time after exposure becomes long. The photosensitive resin composition of the present invention has a composition suitable for this characteristic.

[0077] In the photosensitive resin composition of the present embodiment, when the (A) alkali-soluble polymer includes a plurality of alkali-soluble polymers, by making the structural units of styrene and / or styrene derivatives in the entire (A) alkali-soluble polymer 15 mass % or more, it is possible to significantly improve the adhesion when developing after heating after exposure, and in particular, even when the time after exposure becomes long, good adhesion can be obtained.

[0078] Hereinafter, each component will be described in order.

[0079] <(A) Alkali-soluble polymer>

[0080] In the present application, (A) alkali-soluble polymers include polymers that are easily soluble in alkaline substances. More specifically, the amount of carboxyl groups contained in (A) alkali-soluble polymers is 100 to 600, preferably 250 to 450, in terms of acid equivalent. Acid equivalent refers to the mass (unit: gram) of a polymer having 1 equivalent of carboxyl groups in its molecule. The carboxyl groups in (A) alkali-soluble polymers are required to impart developability and stripping properties to the photosensitive resin layer relative to aqueous alkaline solutions. From the viewpoint of improving development tolerance, resolution and adhesion, it is preferred that the acid equivalent is 100 or more. Furthermore, it is more preferred that the acid equivalent is 250 or more. On the other hand, from the viewpoint of improving developability and stripping properties, it is preferred that the acid equivalent is 600 or less. Furthermore, it is more preferred that the acid equivalent is 450 or less. In the present application, the acid equivalent is a value measured by a potentiometric titration method using a potentiometric titration apparatus and titrating with a 0.1 mol / L NaOH aqueous solution.

[0081] (A) The weight average molecular weight of the alkali-soluble polymer is preferably 5,000 to 500,000. From the viewpoint of improving resolution and developability, the weight average molecular weight is preferably 500,000 or less. More preferably, the weight average molecular weight is 100,000 or less, further preferably 70,000 or less, further preferably 60,000 or less, and particularly preferably 50,000 or less. On the other hand, from the viewpoint of controlling the properties of the developed aggregates and the properties of the unexposed film such as the edge fuse and cut chip properties when the photosensitive resin laminate is made, the weight average molecular weight is preferably 5,000 or more. More preferably, the weight average molecular weight is 10,000 or more, further preferably 20,000 or more. Edge fuse refers to the degree of ease with which the photosensitive resin layer (i.e., the layer formed by the photosensitive resin composition) is exposed from the end surface of the roll when the photosensitive resin laminate is rolled into a roll. Cutting property refers to the degree of splattering of chips when the unexposed film is cut with a cutter. If the chips adhere to the upper surface of the photosensitive resin laminate, they will be transferred to the mask in the subsequent exposure process, causing defective products. The dispersion degree of the (A) alkali-soluble polymer is preferably 1.0 to 6.0, more preferably 1.0 to 5.0, further preferably 1.0 to 4.0, and further preferably 1.0 to 3.0.

[0082] In the present embodiment, for the photosensitive resin composition, from the viewpoint of being able to significantly improve the adhesion when heating after exposure and then developing, especially showing good adhesion even when the time after exposure becomes longer, as (A) alkali-soluble polymer, it is preferred to include a monomer component having an aromatic hydrocarbon group. It should be noted that as such an aromatic hydrocarbon group, for example, substituted or unsubstituted phenyl, substituted or unsubstituted aralkyl can be cited. The content ratio of the monomer component having an aromatic hydrocarbon group in the (A) alkali-soluble polymer is based on the total mass of all monomer components, preferably 20% by mass or more, more preferably 40% by mass or more, further preferably 50% by mass or more, particularly preferably 55% by mass or more, and most preferably 60% by mass or more. As an upper limit, there is no particular limitation, preferably 95% by mass or less, more preferably 80% by mass or less. It should be noted that the content ratio of the monomer component having an aromatic hydrocarbon group when containing a plurality of (A) alkali-soluble polymers is calculated as a weight average.

[0083] Examples of the monomer having an aromatic hydrocarbon group include monomers having an aralkyl group, styrene, and polymerizable styrene derivatives. Among them, monomers having an aralkyl group or styrene are preferred.

[0084] Examples of the aralkyl group include substituted or unsubstituted phenylalkyl (excluding benzyl) and substituted or unsubstituted benzyl. Preferably, it is a substituted or unsubstituted benzyl.

[0085] Examples of the comonomer having a phenylalkyl group include phenylethyl (meth)acrylate and the like.

[0086] Examples of the comonomer having a benzyl group include (meth)acrylates having a benzyl group, such as benzyl (meth)acrylate and benzyl (meth)acrylate chloride, and vinyl monomers having a benzyl group, such as vinylbenzyl chloride and vinylbenzyl alcohol, among which benzyl (meth)acrylate is preferred.

[0087] The (A) alkali-soluble polymer containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing a monomer having an aromatic hydrocarbon group with at least one first monomer described below and / or at least one second monomer described below.

[0088] The (A) alkali-soluble polymer not containing a monomer component having an aromatic hydrocarbon group is preferably obtained by polymerizing at least one first monomer described below, and more preferably by copolymerizing at least one first monomer and at least one second monomer described below.

[0089] The first monomer is a monomer having a carboxyl group in the molecule. Examples of the first monomer include (meth)acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, 4-vinylbenzoic acid, maleic anhydride, and maleic acid half ester. Among these, (meth)acrylic acid is preferred.

[0090] In the present specification, “(meth)acrylic acid” means acrylic acid or methacrylic acid, “(meth)acryloyl” means acryloyl or methacryloyl, and “(meth)acrylate” means “acrylate” or “methacrylate”.

[0091] The copolymerization ratio of the first monomer is preferably 10 to 50% by mass based on the total mass of all monomer components. From the viewpoint of showing good developability, controlling edge fusion, etc., it is preferred that the copolymerization ratio is 10% by mass or more, more preferably 15% by mass or more, and further preferably 20% by mass or more. From the viewpoint of the high resolution and hem shape of the resist pattern, and further from the viewpoint of the chemical resistance of the resist pattern, it is preferred that the copolymerization ratio is 50% by mass or less, and from these viewpoints, it is more preferred that it is 35% by mass or less, further preferably 32% by mass or less, and particularly preferably 30% by mass or less.

[0092] The second monomer is a non-acidic monomer having at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include (meth)acrylate methyl, (meth)acrylate ethyl, (meth)acrylate n-propyl, (meth)acrylate isopropyl, (meth)acrylate n-butyl, (meth)acrylate isobutyl, (meth)acrylate tert-butyl, (meth)acrylate 2-hydroxyethyl, (meth)acrylate 2-hydroxypropyl, (meth)acrylate cyclohexyl, (meth)acrylate 2-ethylhexyl (meth)acrylate and other (meth)acrylate esters; esters of vinyl alcohol such as vinyl acetate; and (meth)acrylonitrile. Among them, methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate and n-butyl (meth)acrylate are preferred.

[0093] From the viewpoint of being able to significantly improve the adhesion when developing after heating after exposure, and especially showing good adhesion even when the time after exposure becomes long, it is preferred to contain a monomer having an aralkyl group and / or styrene as a monomer. For example, a copolymer containing methacrylic acid, benzyl methacrylate and styrene, a copolymer containing methacrylic acid, methyl methacrylate, benzyl methacrylate and styrene, etc. are preferred.

[0094] (A) Alkali-soluble polymers may be used alone or in combination of two or more. When two or more are used in combination, it is preferred that two alkali-soluble polymers containing monomer components having aromatic hydrocarbon groups are used in combination; or an alkali-soluble polymer containing monomer components having aromatic hydrocarbon groups is mixed with an alkali-soluble polymer not containing monomer components having aromatic hydrocarbon groups. In the latter case, the proportion of the alkali-soluble polymer containing monomer components having aromatic hydrocarbon groups relative to the total amount of the alkali-soluble polymers (A) is preferably 50% by mass or more, more preferably 70% by mass or more, preferably 80% by mass or more, more preferably 90% by mass or more, and most preferably 95% by mass or more.

[0095] In the (A) alkali-soluble polymer of the present embodiment, it is preferred to include an alkali-soluble polymer (A-1) of 3% or more by mass relative to the solid content in the photosensitive resin composition, and the alkali-soluble polymer (A-1) includes 52% or more by mass of structural units of styrene and / or styrene derivatives as monomer components. Thus, the adhesion when heating after exposure and then developing can be significantly improved, and even when the time after exposure becomes longer, good adhesion can be obtained. From the same point of view, (A) alkali-soluble polymer more preferably includes an alkali-soluble polymer (A-1) of 10% or more by mass relative to the solid content in the photosensitive resin composition, further preferably includes 15% or more by mass, particularly preferably includes 20% or more by mass, and most preferably includes 30% or more by mass.

[0096] Examples of the styrene derivatives include methylstyrene, vinyltoluene, tert-butoxystyrene, acetoxystyrene, 4-vinylbenzoic acid, styrene dimer, and styrene trimer.

[0097] In particular, in the present embodiment, when (A) the alkali-soluble polymer comprises a plurality of alkali-soluble polymers, the structural units of styrene and / or styrene derivatives in the alkali-soluble polymer (A) as a whole are 15% by mass or more. Thus, the adhesion when developing after heating after exposure can be significantly improved, and in particular, good adhesion can be obtained even when the time after exposure becomes longer. The styrene skeleton is hydrophobic, and therefore, the swelling property to the developer can be suppressed, and good adhesion can be exhibited. The structural units of styrene and / or styrene derivatives in the alkali-soluble polymer (A) are preferably 25% by mass or more, more preferably 30% by mass or more, further preferably 35% by mass or more, and particularly preferably 40% by mass or more.

[0098] Among them, if the content of the styrene skeleton is high, the fluidity of the resin decreases, so the reactivity cannot be fully improved and the desired adhesion cannot be obtained. In addition, if the time after exposure becomes longer, the free radicals in the system gradually deactivate, so the effect of improving the adhesion by heating after exposure gradually decreases. The upper limit of the structural unit of styrene and / or styrene derivatives in (A) the alkali-soluble polymer is preferably 90% by mass or less, more preferably 80% by mass or less, further preferably 75% by mass or less, and particularly preferably 70% by mass or less.

[0099] As such, in the present invention, by making the structural unit of styrene and / or styrene derivative in the whole alkali-soluble polymer (A) to be 15% by mass or more, and heating and then developing after exposure, even in a system with a high content of styrene skeleton, the fluidity of the resin can be improved by heating, and the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly taken into account, and as a result, it is believed that the adhesion can be significantly improved. It is also believed that: by significantly improving the adhesion, even when the time after exposure becomes long, good adhesion can be obtained.

[0100] In addition, from the viewpoint of being able to significantly improve the adhesion when developing after heating after exposure, and in particular showing good adhesion even when the time after exposure becomes long, the alkali-soluble polymer (A-1) preferably contains 25% by mass or more of the structural unit of (meth)acrylic acid as a monomer component, more preferably 26% by mass or more, further preferably 27% by mass or more, particularly preferably 28% by mass or more, and most preferably 29% by mass or more. From the same viewpoint, it is preferably 35% by mass or less, more preferably 32% by mass or less, and further preferably 30% by mass or less.

[0101] (A) The synthesis of alkali-soluble polymers is preferably carried out by adding an appropriate amount of a free radical polymerization initiator such as benzoyl peroxide or azoisobutyronitrile to a solution obtained by diluting the above-described single or multiple monomers with a solvent such as acetone, methyl ethyl ketone, isopropanol, etc., and heating and stirring. Sometimes, the synthesis is carried out while a portion of the mixture is added dropwise to the reaction solution. Sometimes, after the reaction is completed, a solvent is further added to adjust the concentration to a desired concentration. As a synthesis method, in addition to solution polymerization, bulk polymerization, suspension polymerization or emulsion polymerization can also be used.

[0102] (A) Weighted average value of glass transition temperature Tg of alkali-soluble polymer total It is preferably 30°C or higher and 150°C or lower. Tg total The calculation is performed by the method described in the examples below. In the photosensitive resin composition, by using a photosensitive resin having a Tg of 150°C or less total The alkali-soluble polymer (A) can significantly improve the adhesion when heated and then developed after exposure, and can show good adhesion even when the time after exposure becomes long. From this point of view, the Tg of the alkali-soluble polymer (A) total It is more preferably 135°C or less, further preferably 130°C or less, most preferably 125°C or less, further preferably 120°C or less, and particularly preferably 110°C or less. In addition, from the viewpoint of improving edge fusion resistance, it is preferred to use a Tg of 30°C or more. total From this point of view, the Tg of the alkali-soluble polymer (A) total It is more preferably 40°C or higher, further preferably 50°C or higher, and particularly preferably 60°C or higher.

[0103] The ratio of the (A) alkali-soluble polymer to the total solid content of the photosensitive resin composition is preferably in the range of 10% to 90% by mass, more preferably 30% to 70% by mass, and further preferably 40% to 60% by mass. From the viewpoint of controlling the development time, it is preferred that the ratio of the (A) alkali-soluble polymer to the photosensitive resin composition is 90% by mass or less. On the other hand, from the viewpoint of improving the edge fusion resistance, it is preferred that the ratio of the (A) alkali-soluble polymer to the photosensitive resin composition is 10% by mass or more.

[0104] <(B) Compounds Having Ethylenically Unsaturated Double Bonds>

[0105] From the viewpoint of curability and compatibility with the alkali-soluble polymer (A), the compound having an ethylenically unsaturated double bond (B) preferably includes a compound having a (meth)acryloyl group in the molecule. The number of (meth)acryloyl groups in the compound (B) may be 1 or more.

[0106] (B) The compound having an ethylenically unsaturated bond is a compound having polymerizability by having an ethylenically unsaturated group in its structure. The ethylenically unsaturated bond is more preferably derived from a methacryloyl group. From the viewpoint of adhesion and the viewpoint of suppressing the foaming property of the developer, the compound having an ethylenically unsaturated bond (B) preferably has an alkylene oxide structure having 3 or more carbon atoms. The number of carbon atoms in the alkylene oxide structure is more preferably 3 to 6, and further preferably 3 to 4.

[0107] Examples of the compound (B) having one (meth)acryloyl group include compounds obtained by adding (meth)acrylic acid to one terminal of a polyalkylene oxide, compounds obtained by adding (meth)acrylic acid to one terminal of a polyalkylene oxide and alkyl etherifying or allyl etherifying the other terminal, and phthalic acid compounds. These are preferred from the viewpoint of releasability and flexibility of the cured film.

[0108] Examples of such compounds include phenoxyhexaethylene glycol mono(meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polyethylene glycol to a phenyl group; 4-n-nonylphenoxyheptaethylene glycol dipropylene glycol (meth)acrylate, which is a (meth)acrylate of a compound obtained by adding polypropylene glycol to which an average of 2 mol of propylene oxide is added and polyethylene glycol to which an average of 7 mol of ethylene oxide is added to nonylphenol; and 1-hydroxy-2-nitro-1-ol-1-ol-2-nitro ... (Meth)acrylate of a compound obtained by adding polypropylene glycol of propylene oxide and polyethylene glycol to which an average of 5 mol of ethylene oxide is added to nonylphenol, i.e., 4-n-nonylphenoxypentaethylene glycol monopropylene glycol (meth)acrylate; acrylate of a compound obtained by adding polyethylene glycol to which an average of 8 mol of ethylene oxide is added to nonylphenol, i.e., 4-n-nonylphenoxyoctaethylene glycol (meth)acrylate (e.g., M-114 manufactured by Toagosei Co., Ltd.), etc.

[0109] Furthermore, when γ-chloro-β-hydroxypropyl-β'-methacryloyloxyethyl phthalate is contained, it is preferred not only from the above viewpoints but also from the viewpoints of sensitivity, resolution, and adhesion.

[0110] Examples of the compound having two (meth)acryloyl groups in the molecule include compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain, and compounds having (meth)acryloyl groups at both ends of an alkylene oxide chain in which an ethylene oxide chain and a propylene oxide chain are randomly or block-bonded.

[0111] Examples of such compounds include polyethylene glycol (meth)acrylates such as tetraethylene glycol di(meth)acrylate, pentaethylene glycol di(meth)acrylate, hexaethylene glycol di(meth)acrylate, heptaethylene glycol di(meth)acrylate, octaethylene glycol di(meth)acrylate, nonaethylene glycol di(meth)acrylate, decaethylene glycol di(meth)acrylate, and compounds having (meth)acryloyl groups at both ends of 12 mols of ethylene oxide chains, as well as polypropylene glycol di(meth)acrylate and polybutylene glycol di(meth)acrylate. Examples of the polyalkylene oxide di(meth)acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound include dimethacrylate of a diol obtained by further adding an average of 3 mol of ethylene oxide to each of the two ends of a polypropylene glycol to which an average of 12 mol of propylene oxide has been added, dimethacrylate of a diol obtained by further adding an average of 15 mol of ethylene oxide to each of the two ends of a polypropylene glycol to which an average of 18 mol of propylene oxide has been added, FA-023M, FA-024M, FA-027M (product names, manufactured by Hitachi Chemical Co., Ltd.), etc. These are preferred from the viewpoints of flexibility, resolution, adhesion, etc.

[0112] As another example of the compound having two (meth)acryloyl groups in the molecule, a compound obtained by modifying bisphenol A with an alkylene oxide to have (meth)acryloyl groups at both terminals is preferred from the viewpoint of resolution and adhesion.

[0113] Specifically, a compound represented by the following general formula (I) can be used.

[0114]

[0115] {In the formula, R1 and R2 each independently represent a hydrogen atom or a methyl group, A is C2H4, B is C3H6, n1 and n3 each independently represent an integer of 1 to 39, and n1+n3 represents an integer of 2 to 40, n2 and n4 each independently represent an integer of 0 to 29, and n2+n4 represents an integer of 0 to 30, and the arrangement of the repeating units of -(AO)- and -(BO)- may be random or block. In the case of a block, any of -(AO)- and -(BO)- may be on the biphenyl side.}

[0116] For example, from the viewpoint of resolution and adhesion, preferred are polyethylene glycol dimethacrylates having an average of 5 mol of ethylene oxide added to each of the two ends of bisphenol A, polyethylene glycol dimethacrylates having an average of 2 mol of ethylene oxide added to each of the two ends of bisphenol A, and polyethylene glycol dimethacrylates having an average of 1 mol of ethylene oxide added to each of the two ends of bisphenol A.

[0117] Furthermore, the aromatic ring in the above general formula (I) may contain a heteroatom and / or a substituent.

[0118] Examples of the hetero atom include a halogen atom, and examples of the substituent include an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms, an aryl group having 6 to 18 carbon atoms, a phenacyl group, an amino group, an alkylamino group having 1 to 10 carbon atoms, a dialkylamino group having 2 to 20 carbon atoms, a nitro group, a cyano group, a carbonyl group, a mercapto group, an alkylmercapto group having 1 to 10 carbon atoms, an aryl group, a hydroxyl group, a hydroxyalkyl group having 1 to 20 carbon atoms, a carboxyl group, a carboxyalkyl group having 1 to 10 carbon atoms in an alkyl group, an acyl group having 1 to 10 carbon atoms in an alkyl group, an alkoxy group having 1 to 20 carbon atoms, an alkoxycarbonyl group having 1 to 20 carbon atoms, an alkylcarbonyl group having 2 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an N-alkylcarbamoyl group having 2 to 10 carbon atoms, a group containing a heterocycle, or an aryl group substituted with these substituents. These substituents may form a condensed ring or the hydrogen atoms in these substituents may be substituted with heteroatoms such as halogen atoms. When the aromatic ring in the general formula (I) has a plurality of substituents, the plurality of substituents may be the same or different.

[0119] The compound having three or more (meth)acryloyl groups in the molecule can be obtained by adding an alkylene oxide group such as ethyleneoxy, propyleneoxy, or butyleneoxy to an alcohol having three or more moles of a group as a central skeleton to which an alkylene oxide group can be added in the molecule, and converting the resultant alcohol into (meth)acrylate. In this case, examples of the compound capable of forming the central skeleton include glycerol, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate ring. Examples of these compounds include tri(meth)acrylates such as ethoxylated glycerol tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and trimethylolpropane tri(meth)acrylate (for example, from the viewpoint of flexibility, adhesion, and suppression of bleed-out, trimethacrylate obtained by adding an average of 21 mol of ethylene oxide to trimethylolpropane and trimethacrylate obtained by adding an average of 30 mol of ethylene oxide to trimethylolpropane are preferred); tetra(meth)acrylates such as di(trimethylolpropane) tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, and dipentaerythritol tetra(meth)acrylate; penta(meth)acrylates such as dipentaerythritol penta(meth)acrylate; and hexa(meth)acrylates such as dipentaerythritol hexa(meth)acrylate. From the viewpoint of being able to significantly improve the adhesion when developing after heating after exposure, and in particular showing good adhesion even when the time after exposure becomes long, a compound having three or more (meth)acryloyl groups is preferred, and a compound having three or more methacryloyl groups is more preferred.

[0120] The tetra(meth)acrylate is preferably pentaerythritol tetra(meth)acrylate. The pentaerythritol tetra(meth)acrylate may be a tetra(meth)acrylate obtained by adding 1 to 40 mol of alkylene oxide in total to four terminals of pentaerythritol.

[0121] The hexa(meth)acrylate is preferably one obtained by adding 1 to 40 mol of ethylene oxide in total to the six terminals of dipentaerythritol or one obtained by adding 1 to 20 mol of ε-caprolactone in total to the six terminals of dipentaerythritol.

[0122] As the aforementioned (B) compound having an ethylenically unsaturated double bond, from the viewpoint of being able to significantly improve the adhesion when developing after heating after exposure, and especially being able to obtain good adhesion even when the time after exposure becomes longer, it is preferred to include a (meth)acrylate compound having 3 or more ethylenically unsaturated double bonds. From the same viewpoint, it is more preferred to include a (meth)acrylate compound having 4 or more ethylenically unsaturated double bonds, further preferably to include a (meth)acrylate compound having 5 or more ethylenically unsaturated double bonds, and particularly preferably to include a (meth)acrylate compound having 6 or more ethylenically unsaturated double bonds. In addition, from the same viewpoint, they are preferably methacrylate compounds.

[0123] It is believed that compounds having 3 or more, 4 or more, 5 or more, or 6 or more ethylenically unsaturated double bonds have the effect of increasing the crosslinking density during polymerization based on exposure, but the desired crosslinking density is often not obtained due to the influence of stereo hindrance caused by the large number of functional groups. The present invention has found that by subjecting preferably compounds having 3 or more ethylenically unsaturated double bonds, more preferably compounds having 4 or more ethylenically unsaturated double bonds, further preferably compounds having 5 or more ethylenically unsaturated double bonds, and particularly preferably compounds having 6 or more ethylenically unsaturated double bonds to heat treatment after exposure, the fluidity in the system is improved, thereby reducing the influence of stereo hindrance even if the number of functional groups is large, and high adhesion can be obtained.

[0124] The content of the compound preferably having 3 or more ethylenically unsaturated double bonds, more preferably having 4 or more ethylenically unsaturated double bonds, further preferably having 5 or more ethylenically unsaturated double bonds, and particularly preferably having 6 or more ethylenically unsaturated double bonds is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 7% by mass or more, and particularly preferably 10% by mass or more relative to the solid content of the photosensitive resin composition. In addition, as the upper limit of the content, from the viewpoint of showing the effect of the heat treatment after exposure, it is preferably 30% by mass or less, more preferably 25% by mass or less, further preferably 20% by mass or less, and particularly preferably 15% by mass or less.

[0125] Examples of the (b1) (meth)acrylate compound having three or more ethylenically unsaturated bonds include:

[0126] tri(meth)acrylates, such as ethoxylated glycerol tri(meth)acrylate, ethoxylated isocyanuric acid tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and trimethylolpropane tri(meth)acrylate (for example, tri(meth)acrylate obtained by adding an average of 21 mol of ethylene oxide to trimethylolpropane and tri(meth)acrylate obtained by adding an average of 30 mol of ethylene oxide to trimethylolpropane as suitable examples from the viewpoint of flexibility, adhesion, and suppression of bleed-out);

[0127] Tetra(meth)acrylates, such as di(trimethylolpropane)tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, etc.;

[0128] Penta(meth)acrylates, such as dipentaerythritol penta(meth)acrylate, etc.;

[0129] Hexa(meth)acrylate, for example, dipentaerythritol hexa(meth)acrylate, etc.

[0130] Among these, tetra-, penta- or hexa-(meth)acrylate is preferred.

[0131] From the viewpoint of suppressing bleed-out, the (meth)acrylate compound (b1) having three or more ethylenically unsaturated bonds preferably has a weight average molecular weight of 500 or more, more preferably 700 or more, and even more preferably 900 or more.

[0132] As the tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate is preferred. As the pentaerythritol tetra(meth)acrylate, tetra(meth)acrylate obtained by adding 1 to 40 mol of alkylene oxide in total to four terminals of pentaerythritol is preferred.

[0133] The tetra(meth)acrylate is more preferably a tetramethacrylate compound represented by the following general formula (II).

[0134]

[0135] {wherein, R3 to R6 each independently represent an alkyl group having 1 to 4 carbon atoms, X represents an alkylene group having 2 to 6 carbon atoms, m1, m2, m3 and m4 each independently represent an integer of 0 to 40, m1+m2+m3+m4 is 1 to 40, and when m1+m2+m3+m4 is 2 or more, multiple Xs may be the same or different}

[0136] Although not wishing to be bound by theory, it is believed that the tetramethacrylate compound represented by the general formula (II) has R3 to R6 groups, and therefore, compared with the tetraacrylate having the H2C=CH-CO-O- portion, the hydrolysis in an alkaline solution is suppressed. From the viewpoint of being able to significantly improve the adhesion when developing after heating after exposure, and especially achieving good adhesion even when the time after exposure becomes long, it is preferred to use a photosensitive resin composition containing the tetramethacrylate compound represented by the general formula (II).

[0137] In the general formula (II), it is preferred that at least one of the R3 to R6 groups is a methyl group, and it is more preferred that all of the R3 to R6 groups are methyl groups.

[0138] From the viewpoint of obtaining desired resolution, hem shape, and residual film rate for the resist pattern, in the general formula (II), X is preferably -CH2-CH2-.

[0139] From the viewpoint of obtaining the desired resolution, hem shape and residual film rate for the resist pattern, in the general formula (II), m1, m2, m3 and m4 are each independently preferably an integer of 1 to 20, more preferably an integer of 2 to 10. Furthermore, in the general formula (II), m1+m2+m3+m4 is preferably 1 to 36 or 4 to 36.

[0140] As the compound represented by the general formula (II), for example, pentaerythritol (poly) alkoxytetramethacrylate and the like can be cited. In addition, in the present application, "pentaerythritol (poly) alkoxytetramethacrylate" includes both "pentaerythritol alkoxytetramethacrylate" with m1+m2+m3+m4=1 in the general formula (II) and "pentaerythritol polyalkoxytetramethacrylate" with m1+m2+m3+m4=2 to 40. As the compound represented by the general formula (II), the compounds listed in Japanese Patent Publication No. 2013-156369, for example, pentaerythritol (poly) alkoxytetramethacrylate and the like can be cited.

[0141] The hexa(meth)acrylate compound is preferably a hexa(meth)acrylate obtained by adding 1 to 24 mol of ethylene oxide in total to the six terminals of dipentaerythritol, or a hexa(meth)acrylate obtained by adding 1 to 10 mol of ε-caprolactone in total to the six terminals of dipentaerythritol.

[0142] From the viewpoint of being able to significantly improve the adhesion when developing after heating after exposure, and especially achieving good adhesion even when the time after exposure becomes long, in the photosensitive resin composition described in this embodiment, as the compound (B) having an ethylenically unsaturated bond, it is particularly preferred to include a (meth)acrylate compound having 4 or more ethylenically unsaturated bonds and an alkylene oxide chain. In this case, the ethylenically unsaturated bond is more preferably derived from a methacryloyl group, and the alkylene oxide chain is more preferably an ethylene oxide chain.

[0143] In the present embodiment, from the viewpoint of being able to significantly improve the adhesion when heating and then developing after exposure, especially achieving good adhesion even when the time after exposure becomes long, in the photosensitive resin composition, as (B) a compound having an ethylenically unsaturated bond, it is preferred to include a (meth) acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton. As an alkylene oxide chain, for example, an ethylene oxide chain, a propylene oxide chain, a butylene oxide chain, a pentene oxide chain, a hexene oxide chain, etc. can be listed. When the photosensitive resin composition includes a plurality of alkylene oxide chains, they may be the same or different from each other. From the above viewpoint, as an alkylene oxide chain, an ethylene oxide chain, a propylene oxide chain and a butylene oxide chain are more preferably used, an ethylene oxide chain and a propylene oxide chain are further preferably used, and an ethylene oxide chain is particularly preferably used.

[0144] In the photosensitive resin composition, by using (A) an alkali-soluble polymer in combination with a (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, there is a tendency that the chemical resistance, adhesion, and resolution of the resist pattern can be balanced.

[0145] The (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton is an ester formed by a dipentaerythritol compound and (meth)acrylic acid, wherein at least one of the multiple hydroxyl groups is modified with an alkylene oxide. The six hydroxyl groups of the dipentaerythritol skeleton are optionally modified with an alkylene oxide. The number of ester bonds in one ester molecule can be 1 to 6, preferably 6.

[0146] Examples of the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton include hexa(meth)acrylates obtained by adding 4 to 30 mol, 6 to 24 mol, or 10 to 14 mol of alkylene oxide to dipentaerythritol.

[0147] Specifically, as the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton, a compound represented by the following general formula (III) is preferred from the viewpoint of significantly improving the adhesion when developing after heating after exposure, and in particular achieving good adhesion even when the time after exposure becomes long.

[0148]

[0149] {wherein, R each independently represents a hydrogen atom or a methyl group, and n is an integer of 0 to 30, and the total value of all n is 1 or more}. In the general formula (III), it is preferred that the average value of all n is 4 or more or n is 1 or more. R is preferably a methyl group.

[0150] From the same viewpoint, the content of the (meth)acrylate compound having an alkylene oxide chain and a dipentaerythritol skeleton is preferably in the range of 1% by mass to 50% by mass, more preferably 5% by mass to 40% by mass, and even more preferably 7% by mass to 30% by mass, based on the total solid content in the photosensitive resin composition.

[0151] The content of the (meth)acrylate compound (b1) having three or more ethylenically unsaturated bonds is preferably greater than 0% by mass and less than 40% by mass relative to the total solid content of the photosensitive resin composition. If the content exceeds 0% by mass, there is a tendency to significantly improve the adhesion when developing after heating after exposure, especially to achieve good adhesion even when the time after exposure becomes longer. If it is less than 40% by mass, there is a tendency to improve the flexibility of the cured resist and shorten the stripping time. The content is more preferably 2% by mass or more and 30% by mass or less, and more preferably 4% by mass or more and 25% by mass or less.

[0152] From the viewpoint of adhesion and suppression of developer foaming, the photosensitive resin composition preferably contains (b2) a compound having a butylene oxide chain or a propylene oxide chain and having one or two (meth)acryloyl groups as the compound having (B) an ethylenically unsaturated bond.

[0153] From the viewpoint of suppressing bleed-out, the compound (b2) having a butylene oxide chain or a propylene oxide chain and having one or two (meth)acryloyl groups preferably has a molecular weight of 500 or more, more preferably 700 or more, and even more preferably 1000 or more.

[0154] Examples of (b2) compounds having a butylene oxide chain or a propylene oxide chain and having one or two (meth)acryloyl groups include polypropylene glycol (meth)acrylate, polypropylene glycol di(meth)acrylate, poly-1,4-butylene glycol (meth)acrylate, poly-1,4-butylene glycol di(meth)acrylate, etc. (b2) compounds having a butylene oxide chain or a propylene oxide chain and having one or two (meth)acryloyl groups may further include an ethylene oxide chain in addition to the butylene oxide chain or the propylene oxide chain.

[0155] Specifically, the compound (b2) having a butylene oxide chain or a propylene oxide chain and having 1 or 2 (meth)acryloyl groups is a (meth)acrylate or di(meth)acrylate having preferably 1 to 20, more preferably 4 to 15, and even more preferably 6 to 12 C4H8O or C3H6O.

[0156] The content of the compound (b2) having a butylene oxide chain or a propylene oxide chain and having one or two (meth)acryloyl groups is preferably more than 0% by mass and not more than 20% by mass based on the total solid content of the photosensitive resin composition.

[0157] In the present embodiment, in order to suppress the oozing out of the constituent components of the dry film resist and improve the storage stability, based on the total solid content of the compound (B) having an ethylenically unsaturated bond, preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 100% by mass are compounds having a weight average molecular weight of 500 or more. From the viewpoint of suppressing oozing out and chemical resistance of the resist pattern, the weight average molecular weight of the compound (B) having an ethylenically unsaturated bond is preferably 760 or more, more preferably 800 or more, further preferably 830 or more, and particularly preferably 900 or more. The weight average molecular weight of the compound (B) having an ethylenically unsaturated bond can be obtained in the form of a molecular weight calculated from the molecular structure of the compound (B) having an ethylenically unsaturated bond. When there are a plurality of compounds (B) having an ethylenically unsaturated bond, the molecular weight of each compound can be obtained by weighted averaging the content.

[0158] From the viewpoint of chemical resistance, adhesion, high resolution and hem shape of the resist pattern, the concentration of the methacryloyl group in the compound (B) having an ethylenically unsaturated bond is preferably 0.20 mol / 100 g or more, more preferably 0.30 mol / 100 g or more, and further preferably 0.35 mol / 100 g or more. The upper limit of the concentration of the methacryloyl group is not limited as long as polymerizability and alkali developability are ensured, and for example, it may be 0.90 mol / 100 g or less or 0.80 mol / 100 g or less.

[0159] From the same viewpoint, the value of the concentration of methacryloyl groups in the compound (B) having an ethylenically unsaturated bond / (concentration of methacryloyl groups + concentration of acryloyl groups) is preferably 0.50 or more, more preferably 0.60 or more, further preferably 0.80 or more, particularly preferably 0.90 or more, and most preferably 0.95 or more.

[0160] The (meth)acrylate compounds described above can be used independently or in combination. In the photosensitive resin composition, as (B) a compound having an ethylenically unsaturated bond, other compounds may also be included. As other compounds, (meth)acrylates having an urethane bond, compounds obtained by reacting a polyol with an α,β-unsaturated carboxylic acid, compounds obtained by reacting a compound containing a glycidyl group with an α,β-unsaturated carboxylic acid, 1,6-hexanediol di(meth)acrylate, etc. can be cited.

[0161] (B) The ratio of the compound having an ethylenically unsaturated double bond to the total solid content of the photosensitive resin composition is preferably 5% to 70% by mass. From the viewpoint of sensitivity, resolution and adhesion, it is preferred that the ratio is 5% by mass or more. It is more preferred that the ratio is 20% by mass or more, and further preferably 30% by mass or more. On the other hand, from the viewpoint of suppressing edge fusion and delayed peeling of the cured resist, it is preferred that the ratio is 70% by mass or less. It is more preferred that the ratio is 50% by mass or less.

[0162] As the compound (B) having an ethylenically unsaturated double bond, the content of the compound (B-1) having a bisphenol A skeleton concentration of 0.18 mol / 100 g or more is preferably 0 or more and 18% by mass or less relative to the solid content of the photosensitive resin composition. Thus, the adhesion when developing after heating after exposure can be significantly improved, and in particular, good adhesion can be obtained even when the time after exposure becomes long. Compounds having an ethylenically unsaturated double bond with a high concentration of bisphenol A skeleton generally have improved adhesion due to their hydrophobicity.

[0163] The present invention has found that due to the rigid skeleton of bisphenol A, even if heated after exposure, the fluidity does not improve, and the effect of improving the adhesion is small. Therefore, in the present invention, from the above viewpoint, as the compound (B) having an ethylenically unsaturated double bond, the content of the compound (B-1) having a bisphenol A skeleton concentration of 0.18 mol / 100 g or more is preferably 18% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, most preferably 6% by mass or less, particularly preferably 3% by mass or less, and most preferably 1% by mass or less relative to the solid content of the photosensitive resin composition. From the same viewpoint, as the compound (B) having an ethylenically unsaturated double bond, the content of the compound (B-1) having a bisphenol A skeleton concentration of 0.20 mol / 100 g or more is preferably 18% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, most preferably 6% by mass or less, particularly preferably 3% by mass or less, and most preferably 1% by mass or less relative to the solid content of the photosensitive resin composition.

[0164] In particular, in the present embodiment, the value of [(A) alkali-soluble polymer content] / [(B) content of compounds having ethylenically unsaturated double bonds] is preferably 0.94 or more. Thus, the adhesion when developing after heating after exposure can be significantly improved, and in particular, good adhesion can be obtained even when the time after exposure becomes long. From the same viewpoint, [(A) alkali-soluble polymer content] / [(B) content of compounds having ethylenically unsaturated double bonds] is more preferably 1.04 or more, further preferably 1.11 or more, particularly preferably 1.21 or more, most preferably 1.30 or more, and most preferably 1.35 or more.

[0165] When the value of [(A) alkali-soluble polymer content] / [(B) content of compound having ethylenically unsaturated double bonds] is increased, the alkali-soluble, in other words, hydrophilic component generally increases, and the Tg in the system also increases, the fluidity decreases, and thus the double bond reaction rate decreases, and as a result, the adhesion generally decreases. However, it is considered that in the present invention, since the value of [(A) alkali-soluble polymer content] / [(B) content of compound having ethylenically unsaturated double bonds] is large and heat treatment is also performed after exposure, even if the value of [(A) alkali-soluble polymer content] / [(B) content of compound having ethylenically unsaturated double bonds] is large, the fluidity in the system is improved, the double bond reaction rate is also improved, and further, there is an effect of improving adhesion by the interaction between the carboxyl group of the alkali-soluble polymer and copper, and the effect of the present invention can be achieved.

[0166] The value of [(A) alkali-soluble polymer content] / [(B) compound having an ethylenically unsaturated double bond content] is preferably 5 or less, more preferably 4 or less, further preferably 3 or less, particularly preferably 2 or less, and most preferably 1.5 or less.

[0167] <(C) Photopolymerization Initiator>

[0168] (C) The photopolymerization initiator is a compound that polymerizes monomers using light.

[0169] (C-1) Photopolymerization initiator

[0170] The photosensitive resin composition of the present embodiment contains a compound generally known in the technical field as the (C-1) photopolymerization initiator ((C) photopolymerization initiator).

[0171] The total content of the photopolymerization initiator (C-1) in the photosensitive resin composition is preferably in the range of 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, further preferably 0.1 to 7% by mass, and particularly preferably 0.1 to 6% by mass. From the viewpoint of obtaining sufficient sensitivity, the total content of the photopolymerization initiator (C-1) is preferably 0.01% by mass or more, and from the viewpoint of allowing light to fully penetrate to the bottom surface of the resist and obtaining good high resolution, it is preferably 20% by mass or less.

[0172] Examples of the photopolymerization initiator (C-1) include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, oxime esters, acridines (for example, from the viewpoint of sensitivity, resolution, and adhesion, preferably 9-phenylacridine, bisacridylheptane, 9-(p-methylphenyl)acridine, 9-(m-methylphenyl)acridine), and further examples include hexaarylbiimidazoles, dihydropyrazole compounds, anthracene compounds ( For example, from the viewpoint of sensitivity, resolution, and adhesion, preferably 9,10-diphenylanthracene, 9,10-dibutoxyanthracene, 9,10-diethoxyanthracene), coumarin compounds (for example, from the viewpoint of sensitivity, resolution, and adhesion, preferably 7-diethylamino-4-methylcoumarin), N-aryl amino acids or their ester compounds (for example, from the viewpoint of sensitivity, resolution, and adhesion, preferably N-phenylglycine), and halides (for example, tribromomethylphenyl sulfone), etc. They can be used alone or in combination of two or more. In addition, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, and triphenylphosphine oxide can also be used.

[0173] As aromatic ketones, for example, benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone can be listed. These can be used alone or in combination of two or more. Among these, 4,4'-bis(diethylamino)benzophenone is preferred from the viewpoint of adhesion.

[0174] Furthermore, from the viewpoint of transmittance, the content of the aromatic ketone in the photosensitive resin composition is preferably in the range of 0.01% by mass to 0.5% by mass, and more preferably 0.02% by mass to 0.3% by mass.

[0175] Examples of the hexaarylbiimidazoles include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris(o-chlorophenyl)-diphenylbiimidazole, 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'-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)- phenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3,4,5-tetrafluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, 2,2'-bis(2,3,4,6-tetrafluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole and 2,2'-bis(2,3,4,5,6-pentafluorophenyl)-4,4',5,5'-tetrakis(3-methoxyphenyl)-biimidazole, etc., which can be used alone or in combination of two or more. From the viewpoint of high sensitivity, resolution and adhesion, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred.

[0176] In the present embodiment, from the viewpoint of improving the release characteristics and / or sensitivity of the photosensitive resin layer, the content of the hexaarylbiimidazole compound in the photosensitive resin composition is preferably in the range of 0.05% by mass to 7% by mass, more preferably 0.1% by mass to 6% by mass, and even more preferably 1% by mass to 5% by mass.

[0177] From the viewpoint of the peeling characteristics or sensitivity, resolution and adhesion of the photosensitive resin layer, the photosensitive resin composition preferably further contains a dihydropyrazole compound or anthracene compound (for example, from the viewpoint of sensitivity, resolution and adhesion, preferably a dialkoxyanthracene such as 9,10-diphenylanthracene, 9,10-dibutoxyanthracene and 9,10-diethoxyanthracene) as a photosensitizer.

[0178] As the dihydropyrazole compound, from the above viewpoint, preferably, for example, 1-phenyl-3-(4-tert-butyl-phenyl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-(4-(benzoxazol-2-yl)phenyl)-3-(4-tert-butyl-phenyl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-phenyl-3-(4-biphenylyl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-phenyl-3-(4-biphenylyl)-5-(4-tert-octyl-phenyl)-dihydropyrazole, 1-phenyl-3-(4-isopropylphenyl)-5-(4-isopropylphenyl)-dihydropyrazole, 1-phenyl-3-(4-methoxyphenyl)-5-(4-methoxyphenyl)-dihydropyrazole , 1-phenyl-3-(3,5-dimethoxyphenylvinyl)-5-(3,5-dimethoxyphenyl)-dihydropyrazole, 1-phenyl-3-(3,4-dimethoxyphenylvinyl)-5-(3,4-dimethoxyphenyl)-dihydropyrazole, 1-phenyl-3-(2,6-dimethoxyphenylvinyl)-5-(2,6-dimethoxyphenyl)-dihydropyrazole, 1-phenyl-3-(2,5-dimethoxyphenylvinyl)-5-(2,5-dimethoxyphenyl)-dihydropyrazole, 1-phenyl-3-(2,3-dimethoxyphenylvinyl)-5-(2,3-dimethoxyphenyl)-dihydropyrazole, 1-phenyl-3-(2,4-dimethoxyphenylvinyl)-5-(2,4-dimethoxyphenyl)-dihydropyrazole, etc. Among these, 1-phenyl-3-(4-biphenylyl)-5-(4-tert-butyl-phenyl)-dihydropyrazole is more preferred.

[0179] In the present embodiment, from the viewpoint of transmittance and from the viewpoint of improving the peeling characteristics and / or sensitivity of the photosensitive resin layer, the content of the photosensitizer in the photosensitive resin composition is preferably in the range of 0.05% by mass to 5% by mass, more preferably 0.1% by mass to 3% by mass, further preferably 0.1% by mass to 1% by mass, and particularly preferably 0.1% by mass to 0.7% by mass.

[0180] (C-2) Photopolymerization initiator

[0181] Furthermore, in the present embodiment, in the photosensitive resin composition, as the (C-2) photopolymerization initiator ((C) photopolymerization initiator), a photopolymerization initiator containing anthracene and / or anthracene derivative can be used.

[0182] When at least anthracene and / or anthracene derivatives are used as the photopolymerization initiator (C-2), it is advantageous from the viewpoint that the adhesion when developing after heating after exposure can be significantly improved, and in particular, good adhesion can be obtained even when the time after exposure becomes long. In addition, anthracene and / or anthracene derivatives can function as a polymerization initiator by absorbing the first active light having a central wavelength of less than 390 nm and the second active light having a central wavelength of more than 390 nm. The active light is, for example, laser.

[0183] Therefore, in one embodiment, the photosensitive resin composition may have photosensitivity to the first active light and the second active light, and may also be used for two-wavelength exposure. Anthracene and / or anthracene derivatives may also be selected in a manner that has multiple maximum absorption in the wavelength range of the first active light and the second active light. The central wavelength of the first active light is preferably 350 to 380 nm, more preferably 355 to 375 nm, and particularly preferably 375 nm. The central wavelength of the second active light is preferably 400 to 410 nm, more preferably 402 to 408 nm, and particularly preferably 405 nm (h-ray).

[0184] The total content of the photopolymerization initiator (C-2) in the photosensitive resin composition is preferably in the range of 0.01 to 20% by mass, more preferably 0.05 to 10% by mass, further preferably 0.1 to 7% by mass, and particularly preferably 0.1 to 6% by mass. From the viewpoint of obtaining sufficient sensitivity, the total content of the photopolymerization initiator (C-2) is preferably 0.01% by mass or more, and from the viewpoint of allowing light to fully penetrate to the bottom surface of the resist and obtaining good high resolution, the total content of the photopolymerization initiator (C-2) is preferably 20% by mass or less.

[0185] Anthracene and anthracene derivatives are advantageous from the viewpoint of being able to significantly improve the adhesion when developing after heating after exposure, and especially achieving good adhesion even when the time after exposure becomes long. From the same viewpoint, the anthracene derivative preferably has an alkoxy group having 1 to 40 carbon atoms and / or an aryl group having 6 to 40 carbon atoms, which may have a substituent, at the 9- and / or 10-positions, and more preferably at the 9- and 10-positions.

[0186] In one embodiment, the anthracene derivative preferably has an alkoxy group having 1 to 40 carbon atoms which may have a substituent at at least one of the 9-position or the 10-position, and more preferably has an alkoxy group having 1 to 30 carbon atoms which may have a substituent at at least one of the 9-position or the 10-position, from the viewpoint of significantly improving the adhesion when developing after heating after exposure, and especially achieving good adhesion even when the time after exposure becomes long. From the viewpoint of obtaining good adhesion and resolution, it is preferred to have an alkoxy group having 1 to 40 carbon atoms which may have a substituent at the 9- and 10-positions, and it is further preferred to have an alkoxy group having 1 to 30 carbon atoms which may have a substituent at the 9- and 10-positions. The number of carbon atoms of the groups at the 9- and 10-positions may be the same or different.

[0187] Examples of the alkoxy group which may have a substituent include:

[0188] methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, 2-methylpropoxy, 1-methylpropoxy, n-pentyloxy, isopentyloxy, n-hexyloxy, 2-ethylhexyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy, tetradecyloxy, hexadecyloxy, eicosyloxy, cyclohexyloxy, norbornyloxy, tricyclodecyloxy, tetracyclododecyloxy, adamantyloxy, methyladamantyloxy, ethyladamantyloxy and butyladamantyloxy;

[0189] Alkoxy groups modified with halogen, such as chlorobutoxy and chloropropoxy;

[0190] Alkoxy groups having a hydroxyl group added thereto, such as hydroxybutoxy;

[0191] Alkoxy groups to which a cyano group is added, such as cyanobutyloxy;

[0192] An alkoxy group to which an alkylene oxide group is added, such as a methoxybutoxy group;

[0193] Alkoxy groups to which aryl groups are added include, for example, phenoxybutoxy groups.

[0194] Among them, n-butoxy is more preferred.

[0195] In one embodiment, from the viewpoint of significantly improving the adhesion when developing after heating after exposure, and in particular achieving good adhesion even when the time after exposure becomes long, the anthracene derivative preferably has an aromatic group having 6 to 40 carbon atoms which may have a substituent at at least one of the 9-position or the 10-position, and more preferably has an aromatic group having 6 to 30 carbon atoms which may have a substituent at at least one of the 9-position or the 10-position.

[0196] From the viewpoint of being able to significantly improve the adhesion when developing after heating after exposure, and especially achieving good adhesion even when the time after exposure becomes long, it is preferred to have an aryl group having 6 to 40 carbon atoms and optionally having a substituent at the 9 and 10 positions, and it is more preferred to have an aryl group having 6 to 30 carbon atoms and optionally having a substituent at the 9 and 10 positions. The number of carbon atoms of the groups at the 9 and 10 positions may be the same or different. In addition, the groups at the 9 and 10 positions may be the same group or different groups. For example, the group at the 9 position may be an alkoxy group having 1 to 40 carbon atoms and optionally having a substituent, and the group at the 10 position may be an aryl group having 6 to 40 carbon atoms and optionally having a substituent.

[0197] Examples of the aryl group having 6 to 40 carbon atoms which may have a substituent include phenyl, biphenyl, naphthyl, anthracenyl; aryl groups to which an alkoxy group is added, such as methoxyphenyl and ethoxyphenyl; aryl groups to which an alkyl group is added, such as tolyl, xylyl, mesityl, and nonylphenyl; aryl groups to which a halogen is added, such as chlorophenyl; aryl groups to which a hydroxyl group is added, such as hydroxyphenyl, etc. Among them, phenyl is more preferred.

[0198] The anthracene derivative is preferably represented by the following general formula (IV).

[0199]

[0200] R 1 independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group or an N(R')2 group, and two or more R 1 They are optionally bonded to each other to form a ring structure, which optionally contains heteroatoms.

[0201] X independently represents a single bond, an oxygen atom, a sulfur atom, a carbonyl group, a sulfonyl group, a -N(R')- group, a -CO-O- group, a -CO-S- group, a -SO2-O- group, a -SO2-S- group, a -SO2-N(R')- group, a -O-CO- group, a -S-CO- group, a -O-SO2- group or a S-SO2- group. 1 is a combination of hydrogen atoms (i.e., unsubstituted anthracene).

[0202] The above R' represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms, a substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms, an alkenyl group having 2 to 4 carbon atoms, a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or a substituted or unsubstituted heteroaryl group, and R' may be optionally bonded to each other to form a cyclic structure, and the cyclic structure may optionally contain a heteroatom.

[0203] p is an integer of 1-10, and preferably 2-4.

[0204] As the above R 1 and R' are substituted or unsubstituted alkyl groups having 1 to 40 carbon atoms, specifically, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tetradecyl, n-hexadecyl, n-eicosyl, isopropyl, isobutyl, sec-butyl and tert-butyl.

[0205] As the above R 1 Specific examples of the substituted or unsubstituted alicyclic group having 3 to 20 carbon atoms in R' include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and bridged alicyclic hydrocarbon groups having 6 to 20 carbon atoms (for example, norbornyl, tricyclodecanyl, tetracyclododecyl, adamantyl, methyladamantyl, ethyladamantyl and butyladamantyl).

[0206] As the above R 1 Specific examples of the alkenyl group having 2 to 4 carbon atoms in R′ include vinyl group and propenyl group.

[0207] As the above R 1 Specific examples of the substituted or unsubstituted aryl group having 6 to 40 carbon atoms in R′ include phenyl, biphenyl, naphthyl, anthracenyl, methoxyphenyl, ethoxyphenyl, tolyl, xylyl, mesityl, nonylphenyl, chlorophenyl, and hydroxyphenyl.

[0208] As the above R 1 Examples of the substituted or unsubstituted heteroaryl group in R' include groups containing one or more heteroatoms such as sulfur atoms, oxygen atoms, and nitrogen atoms in substituted or unsubstituted aryl groups, such as pyridyl, imidazolyl, morpholinyl, piperidinyl, and pyrrolidinyl.

[0209] In addition, the above R 1Each hydrocarbon group of R and R' may be substituted with a substituent. Examples of such substituents include hydroxyl, carboxyl, hydroxyalkyl having 1 to 4 carbon atoms (e.g., hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxypropyl, 2-hydroxypropyl, 3-hydroxypropyl, 1-hydroxybutyl, 2-hydroxybutyl, 3-hydroxybutyl, 4-hydroxybutyl, etc.), alkoxy having 1 to 4 carbon atoms (e.g., methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, 2-methylpropoxy, 1-methylpropoxy, tert-butyl, etc.), R is preferably a cyano group, a cyanoalkyl group having 2 to 5 carbon atoms (e.g., cyanomethyl, 2-cyanoethyl, 3-cyanopropyl, 4-cyanobutyl, etc.), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, etc.), an alkoxycarbonylalkoxy group (e.g., methoxycarbonylmethoxy, ethoxycarbonylmethoxy, tert-butoxycarbonylmethoxy, etc.), a halogen atom (e.g., fluorine, chlorine, etc.), and a fluoroalkyl group (e.g., fluoromethyl, trifluoromethyl, pentafluoroethyl, etc.). 1 Each hydrocarbon group of R and R' is preferably substituted with a halogen atom. In particular, the anthracene derivative preferably has an alkoxy group substituted with a halogen atom at the 9-position and / or the 10-position.

[0210] As the above R 1 Preferred specific examples of R' include a hydrogen atom, a methyl group, an ethyl group, a n-propyl group, an isopropyl group, a n-butyl group, a tert-butyl group, a n-pentyl group, a n-hexyl group, a n-heptyl group, a n-octyl group, a cyclopentyl group, a cyclohexyl group, a camphoryl group, a norbornyl group, a p-toluoyl group, a benzyl group, a methylbenzyl group, a phenyl group and a 1-naphthyl group.

[0211] Preferred specific examples of X include a single bond, an oxygen atom, a sulfur atom, an -N(R')- group, an -O-CO- group, and an O-SO2- group. When X is an -N(R')- group, R' is preferably a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a cyclopentyl group, a cyclohexyl group, a camphoryl group, a norbornyl group, or a benzyl group.

[0212] Examples of the compound represented by the general formula (IV) include 1-methylanthracene, 2-methylanthracene, 2-ethylanthracene, 2-tert-butylanthracene, 9-methylanthracene, 9,10-dimethylanthracene, 9-vinylanthracene, 9-phenylanthracene, 9,10-diphenylanthracene, 2-bromo-9,10-diphenylanthracene, 9-(4-bromophenyl)-10-phenylanthracene, 9-(1-naphthyl)anthracene, 9-(2-naphthyl)anthracene, 2-bromo-9,10-bis(2-naphthyl)anthracene, 2,6- Dibromo-9,10-bis(2-naphthyl)anthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-di(2-ethylhexyloxy)anthracene, 1,2-benzanthracene, dihydroxyanthraquinone, 1,4,9,10-tetrahydroxyanthracene, 9-anthracenemethanol, 1-aminoanthracene, 2-aminoanthracene, 9-(methylaminomethyl)anthracene, 9-acetylanthracene, 9-anthraldehyde, 10-methyl-9-anthraldehyde, 1,8,9-triacetoxyanthracene, etc. Among these, 9,10-dimethylanthracene, 9,10-diphenylanthracene, 9,10-diethoxyanthracene, 9,10-dipropoxyanthracene, 9,10-dibutoxyanthracene, 9,10-di(2-ethylhexyloxy)anthracene, and 9,10-bis(3-chloropropoxy)anthracene are preferred. In particular, from the viewpoint of significantly improving the adhesion when developing after heating after exposure, and achieving good adhesion even when the time after exposure becomes long, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 9,10-bis(3-chloropropoxy)anthracene are more preferred. 9,10-dibutoxyanthracene, 9,10-diphenylanthracene, and 9,10-bis(3-chloropropoxy)anthracene are particularly preferred. The compound represented by the above general formula (IV) can be used alone or in combination of two or more.

[0213] From the viewpoint of being able to significantly improve the adhesion when developing after heating after exposure, and in particular being able to obtain good adhesion even when the time after exposure becomes long, the (C-2) photopolymerization initiator preferably (1) includes 9,10-diphenylanthracene; (2) includes 9,10-dialkoxyanthracene; (3) includes anthracene derivatives having halogen atoms; (4) includes halogenated compounds of 9,10-dialkoxyanthracene; (5) includes compounds in which the alkoxy groups at the 9-position and / or 10-position of 9,10-dialkoxyanthracene are modified with one or more halogen atoms; and / or, (6) includes compounds having halogen atoms directly bonded to the anthracene skeleton.

[0214] The compound represented by the general formula (IV) is advantageous from the viewpoint of being able to significantly improve the adhesion when developing after heating after exposure, and in particular, being able to obtain good adhesion even when the time after exposure becomes long. Furthermore, it is also advantageous from the viewpoint of being able to provide a photosensitive resin composition showing excellent sensitivity, adhesion and resolution by being applicable to two-wavelength exposure using a first active light having a central wavelength of less than 390 nm and a second active light having a central wavelength of 390 nm or more.

[0215] In one embodiment, the photopolymerization initiator (C-2) preferably contains an anthracene derivative having a halogen atom. A suitable example of the anthracene derivative having a halogen atom is a halogenated compound of 9,10-dialkoxyanthracene. A suitable example of the halogenated compound is a compound in which the alkoxy group at the 9-position and / or 10-position of 9,10-dialkoxyanthracene is modified with one or more halogens. Preferred alkoxy groups include the alkoxy groups exemplified above as alkoxy groups having 1 to 40 carbon atoms.

[0216] In one embodiment, as anthracene derivatives, compounds having a halogen atom directly bonded to the anthracene skeleton are also preferred. Examples of such anthracene compounds include 9-bromo-10-phenylanthracene, 9-chloro-10-phenylanthracene, 9-bromo-10-(2-naphthyl)anthracene, 9-bromo-10-(1-naphthyl)anthracene, 9-(2-biphenyl)-10-bromoanthracene, 9-(4-biphenyl)-10-bromoanthracene, 9-bromo-10-(9-phenanthracene), 2-bromoanthracene, 9-bromoanthracene, 2-chloroanthracene, and 9,10-dibromoanthracene.

[0217] The total amount of anthracene and anthracene derivatives or the compound represented by the general formula (IV) is preferably in the range of 0.05 to 5% by mass, more preferably 0.1 to 3% by mass, and particularly preferably 0.1 to 1.0% by mass based on the total solid content of the photosensitive resin composition.

[0218] (C-2) The photopolymerization initiator may further contain compounds other than anthracene and anthracene derivatives, and examples of such compounds include quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoic acid esters, oxime esters, acridines (for example, preferably 9-phenylacridine, bisacridylheptane, 9-(p-methylphenyl)acridine, 9-(m-methylphenyl)acridine from the viewpoints of sensitivity, resolution and adhesion), hexaarylbiimidazoles, dihydropyrazole compounds, coumarin compounds (for example, preferably 7-diethylamino-4-methylcoumarin from the viewpoints of sensitivity, resolution and adhesion), N-aryl amino acids or ester compounds thereof (for example, preferably N-phenylglycine from the viewpoints of sensitivity, resolution and adhesion), and halides (for example, tribromomethylphenylsulfone). These may be used alone or in combination of two or more. In addition, 2,2-dimethoxy-1,2-diphenylethane-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, triphenylphosphine oxide, and the like can also be used.

[0219] As aromatic ketones, for example, benzophenone, Michler's ketone [4,4'-bis(dimethylamino)benzophenone], 4,4'-bis(diethylamino)benzophenone, and 4-methoxy-4'-dimethylaminobenzophenone can be listed. One of them can be used alone or two or more can be used in combination. Among these, 4,4'-bis(diethylamino)benzophenone is preferred from the viewpoint of adhesion. Furthermore, from the viewpoint of transmittance, the content of aromatic ketones in the photosensitive resin composition is preferably in the range of 0.01% to 0.5% by mass, and more preferably in the range of 0.02% to 0.3% by mass.

[0220] Examples of the hexaarylbiimidazole include 2-(o-chlorophenyl)-4,5-diphenylbiimidazole, 2,2',5-tris(o-chlorophenyl)-4-(3,4-dimethoxyphenyl)-4',5'-diphenylbiimidazole, 2,4-bis(o-chlorophenyl)-5-(3,4-dimethoxyphenyl)-diphenylbiimidazole, 2,4,5-tris(o-chlorophenyl)-diphenylbiimidazole, 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, '-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)- 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer is preferred from the viewpoints of sensitivity, resolution and adhesion.

[0221] From the viewpoint of improving the release property and / or sensitivity of the photosensitive resin layer, the content of the hexaarylbiimidazole compound in the photosensitive resin composition is preferably within a range of 0.05 to 8 mass %, more preferably 0.1 to 7 mass %, and even more preferably 1 to 6 mass %.

[0222] The photosensitive resin composition preferably contains one or more dihydropyrazole compounds as the (C-2) photopolymerization initiator from the viewpoint of the peeling characteristics, sensitivity, resolution, and adhesion of the photosensitive resin layer.

[0223] As the dihydropyrazole compound, from the above viewpoint, for example, 1-phenyl-3-(4-tert-butyl-phenyl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-(4-(benzoxazol-2-yl)phenyl)-3-(4-tert-butyl-phenyl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-phenyl-3-(4-biphenylyl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-phenyl-3-(4-biphenylyl)-5-(4-tert-octyl-phenyl)-dihydropyrazole, 1-phenyl-3-(4-isopropylphenyl)-5-(4-isopropylphenyl)-dihydropyrazole, 1-phenyl-3-(4-methoxyphenyl)-5-(4-methoxyphenyl)-dihydropyrazole, 1-phenyl-3-(3,5-dimethoxyphenyl)- dihydropyrazole, 1-phenyl-3-(4-biphenylyl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-phenyl-3-(4-biphenylyl)-5-(4-tert-butyl-phenyl)-dihydropyrazole, 1-phenyl-3-(2,5-dimethoxyphenyl-5-(2,3-dimethoxyphenyl-5-(2,3-dimethoxyphenyl-)-dihydropyrazole, 1-phenyl-3-(2,4-dimethoxyphenyl-5-(2,4-dimethoxyphenyl)-dihydropyrazole, and the like, more preferably 1-phenyl-3-(4-biphenylyl)-5-(4-tert-butyl-phenyl)-dihydropyrazole.

[0224] <(D) Inhibitor>

[0225] In this embodiment, from the viewpoint that the shortest development time of the unexposed portion is not extended even if heating after exposure is performed, it is preferred that the photosensitive resin composition further contains (D) an inhibitor. From the same viewpoint, as the (D) inhibitor, a free radical inhibitor or a phenol derivative is preferred, and a phenol derivative is more preferred. The (D) inhibitor may be originally contained in the raw material components used, or may be added when preparing the photosensitive resin composition preparation liquid. In the case where it is originally contained in the raw material components used, the inhibitor content may be quantified by GC-MS analysis or the like after the photosensitive resin laminate is prepared.

[0226] Examples of the radical polymerization inhibitor include naphthylamine, cuprous chloride, nitrosophenylhydroxylamine aluminum salt, diphenylnitrosoamine, etc. In order not to impair the sensitivity of the photosensitive resin composition, nitrosophenylhydroxylamine aluminum salt is preferred.

[0227] Examples of the phenol derivatives include p-methoxyphenol, hydroquinone, pyrogallol, tert-butylcatechol, 2,6-di-tert-butyl-p-cresol, 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-ethyl-6-tert-butylphenol), 2,6-di-tert-butyl-4-methylphenol, 2,5-di-tert-amylhydroquinone, 2,5-di-tert-butylhydroquinone, 2, 2'-Methylenebis(4-methyl-6-tert-butylphenol), bis(2-hydroxy-3-tert-butyl-5-ethylphenyl)methane, triethylene glycol bis[3-(3-tert-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], pentaerythritol-tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] , 2,2-dithiodiethylene-bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate octadecyl ester, N,N'-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamic acid amide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tri(3 ,5-di-tert-butyl-4-hydroxybenzyl)benzene, tris(3,5-di-tert-butyl-4-hydroxybenzyl)-isocyanurate, 4,4'-thiobis(6-tert-butyl-m-cresol), 4,4'-butylenebis(3-methyl-6-tert-butylphenol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane, styrenated phenol (e.g., ANTAGE SP manufactured by Kawaguchi Chemical Industries, Ltd.), tribenzylphenol (e.g., TBP manufactured by Kawaguchi Chemical Industries, Ltd., phenol having 1 to 3 benzyl groups), biphenol, etc.

[0228] The ratio of the inhibitor (D) to the total solid content of the photosensitive resin composition is preferably 0.001% to 10% by mass. From the viewpoint that the shortest development time of the unexposed portion is not prolonged even by heating after exposure, the ratio is preferably 0.001% by mass or more, more preferably 0.005% by mass or more, further preferably 0.01% by mass or more, most preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. On the other hand, from the viewpoint of less reduction in sensitivity and improved resolution, the ratio is preferably 10% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and most preferably 0.3% by mass or less.

[0229] <(E) Benzotriazole derivatives>

[0230] Furthermore, from the viewpoint that no discoloration is observed on the copper surface after the photosensitive resin composition layer is removed by development even after heating after exposure, it is preferred to include a (E) benzotriazole derivative. As the (E) benzotriazole derivative, it is preferred to include at least one compound selected from the group consisting of benzotriazoles and carboxybenzotriazoles.

[0231] Examples of the benzotriazoles include 1,2,3-benzotriazole, 1-chloro-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-benzotriazole, bis(N-2-ethylhexyl)aminomethylene-1,2,3-tolyltriazole, and bis(N-2-hydroxyethyl)aminomethylene-1,2,3-benzotriazole.

[0232] Examples of the carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, N-(N,N-di-2-ethylhexyl)aminomethylenecarboxybenzotriazole, N-(N,N-di-2-hydroxyethyl)aminomethylenecarboxybenzotriazole, and N-(N,N-di-2-ethylhexyl)aminoethylenecarboxybenzotriazole.

[0233] Among these, carboxybenzotriazoles are particularly preferred.

[0234] When the total solid content of the photosensitive resin composition is 100% by mass, the content of the (E) benzotriazole derivative is preferably 0.001% to 3% by mass. From the viewpoint that no discoloration is observed on the copper surface after the photosensitive resin composition layer is removed by development even after heating after exposure, it is preferred that the content be 0.001% by mass or more, more preferably 0.02% by mass or more, and further preferably 0.05% by mass or more. On the other hand, from the viewpoint of maintaining sensitivity and inhibiting dye bleaching, it is preferred that the content be 3% by mass or less, more preferably 2% by mass or less, further preferably 1% by mass or less, particularly preferably 0.5% by mass or less, and most preferably 0.3% by mass or less.

[0235] The decolorization of the dye can be measured at the transmittance at a wavelength of 630 nm. A high transmittance at a wavelength of 630 nm indicates that the dye has been decolorized. The transmittance at a wavelength of 630 nm of the laminate of the support film and the photosensitive resin composition layer is preferably 80% or less, preferably 78% or less, preferably 75% or less, preferably 72% or less, preferably 70% or less, preferably 68% or less, preferably 65% ​​or less, preferably 62% or less, preferably 60% or less, preferably 58% or less, preferably 55% or less, preferably 52% or less, preferably 50% or less. The transmittance is the transmittance of the laminate of the support film and the photosensitive resin composition layer, excluding the protective layer.

[0236] <Additives>

[0237] The photosensitive resin composition may contain additives such as a dye, a plasticizer, an antioxidant, and a stabilizer as desired. For example, additives listed in Japanese Patent Application Laid-Open No. 2013-156369 may be used.

[0238] (Dyes and coloring matter)

[0239] In the present embodiment, the photosensitive resin composition may further contain at least one selected from the group consisting of a dye (for example, a leuco dye, a fluoran dye, etc.) and a coloring substance as desired.

[0240] As coloring materials, for example, magenta, phthalocyanine green, basic yellow, para-magenta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (for example, Hodogaya Chemical Co., Ltd., Aizen (registered trademark) MALACHITEGREEN), basic blue 20, diamond green (for example, Hodogaya Chemical Co., Ltd., Aizen (registered trademark) DIAMOND GREEN GH). When the total solid content mass of the photosensitive resin composition is set to 100% by mass, the content of the coloring material in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass. From the viewpoint of improving the handleability of the photosensitive resin composition, it is preferred that the content is 0.001% by mass or more. On the other hand, from the viewpoint of maintaining the storage stability of the photosensitive resin composition, it is preferred that the content is 1% by mass or less.

[0241] The photosensitive resin composition contains a dye to color the exposed part, so it is preferred from the viewpoint of visual observation. In addition, when the alignment mark for exposure is read by an inspection machine, it is advantageous to easily identify the exposed part when the contrast between the exposed part and the unexposed part is large. From this viewpoint, preferred dyes include leuco dyes and fluorane dyes.

[0242] As leuco dyes, tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenyl methane [leuco malachite green], etc. can be cited. In particular, from the viewpoint of good contrast, leuco crystal violet is preferably used as a leuco dye. The content of the leuco dye in the photosensitive resin composition is preferably 0.1% by mass to 10% by mass relative to the total solid content mass of the photosensitive resin composition. From the viewpoint of making the contrast between the exposed part and the unexposed part good, it is preferred that the content is 0.1% by mass or more. It is more preferred that the content is 0.2% by mass or more, and particularly preferably 0.4% by mass or more. On the other hand, from the viewpoint of maintaining storage stability, it is preferred that the content is 10% by mass or less. It is more preferred that the content is 5% by mass or less, and particularly preferably 2% by mass or less.

[0243] In addition, from the viewpoint of optimizing adhesion and contrast, it is preferred to use a leuco dye in combination with the halogenated compound described in (C) the photopolymerization initiator in the photosensitive resin composition. When a leuco dye is used in combination with the halogenated compound, from the viewpoint of maintaining the storage stability of the hue in the photosensitive layer, the content of the halogenated compound in the photosensitive resin composition is preferably 0.01% to 3% by mass when the total solid content mass of the photosensitive resin composition is 100% by mass.

[0244] (Other additives)

[0245] In this embodiment, the photosensitive resin composition may further contain epoxy compounds of bisphenol A. Examples of epoxy compounds of bisphenol A include compounds obtained by modifying bisphenol A with polypropylene glycol and performing terminal epoxidation.

[0246] In the present embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of the plasticizer include phthalates (e.g., diethyl phthalate), o-toluenesulfonamide, p-toluenesulfonamide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, acetyl tri-n-propyl citrate, acetyl tri-n-butyl citrate, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, polypropylene glycol alkyl ether, and the like. In addition, compounds having a bisphenol skeleton may also be listed, such as ADEKANOLSDX-1569, ADEKANOL SDX-1570, ADEKANOL SDX-1571, and ADEKANOL SDX-479 (all manufactured by Asahi Denka Corporation); NEWPOL BP-23P, NEWPOL BP-3P, NEWPOL BP-5P, NEWPOL BPE-20T, NEWPOL BPE-60, NEWPOL BPE-100, and NEWPOL BPE-180 (all manufactured by Sanyo Chemical Co., Ltd.); UNIOL DB-400, UNIOL DAB-800, UNIOL DA-350F, UNIOL DA-400, and UNIOL DA-700 (all manufactured by NOF Corporation); BA-P4UGLYCOL and BA-P8 GLYCOL (all manufactured by Nippon Emulsifier Co., Ltd.).

[0247] The content of the plasticizer in the photosensitive resin composition is preferably 1% to 50% by mass, more preferably 1% to 30% by mass, relative to the total solid content of the photosensitive resin composition. From the viewpoint of suppressing the delay of the development time and imparting flexibility to the cured film, it is preferred that the content be 1% by mass or more. On the other hand, from the viewpoint of suppressing insufficient curing and cold flow, it is preferred that the content be 50% by mass or less.

[0248] If the amount of water in the photosensitive resin composition is high, local plasticization of the photosensitive resin composition is rapidly promoted, and edge fusion occurs. From the viewpoint of suppressing edge fusion, the amount of water in the photosensitive resin composition is preferably 0.7% or less, based on the photosensitive resin composition after the photosensitive resin composition formulation is applied to the support film and dried. The amount of water in the photosensitive resin composition is preferably 0.65% or less, preferably 0.6% or less, preferably 0.55% or less, preferably 0.5% or less, preferably 0.45% or less, preferably 0.4% or less, preferably 0.35% or less, preferably 0.3% or less, preferably 0.25% or less, and preferably 0.2% or less.

[0249] [Solvent]

[0250] The photosensitive resin composition can be dissolved in a solvent and used in the form of a photosensitive resin composition preparation liquid to manufacture a photosensitive resin laminate. Examples of the solvent include ketones, alcohols, and the like. The aforementioned ketones are represented by methyl ethyl ketone (MEK) and acetone. The aforementioned alcohols are represented by methanol, ethanol, and isopropanol. When manufacturing a photosensitive resin laminate, the solvent is preferably added to the photosensitive resin composition in an amount such that the viscosity of the photosensitive resin composition preparation liquid applied to the support layer at 25°C reaches 500 mPa·s to 4,000 mPa·s.

[0251] [Photosensitive resin laminate]

[0252] As the support film, a transparent support film that transmits light emitted from the exposure light source is preferred. Examples of such support films include polyethylene terephthalate films, polyvinyl alcohol films, polyvinyl chloride films, vinyl chloride copolymer films, polyvinylidene chloride films, vinylidene chloride copolymer films, polymethyl methacrylate copolymer films, polystyrene films, polyacrylonitrile films, styrene copolymer films, polyamide films, and cellulose derivative films. These films may be stretched as required.

[0253] As a supporting film, from the viewpoint of suppressing light scattering during exposure, a film with a haze of 5% or less is preferred, more preferably 2% or less, further preferably 1.5% or less, and particularly preferably 1.0% or less. From the same viewpoint, the surface roughness Ra of the surface in contact with the photosensitive layer is preferably 30nm or less, more preferably 20nm or less, and particularly preferably 10nm or less. The thinner the film, the more it will improve image formation and economy, so it is advantageous, but in order to maintain the strength of the photosensitive resin laminate, it is preferred to use a film of 10μm to 30μm. The size of the particles such as the lubricant contained in the supporting film is preferably less than 5μm.

[0254] In addition, the supporting film may be a single-layer structure or a multilayer structure in which a resin layer composed of a plurality of components is stacked. In the case of a multilayer structure, an antistatic layer may be provided. In the case of a multilayer structure such as a two-layer structure or a three-layer structure, for example, the following structure may be adopted: a resin layer containing particles is formed on one surface A and the other surface B (1) contains particles in the same manner as surface A, (2) contains a smaller amount of particles than surface A, (3) contains finer particles than surface A, or (4) contains no particles. In the case of structures (2), (3), and (4), it is preferred to form a photosensitive resin layer on the surface B side. At this time, if there is a resin layer containing particles on the surface A side, it is preferred from the viewpoint of the slipperiness of the film. As for the particle size at this time, it is also preferred to be less than 1.5 μm from the viewpoint of the effect of the present invention.

[0255] The important characteristic of the protective layer used in the photosensitive resin laminate is that the adhesion to the photosensitive resin layer is sufficiently small compared with the support layer, and it can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as the protective layer. In addition, a film with excellent peelability shown in Japanese Patent Publication No. 59-202457 can also be used. The film thickness of the protective layer is preferably 10 μm to 100 μm, and more preferably 10 μm to 50 μm.

[0256] Sometimes there is a gel called fisheye on the surface of the polyethylene film. When the polyethylene film with fisheye is used as a protective layer, the fisheye is sometimes transferred to the photosensitive resin layer. If the fisheye is transferred to the photosensitive resin layer, air is sometimes drawn in during lamination to form a gap, resulting in a defect in the resist pattern. From the viewpoint of preventing fisheyes, the material of the protective layer is preferably stretched polypropylene. As a specific example, ALPHAN E-200A manufactured by Prince Paper Co., Ltd. can be cited.

[0257] The thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, but is preferably 1 μm to 300 μm, more preferably 3 μm to 100 μm, particularly preferably 5 μm to 60 μm, and most preferably 10 μm to 30 μm. The thinner the photosensitive resin layer, the higher the resolution, and the thicker the photosensitive resin layer, the higher the film strength.

[0258] Next, a method for producing a photosensitive resin laminate will be described.

[0259] As a method for sequentially laminating a support layer and a photosensitive resin layer, and a protective layer as required to produce a photosensitive resin laminate, a known method can be adopted. For example, a photosensitive resin composition used for a photosensitive resin layer is mixed with a solvent that dissolves the photosensitive resin composition to form a uniform solution, first applied to the support layer using a rod coater or a roller coater, and then dried to remove the solvent, thereby making it possible to laminate a photosensitive resin layer formed of the photosensitive resin composition on the support layer. Then, as required, a protective layer can be laminated on the photosensitive resin layer to produce a photosensitive resin laminate.

[0260] <Method for Forming Resist Pattern>

[0261] Next, an example of a method for preparing a resist pattern using the photosensitive resin laminate of the present embodiment is described. The method may include the following steps: an exposure step of exposing the photosensitive resin composition; a heating step of heating the exposed photosensitive resin composition; and a development step of developing the photosensitive resin composition.

[0262] As the anti-etching pattern, for example, patterns of printed circuit boards, semiconductor elements, printed plates, liquid crystal display panels, touch panels, flexible substrates, lead frame substrates, COF (chip on film) substrates, semiconductor packaging substrates, transparent electrodes for liquid crystals, wiring for liquid crystal TFTs, PDP (plasma display panel) electrodes, etc. can be listed. As an example, the method for manufacturing a printed circuit board is described as follows.

[0263] Printed circuit boards are manufactured through the following steps.

[0264] (1) Lamination process

[0265] First, in the lamination process, a photosensitive resin layer is formed on a substrate using a laminator. Specifically, when the photosensitive resin laminate has a protective layer, the protective layer is peeled off, and then the photosensitive resin layer is heated and pressed onto the substrate surface using a laminator for lamination. Examples of the material of the substrate include copper, stainless steel (SUS), glass, indium tin oxide (ITO), and the like.

[0266] In the present embodiment, the photosensitive resin layer can be laminated only on one side of the substrate surface or on both sides as required. The heating temperature during lamination is generally 40°C to 160°C. In addition, by performing the heat pressing during lamination more than twice, the adhesion of the obtained resist pattern to the substrate can be improved. During the heat pressing, the laminate can be pressed by using a two-stage laminator equipped with two rollers or by repeatedly passing the laminate of the substrate and the photosensitive resin layer through the rollers.

[0267] (2) Exposure process

[0268] In this process, the photosensitive resin layer is exposed by an exposure method in which a mask film having a desired wiring pattern is closely attached to a supporting layer and an active light source is used, an exposure method based on direct drawing of a drawing pattern as the desired wiring pattern, or an exposure method based on projecting an image of a photomask through a lens.

[0269] The exposure step is preferably performed by an exposure method based on direct drawing of a drawing pattern or an exposure method in which an image of a photomask is projected through a lens, and more preferably performed by an exposure method based on direct drawing of a drawing pattern. The advantages of the photosensitive resin composition described in this embodiment are more significant in an exposure method based on direct drawing of a drawing pattern or an exposure method in which an image of a photomask is projected through a lens, and are particularly significant in an exposure method based on direct drawing of a drawing pattern.

[0270] When the exposure process is an exposure method based on direct drawing, it is preferred that the laser has a central wavelength of less than 390nm or a laser with a central wavelength of 390nm or more. More preferably, the laser has a central wavelength of 350nm or more and 380nm or less or a laser with a central wavelength of 400nm or more and 410nm or less. It is preferably carried out by a method of exposing using a first laser with a central wavelength of less than 390nm and a second laser with a central wavelength of 390nm or more. In addition, it is more preferred that the central wavelength of the first laser is 350nm or more and 380nm or less, and the central wavelength of the second laser is 400nm or more and 410nm or less.

[0271] (3) Heating process

[0272] In this process, it is preferred that the exposed photosensitive resin composition be subjected to a heating process at about 30°C to about 200°C, more preferably in the range of 30°C to 150°C, and further preferably in the range of 60°C to 120°C. By implementing this heating process, the resolution and adhesion can be improved. Heating can be performed using a heating furnace, a thermostatic bath, a heating plate, a hot air dryer, an infrared dryer, a hot roller, etc. using hot air, infrared or far infrared. If the heating method is a hot roller, it is preferred from the perspective of being able to process in a short time, and more preferably there are two or more hot rollers.

[0273] In particular, in the present invention, by containing structural units of 15% by mass or more of styrene and / or styrene derivatives and heating and then developing after exposure, even a system with a high content of styrene skeleton can improve the fluidity of the resin due to heating, and can highly take into account the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond.

[0274] Furthermore, in the present invention, by using at least anthracene and / or anthracene derivatives as (C-2) photopolymerization initiator ((C) photopolymerization initiator), and heating and then developing after exposure, the fluidity of the resin is improved by heating. For example, even in a system with a high content of styrene skeleton, the hydrophobicity of the styrene skeleton and the reactivity of the carbon-carbon double bond can be highly taken into account.

[0275] As a result, the adhesion can be significantly improved. Moreover, by significantly improving the adhesion, good adhesion can be obtained even when the time after exposure becomes longer. In addition, from the viewpoint of the effect of the present invention, the above-mentioned heating step is preferably carried out within 15 minutes after exposure, more preferably within 10 minutes, and further preferably within 5 minutes.

[0276] (4) Development process

[0277] In this step, the support layer on the photosensitive resin layer is peeled off after exposure, and then the unexposed portion is developed and removed using a developer of an alkaline aqueous solution, thereby forming a resist pattern on the substrate.

[0278] As the alkaline aqueous solution, an aqueous solution of Na2CO3 or K2CO3 is used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, and a Na2CO3 aqueous solution having a concentration of about 0.2% to 2% by mass and about 20°C to 40°C is preferred.

[0279] A resist pattern can be obtained through the above steps (1) to (4).

[0280] In the method for producing a circuit board of the present invention, the circuit board is formed by etching or plating the substrate having the resist pattern produced by the above method.

[0281] (5) Etching process or plating process

[0282] The substrate surface (for example, the copper surface of a copper-clad laminate) exposed by development is etched or plated to produce a conductor pattern.

[0283] (6) Peeling process

[0284] Thereafter, the resist pattern is peeled off from the substrate using an appropriate stripping solution.

[0285] As the stripping solution used here, for example, an alkaline aqueous solution, an amine stripping solution, etc. can be cited. However, the resist pattern formed by the photosensitive resin composition of the present invention after exposure and heating has the following characteristics: it shows good stripping properties to the amine stripping solution, and the stripping piece is not excessively fine. Therefore, if an amine stripping solution is used as the stripping solution, the advantageous effects of the present invention can be maximized, so it is preferred.

[0286] The amine contained in the amine-based stripping solution may be an inorganic amine or an organic amine.

[0287] Examples of the inorganic amine include ammonia, hydroxylamine, and hydrazine.

[0288] Examples of organic amines include ethanolamine, propanolamine, alkylamines, cyclic amines, and quaternary ammonium salts.

[0289] Examples of the ethanolamine include monoethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, N-ethylethanolamine, N,N-dimethylethanolamine, N,N-diethylethanolamine, and aminoethoxyethanol.

[0290] Examples of the propanolamine include 1-amino-2-propanol, 2-amino-2-methyl-1-propanol, and 2-amino-2-methyl-1,3-propanediol.

[0291] Examples of the alkylamine include monomethylamine, dimethylamine, trimethylamine, ethyleneamine, ethylenediamine, diethylenetriamine, triethylenetetramine, hexamethylenetetramine, and tetraethylenepentamine;

[0292] Examples of the cyclic amine include choline and morpholine;

[0293] Examples of the quaternary ammonium salt include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, N,N,N-triethyl-N-(2-hydroxyethyl)ammonium hydroxide, and N,N-diethyl-N,N-di(2-hydroxyethyl)ammonium hydroxide.

[0294] The amine-based stripping agent used in the present invention may be an aqueous solution containing one or more of the above-exemplified amines. The concentration of the amine in the aqueous solution can be appropriately set depending on the purpose, the composition of the photosensitive resin layer, the development conditions, and the like.

[0295] The amine-based release agent used in the present invention may further contain additives commonly used in release agents, such as surfactants, defoamers, pH adjusters, preservatives, anti-reattachment agents, and the like.

[0296] The peeling step is performed at a temperature of, for example, 0°C to 100°C, preferably room temperature (23°C) to 50°C, for, for example, 1 second to 1 hour, preferably 10 seconds to 10 minutes.

[0297] After the stripping step, the substrate from which the resist pattern has been removed may be washed with, for example, pure water, as desired.

[0298] The photosensitive resin laminate of this embodiment is a photosensitive resin laminate suitable for manufacturing conductor patterns such as printed circuit boards, flexible substrates, lead frame substrates, touch panel substrates, COF substrates, semiconductor package substrates, transparent electrodes for liquid crystals, wiring for liquid crystal TFTs, and electrodes for PDPs.

[0299] It should be noted that, unless otherwise specified, the various parameters described above were measured according to the measurement methods in the examples described below or methods considered equivalent thereto by those skilled in the art.

[0300] Example

[0301] 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 unless the scope of the present invention is exceeded. The physical properties in the examples were measured by the following methods.

[0302] The following describes the measurement of the physical property values ​​of polymers and the method for preparing samples for evaluation of Examples and Comparative Examples. In addition, the evaluation method and the evaluation results of the obtained samples are shown.

[0303] <<First Embodiment>>

[0304] In the first example, a photosensitive resin composition in which the structural unit of styrene and / or a styrene derivative in the entire (A) alkali-soluble polymer is 15% by mass or more was evaluated.

[0305] (1) Determination of physical property values

[0306] <Measurement of Weight Average Molecular Weight or Number Average Molecular Weight of Polymer>

[0307] The weight average molecular weight or number average molecular weight of the polymer is determined in terms of polystyrene using a gel permeation chromatograph (GPC) manufactured by JASCO Corporation (pump: Gulliver, PU-1580 model, columns: four Shodex (registered trademark) (KF-807, KF-806M, KF-806M, KF-802.5) manufactured by Showa Denko K.K. connected in series, mobile layer solvent: tetrahydrofuran, using a calibration curve based on a polystyrene standard sample (Shodex STANDARD SM-105 manufactured by Showa Denko K.K.)).

[0308] Furthermore, the polymer dispersion degree is calculated as the ratio of the weight average molecular weight to the number average molecular weight (weight average molecular weight / number average molecular weight).

[0309] (2) Method for preparing samples for evaluation

[0310] Evaluation samples were prepared as follows.

[0311] <Production of Photosensitive Resin Laminated Body>

[0312] The components shown in Table 1-1 (Table 2-1, Table 3-1) described later (wherein the numbers of each component represent the amount of the solid content (parts by mass)) and the solvent are fully stirred and mixed to obtain a photosensitive resin composition preparation liquid. The names of the components represented by abbreviations in Table 1-1 (Table 2-1, Table 3-1) are shown in the following Table 1-2 (Table 2-2, Table 3-2). A 16 μm thick polyethylene terephthalate film (manufactured by Toray Industries, Inc., FB-40) is used as a supporting film, and the preparation liquid is evenly applied on its surface using a rod coater, and dried in a dryer at 95°C for 3 minutes to form a photosensitive resin composition layer. The dry thickness of the photosensitive resin composition layer is 25 μm.

[0313] Next, a 19 μm thick polyethylene film (GF-818 manufactured by TAMAPOLY Co., Ltd.) was attached as a protective layer to the surface of the photosensitive resin composition layer on which the polyethylene terephthalate film was not laminated, thereby obtaining a photosensitive resin laminate.

[0314] <Substrate leveling>

[0315] As an evaluation substrate for image properties, a 0.4 mm thick copper-clad laminate laminated with 35 μm rolled copper foil was jet-washed and polished using a grinding agent (manufactured by Uji Denka Kogyo Co., Ltd., #400) at a jet pressure of 0.2 MPa, and the substrate surface was cleaned with a 10 mass % H2SO4 aqueous solution.

[0316] <Lamination>

[0317] While peeling off the polyethylene film (protective layer) of the photosensitive resin laminate, the photosensitive resin laminate was laminated on the copper-clad laminate preheated to 50° C. using a hot roll laminator (AL-700 manufactured by Asahi Kasei Corporation) at a roll temperature of 105° C. The air pressure was 0.35 MPa and the lamination speed was 1.5 m / min.

[0318] <Exposure>

[0319] The evaluation substrate was exposed 2 hours after lamination using a direct drawing exposure machine IP-8 8000H using a Stouffer 41-step exposure meter. The exposure was performed at an exposure amount that allowed the highest residual film level to reach 15 levels during exposure and development using the Stouffer 41-step exposure meter as a mask.

[0320] The evaluation substrate was heated 7 minutes after exposure using a hot roll laminator (manufactured by Asahi Kasei Corporation, AL-700). The roll temperature was set to 105°C, the air pressure was set to 0.30 MPa, and the lamination speed was set to 0.5 m / min. It should be noted that if the time after exposure is extended, the effect of heating gradually disappears, so heating is usually performed about 1 minute after exposure. Therefore, heating after 7 minutes of exposure in this embodiment is a very severe condition.

[0321] <Development>

[0322] After the polyethylene terephthalate film (support layer) was peeled off, an alkali developer (manufactured by Fuji Kiko Co., Ltd., a developer for dry films) was used to spray a 30°C 1 mass % Na2CO3 aqueous solution for a predetermined time for development. The development spraying time was set to twice the shortest development time, and the water washing spraying time after development was set to four times the shortest development time. At this time, the shortest time required for the photosensitive resin layer of the unexposed portion to be completely dissolved was set to the shortest development time.

[0323] <Adhesion Evaluation>

[0324] The minimum line width of a pattern in which the mask pattern L / S=X μm / 200 μm was normally formed was measured using an optical microscope. This measurement was performed for 8 lines, and the average value of the 8 line widths was determined as the value of adhesion.

[0325] <Discoloration of copper surface>

[0326] The same steps as above were carried out until development, and the copper surface after the photosensitive resin composition layer was removed by development was visually observed for the unexposed portion on which the photosensitive resin composition layer was laminated.

[0327] ○: No color change

[0328] △: Slight discoloration was observed

[0329] <Minimum development time delay>

[0330] The shortest development time was measured under the following two conditions.

[0331] (A) Normal shortest development time

[0332] The photosensitive resin laminate was laminated on a substrate, and after the support film was peeled off, the shortest time required for the photosensitive resin layer in the unexposed portion to completely dissolve was measured.

[0333] (B) Shortest development time after heating

[0334] After the photosensitive resin laminate was laminated on the substrate, it was heated by a hot roll laminator (AL-700 manufactured by Asahi Kasei Corporation) with the roll temperature being 105° C., the air pressure being 0.30 MPa, and the lamination speed being 0.1 m / min.

[0335] ○: (B) has the same shortest development time as (A) (no delay)

[0336] △: The shortest developing time of (B) is 1 to 3 seconds longer than the shortest developing time of (A) (there is a delay)

[0337] The above evaluation results are shown in Table 1-1 together with the components of the photosensitive resin compositions of Examples and Comparative Examples. In addition, the component names represented by abbreviations in Table 1-1 are shown in Table 1-2.

[0338] [Table 1-1]

[0339]

[0340] [Table 1-2]

[0341]

[0342] From the results of Tables 1-1 and 1-2, it can be confirmed that the evaluation results of image properties of Examples falling within the technical feature range of the present invention are superior to those of Comparative Examples falling outside the scope of the present invention.

[0343] From the results of Tables 1-1 and 1-2, it can be confirmed that the evaluation results of image properties of Examples falling within the technical feature range of the present invention are superior to those of Comparative Examples falling outside the scope of the present invention.

[0344] It should be noted that the heating condition after exposure in this embodiment is heating after 7 minutes of exposure, so it is a very harsh condition. For example, the adhesion of the compositions of Example 1 and Comparative Example 1 when developed without heating after exposure is 12.0μm. In other words, in the composition of Comparative Example 1, no effect is observed by heating after 7 minutes of exposure, but Example 1 can improve the adhesion even under very harsh conditions. In addition, under the condition of heating after 1 minute of exposure, the compositions of Example 1 and Comparative Example 1 can both obtain a adhesion of 10.0μm.

[0345] According to the above results, even when the adhesion is good under the usual heating conditions after exposure, the adhesion is not good under the harsh conditions of heating 7 minutes after exposure in this embodiment. However, the photosensitive resin composition of the present invention having a specific composition can improve the adhesion for the first time under the harsh heating conditions after exposure. Therefore, when manufacturing a circuit substrate, good adhesion can be obtained even if the time after exposure becomes long, so that a high-precision circuit pattern can be stably formed.

[0346] <<Second Embodiment>>

[0347] In the second example, a photosensitive resin composition in which the (B) compound having an ethylenically unsaturated double bond includes a (meth)acrylate compound having three or more ethylenically unsaturated double bonds was evaluated.

[0348] Using the components shown in Table 2-1 described later, a sample for evaluation was prepared in the same manner as in the first embodiment.

[0349] <Exposure>

[0350] The evaluation substrate was exposed 2 hours after lamination using a direct drawing exposure machine (Nuvogo1000 manufactured by ORBOTECH, light source: 375 nm (30%) + 405 nm (70%)) using a Stouffer 41-step exposure meter. The exposure was performed at an exposure amount such that the maximum residual film level during development reached 19 levels using the Stouffer 41-step exposure meter as a mask.

[0351] <Heating>

[0352] The evaluation substrate was heated 7 minutes after exposure using a hot roll laminator (manufactured by Asahi Kasei Corporation, AL-700). The roll temperature was set to 105°C, the air pressure was set to 0.30 MPa, and the lamination speed was set to 1 m / min. It should be noted that if the time after exposure is extended, the heating effect gradually disappears, so heating is usually performed about 1 minute after exposure. Therefore, heating after 7 minutes of exposure in this embodiment is a very severe condition.

[0353] <Development>

[0354] After the polyethylene terephthalate film (support layer) was peeled off, an alkali developer (manufactured by Fuji Kiko Co., Ltd., a developer for dry films) was used to spray a 1 mass % Na2CO3 aqueous solution at 30°C for a predetermined time for development. The time for the development spray was set to twice the shortest development time, and the time for the water washing spray after development was set to three times the shortest development time. At this time, the shortest time required for the photosensitive resin layer in the unexposed portion to be completely dissolved was set to the shortest development time.

[0355] Evaluation was performed in the same manner as in the first embodiment except that the exposure to development steps were performed as described above.

[0356] The above evaluation results are shown in Table 2-1 together with the components of the photosensitive resin compositions of Examples and Comparative Examples. In addition, the component names represented by abbreviations in Table 2-1 are shown in Table 2-2.

[0357] [Table 2-1]

[0358]

[0359] [Table 2-2]

[0360]

[0361] The results in Tables 2-1 and 2-2 confirm that the results of the image quality evaluation of the Examples falling within the technical feature range of the present invention are superior to those of the Comparative Examples falling outside the scope of the present invention.

[0362] It should be noted that the heating condition after exposure in this embodiment is heating after 7 minutes of exposure, so it is a very harsh condition. For example, the adhesion of the compositions of Example 1 and Comparative Example 1 when developed without heating after exposure is 11.8μm. In other words, in the composition of Comparative Example 1, no effect is observed by heating after 7 minutes of exposure, but Example 1 can improve the adhesion even under very harsh conditions. In addition, under the condition of heating after 1 minute of exposure, the compositions of Example 1 and Comparative Example 1 can both obtain a 9.6μm adhesion.

[0363] According to the above results, even when the adhesion is good under the normal heating conditions after exposure, the adhesion is not improved under the harsh conditions of heating 7 minutes after exposure in the present embodiment. However, according to the present invention, the adhesion can be improved even under the harsh heating conditions after exposure for the first time. Therefore, when manufacturing a circuit substrate, good adhesion can be obtained even if the time after exposure becomes long, so that a high-definition circuit pattern can be stably formed.

[0364] <<Third Embodiment>>

[0365] In the third example, a photosensitive resin composition in which the (C-2) photopolymerization initiator contains anthracene and / or an anthracene derivative was evaluated.

[0366] Using the components shown in Table 3-1 described later, a sample for evaluation was prepared in the same manner as in the first embodiment.

[0367] <Exposure>

[0368] The evaluation substrate was exposed 2 hours after lamination using a direct drawing exposure machine (Nuvogo1000 manufactured by ORBOTECH, light source: 375 nm (30%) + 405 nm (70%)) using a Stouffer 41-step exposure meter. The exposure was performed at an exposure amount such that the maximum residual film level during development reached 21 levels using the Stouffer 41-step exposure meter as a mask.

[0369] <Heating>

[0370] The evaluation substrate was heated 7 minutes after exposure using a hot roll laminator (manufactured by Asahi Kasei Corporation, AL-700). The roll temperature was set to 105°C, the air pressure was set to 0.30 MPa, and the lamination speed was set to 1 m / min. It should be noted that if the time after exposure is extended, the heating effect gradually disappears, so heating is usually performed about 1 minute after exposure. Therefore, heating after 7 minutes of exposure in this embodiment is a very severe condition.

[0371] <Development>

[0372] After the polyethylene terephthalate film (support layer) was peeled off, an alkali developer (manufactured by Fuji Kiko Co., Ltd., a developer for dry films) was used to spray a 1 mass % Na2CO3 aqueous solution at 30°C for a predetermined time for development. The time for the development spray was set to twice the shortest development time, and the time for the water washing spray after development was set to three times the shortest development time. At this time, the shortest time required for the photosensitive resin layer in the unexposed portion to be completely dissolved was set to the shortest development time.

[0373] Evaluation was performed in the same manner as in the first embodiment except that the exposure to development steps were performed as described above.

[0374] The above evaluation results are shown in Table 3-1 together with the components of the photosensitive resin compositions of Examples and Comparative Examples. In addition, the component names represented by abbreviations in Table 3-1 are shown in Table 3-2.

[0375] [Table 3-1]

[0376]

[0377] [Table 3-2]

[0378]

[0379] According to the results of Tables 3-1 and 3-2, it can be confirmed that the image evaluation results of the embodiments falling within the scope of the technical features of the present invention are excellent compared with the comparative examples outside the scope of the present invention. It should be noted that the heating condition after exposure in this embodiment is heating after 7 minutes of exposure, so it is a very harsh condition. For example, the adhesion of the compositions of Example 7 and Comparative Example 1 when developed without heating after exposure is 12.8μm. In other words, in the composition of Comparative Example 1, no effect is observed by heating after 7 minutes of exposure, but Example 7 can improve the adhesion even under very harsh conditions. In addition, under the condition of heating after 1 minute of exposure, the compositions of Example 7 and Comparative Example 1 can both obtain a adhesion of 9.6μm.

[0380] The above results show that even when the adhesion is good under normal heating conditions after exposure, the adhesion is not improved under the harsh conditions of heating 7 minutes after exposure, but according to the present invention, the adhesion can be improved even under the harsh heating conditions after exposure for the first time. That is, according to the composition of the present invention, when manufacturing a circuit substrate, good adhesion can be obtained even if the time after exposure becomes longer, so that a high-definition circuit pattern can be stably formed.

[0381] As mentioned above, although embodiment of this invention was described, this invention is not limited to this, It can change suitably within the range which does not exceed the summary of this invention.

[0382] Industrial Applicability

[0383] By using the photosensitive resin composition of the present invention, the adhesion when developing after heating after exposure can be significantly improved, and good adhesion can be achieved even when the time after exposure is long, and the photosensitive resin composition can be widely used.

Claims

1. A photosensitive resin composition, which is used for heating after exposure and then developing to obtain a resin cured product, characterized in that: The photosensitive resin composition comprises the following components based on the total solid content weight of the photosensitive resin composition: (A) alkali-soluble polymer: 10% to 90% by mass; (B) compounds having an ethylenically unsaturated double bond: 5% to 70% by mass; and (C) Photopolymerization initiator: 0.01% to 20% by mass, The (A) alkali-soluble polymer as a whole contains 15% by mass or more of structural units of styrene and / or styrene derivatives, and the content of monomer components having an aromatic hydrocarbon group is 50% by mass or more, As the compound (B) having an ethylenically unsaturated double bond, the content of the compound (B-1) having a bisphenol A skeleton concentration of 0.18 mol / 100 g or more is 0 to 18% by mass based on the solid content of the photosensitive resin composition, and the (meth)acrylate compound (b1) having three or more ethylenically unsaturated bonds is contained in an amount of 4% to 40% by mass based on the total solid content of the photosensitive resin composition, The value of [(A) content of alkali-soluble polymer] / [(B) content of compound having ethylenically unsaturated double bond] is 1.04 or more, The (C) photopolymerization initiator includes anthracene and / or anthracene derivative. 2 . The photosensitive resin composition according to claim 1 , further comprising (D) an inhibitor. 3 . The photosensitive resin composition according to claim 1 , further comprising (E) a benzotriazole derivative.

4. The photosensitive resin composition according to claim 1, wherein The (B) compound having an ethylenically unsaturated double bond includes a (meth)acrylate compound having four or more ethylenically unsaturated double bonds.

5. The photosensitive resin composition according to claim 4, wherein The (B) compound having an ethylenically unsaturated double bond includes a (meth)acrylate compound having 6 or more ethylenically unsaturated double bonds.

6. The photosensitive resin composition according to claim 1, wherein The value of [(A) content of alkali-soluble polymer] / [(B) content of compound having ethylenically unsaturated double bond] is 1.11 or more.

7. The photosensitive resin composition according to claim 6, wherein The value of [(A) content of alkali-soluble polymer] / [(B) content of compound having ethylenically unsaturated double bond] is 1.21 or more.

8. The photosensitive resin composition according to claim 7, wherein The value of [(A) the content of the alkali-soluble polymer] / [(B) the content of the compound having an ethylenically unsaturated double bond] is 1.30 or more.

9. The photosensitive resin composition according to claim 1 or 2, wherein The value of [(A) content of alkali-soluble polymer] / [(B) content of compound having ethylenically unsaturated double bond] is 5 or less.

10. The photosensitive resin composition according to claim 9, wherein The value of [(A) content of alkali-soluble polymer] / [(B) content of compound having ethylenically unsaturated double bond] is 4 or less.

11. The photosensitive resin composition according to claim 10, wherein The value of [(A) content of alkali-soluble polymer] / [(B) content of compound having ethylenically unsaturated double bond] is 3 or less.

12. The photosensitive resin composition according to claim 11, wherein The value of [(A) content of alkali-soluble polymer] / [(B) content of compound having ethylenically unsaturated double bond] is 2 or less.

13. The photosensitive resin composition according to claim 12, wherein The value of [(A) content of alkali-soluble polymer] / [(B) content of compound having ethylenically unsaturated double bond] is 1.5 or less.

14. The photosensitive resin composition according to claim 1 or 2, wherein The structural units of styrene and / or styrene derivatives in the (A) alkali-soluble polymer are 90% by mass or less.

15. The photosensitive resin composition according to claim 1 or 2, wherein The (A) alkali-soluble polymer further contains benzyl (meth)acrylate as a monomer component. 16 . The photosensitive resin composition according to claim 1 , which is a photosensitive resin composition for obtaining a cured resin by exposure with a first laser having a central wavelength of less than 390 nm and a second laser having a central wavelength of 390 nm or more.

17. The photosensitive resin composition according to claim 16, wherein The center wavelength of the first laser light is greater than or equal to 350 nm and less than or equal to 380 nm, and the center wavelength of the second laser light is greater than or equal to 400 nm and less than or equal to 410 nm.

18. A photosensitive resin composition which is used to obtain a resin cured product by heating after exposure and then developing, characterized in that: The photosensitive resin composition comprises the following components based on the total solid content weight of the photosensitive resin composition: (A) alkali-soluble polymer: 10% to 90% by mass; (B) compounds having an ethylenically unsaturated double bond: 5% to 70% by mass; and (C) Photopolymerization initiator: 0.01% to 20% by mass, The structural units of styrene and / or styrene derivatives in the entire alkali-soluble polymer (A) account for 35.8% by mass or more, The (C) photopolymerization initiator comprises anthracene and / or anthracene derivatives, The anthracene and / or anthracene derivative comprises 9,10-diphenylanthracene.

19. The photosensitive resin composition according to claim 18, wherein The anthracene derivatives further include compounds having an alkoxy group having 1 to 40 carbon atoms which may have a substituent and / or an aryl group having 6 to 40 carbon atoms which may have a substituent at the 9-position and / or the 10-position.

20. The photosensitive resin composition according to claim 18 or 19, wherein The anthracene derivatives further include compounds having an alkoxy group having 1 to 40 carbon atoms which may have a substituent and / or an aryl group having 6 to 40 carbon atoms which may have a substituent at the 9- and 10-positions.

21. The photosensitive resin composition according to claim 18, wherein The (C) photopolymerization initiator further includes 9,10-dialkoxyanthracene.

22. The photosensitive resin composition according to claim 18 or 19, wherein The (C) photopolymerization initiator further includes an anthracene derivative having a halogen atom.

23. The photosensitive resin composition according to claim 18, wherein The (C) photopolymerization initiator further includes a compound in which the alkoxy group at the 9-position and / or the 10-position of 9,10-dialkoxyanthracene is modified with one or more halogen atoms.

24. The photosensitive resin composition according to claim 18 or 19, wherein The (C) photopolymerization initiator further includes a compound having a halogen atom directly bonded to an anthracene skeleton.

25. The photosensitive resin composition according to claim 18, wherein The structural unit of styrene and / or a styrene derivative in the (A) alkali-soluble polymer is 40% by mass or more.

26. A method for forming a resist pattern, comprising the following steps: A step of exposing the photosensitive resin composition according to any one of claims 1 to 25; A heating step of heating the exposed photosensitive resin composition; and A developing step of developing the heated photosensitive resin composition.

27. The method for forming a resist pattern according to claim 26, wherein: The heating temperature in the heating step is in the range of 30°C to 150°C.

28. The method for forming a resist pattern according to claim 26 or 27, wherein: The exposure step is performed by an exposure method based on direct drawing of a drawing pattern or an exposure method based on projecting an image of a photomask through a lens.

29. The method for forming a resist pattern according to claim 26 or 27, wherein: The exposure step is performed by an exposure method based on direct drawing of a drawing pattern.

30. The method for forming a resist pattern according to claim 26 or 27, wherein: The heating step is performed within 15 minutes after the exposure.

31. The method for forming a resist pattern according to claim 26 or 27, wherein: The exposure step is performed by a method of exposing with a first laser beam having a central wavelength of less than 390 nm and a second laser beam having a central wavelength of 390 nm or more.

32. The method for forming a resist pattern according to claim 31, wherein: The center wavelength of the first laser light is greater than or equal to 350 nm and less than or equal to 380 nm, and the center wavelength of the second laser light is greater than or equal to 400 nm and less than or equal to 410 nm.

33. A method for manufacturing a circuit substrate, wherein: A circuit board is formed by etching or plating a substrate having a resist pattern produced by the method according to any one of claims 26 to 32.

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