JP6132505B2 - Photosensitive resin composition and photosensitive resin laminate - Google Patents

Description

  The present invention relates to a photosensitive resin composition and the like.

  In an electronic device such as a personal computer or a mobile phone, a printed wiring board or the like is used for mounting a component or a semiconductor. As a resist for production of printed wiring boards and the like, conventionally, a photosensitive resin laminate comprising a photosensitive resin layer laminated on a support film, and further a protective film laminated on the photosensitive resin layer as necessary, A so-called dry film resist (hereinafter sometimes referred to as DF) is used. Currently, the photosensitive resin layer is generally of an alkali development type using a weak alkaline aqueous solution as a developer. To produce a printed wiring board using DF, if there is a protective film, first peel off the protective film and then use a laminator or the like on a permanent circuit production board such as a copper-clad laminate or a flexible board. Laminate DF and expose through a wiring pattern mask film. Next, if necessary, the support film is peeled off, and the photosensitive resin layer of the unexposed portion (in the case of negative type) is dissolved or dispersed and removed by a developer, and a cured resist pattern (hereinafter simply referred to as a resist pattern) is formed on the substrate. May be called).

  The process of forming a circuit after forming a resist pattern is roughly divided into two methods. The first method is a method in which a substrate surface not covered with a resist pattern (for example, a copper surface of a copper clad laminate) is removed by etching, and then the resist pattern portion is removed with an alkaline aqueous solution stronger than a developer (etching method). It is. In the second method, the substrate surface that is not covered with the resist pattern (for example, copper surface) is plated with copper, solder, nickel, tin, etc., and then the resist pattern portion is removed in the same manner, and the substrate appears further. This is a method (plating method) for etching a surface (for example, a copper surface of a copper clad laminate). For etching, cupric chloride, ferric chloride, a copper ammonia complex solution, or the like is used.

  In such a manufacturing process, high sensitivity is strongly demanded in order to improve productivity. Furthermore, in recent years, with the miniaturization and weight reduction of electronic devices, the miniaturization and high density of printed wiring boards have progressed, and high-performance DFs excellent in resolution and the like have been demanded.

  As a photosensitive resin composition that realizes both such high sensitivity and high resolution, Patent Document 1 discloses hexaarylbiimidazole, N, N′-tetraethyl-4,4′-diaminobenzophenone, N- A photosensitive resin composition containing phenylglycine and a vinyl urethane compound is described.

Japanese Patent Laid-Open No. 9-176253

  However, the technique described in Patent Document 1 does not satisfy the resolution and still has room for improvement.

  Accordingly, the present invention provides a photosensitive resin composition capable of forming a photosensitive resin laminate excellent in resolution, and provides a method for producing the photosensitive resin laminate and a resist pattern using the same. The issue is to provide.

As a result of intensive studies and experiments to solve the above problems, the present inventor has found that the problems can be solved by the following technical means.
That is, it is as follows.

[1] The following:
(A) Alkali-soluble polymer: 10% by mass to 90% by mass;
(B) Compound having ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) Photopolymerization initiator: 0.01% by mass to 20% by mass;
A photosensitive resin composition comprising:
The (A) alkali-soluble polymer has an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000,
The photosensitive resin composition in which the compound which has a sulfide structure, and the compound which has a hindered phenol structure exist in this photosensitive resin composition.
[2] (D) Additive containing sulfide structure or hindered phenol structure or a combination thereof: 0.001% by mass to 10% by mass;
The photosensitive resin composition according to [1], further comprising:
[3] The photosensitive resin composition according to the above [2], wherein the additive (D) is a compound having a sulfide structure.
[4] The photosensitive resin composition according to the above [2] or [3], wherein the additive (D) is a compound having a hindered phenol structure.
[5] A photosensitive resin laminate comprising a support layer and a photosensitive resin layer made of the photosensitive resin composition according to any one of the above [1] to [4] laminated on the support layer.
[6] Lamination step of laminating the photosensitive resin laminate according to [5] above on a substrate, an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate, and unexposed of the photosensitive resin layer A method for producing a resist pattern, comprising a developing step of developing and removing a portion.
[7] The method for producing a resist pattern according to [6], wherein the exposure step is performed by direct drawing of a drawing pattern.

  According to the present invention, a photosensitive resin composition capable of forming a photosensitive resin laminate excellent in resolution is provided, and the photosensitive resin laminate and a method for producing a resist pattern using the same are provided. Can do.

  Hereinafter, exemplary modes for carrying out the present invention (hereinafter abbreviated as “embodiments”) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.

  In the embodiment, the photosensitive resin composition has the following components (A) to (C): (A) alkali-soluble polymer: 10% by mass to 90% by mass, acid equivalent of 100 to 600, and Weight average molecular weight: 5,000 to 500,000; (B) Compound having ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) Photopolymerization initiator: 0.01% by mass to 20%. And a compound having a sulfide structure and a compound having a hindered phenol structure are present in the photosensitive resin composition. Hereinafter, each component will be described in order.

<(A) Alkali-soluble polymer>
(A) The alkali-soluble polymer is a polymer that is easily soluble in an alkaline substance, and typically includes a carboxyl group-containing monomer as a copolymerization component. Moreover, the acid equivalent of (A) alkali-soluble polymer is 100-600, Preferably it is 250-450. The acid equivalent refers to the mass (gram) of a linear polymer having 1 equivalent of a carboxyl group in the molecule. (A) The carboxyl group in the alkali-soluble polymer is necessary for providing the photosensitive resin layer with developability and peelability with respect to an aqueous alkali solution. Setting the acid equivalent to 100 or more is advantageous from the viewpoint of improving development resistance, resolution and adhesion, and it is preferable to set the acid equivalent to 250 or more. On the other hand, setting the acid equivalent to 600 or less is advantageous from the viewpoint of improving developability and peelability, and it is preferable to set the acid equivalent to 450 or less.

  (A) The weight average molecular weight of the alkali-soluble polymer is 5,000 to 500,000. Setting the weight average molecular weight to 500,000 or less is advantageous from the viewpoint of improving resolution and developability, and the weight average molecular weight is preferably 300,000 or less, and preferably 200,000 or less. Further preferred. On the other hand, setting the weight average molecular weight to 5,000 or more is a viewpoint for controlling the properties of the development aggregate and the properties of the unexposed film such as the edge fuse property and the cut chip property when the photosensitive resin laminate is used. The weight average molecular weight is preferably 10,000 or more, and more preferably 20,000 or more. The edge fuse property refers to a phenomenon in which the photosensitive resin composition layer protrudes from the end face of the roll when the photosensitive resin laminate is wound into a roll. The cut chip property refers to a phenomenon in which a chip flies when an unexposed film is cut with a cutter. If this chip adheres to the upper surface of the photosensitive resin laminate or the like, it is transferred to a mask in a later exposure process or the like, resulting in a defective product. (A) The dispersity of the alkali-soluble polymer (sometimes referred to as molecular weight distribution) (calculated from the above weight average molecular weight and the number average molecular weight obtained in the same manner) may be about 1 to 6, Preferably it is 1-4.

  (A) The alkali-soluble polymer contains one or more types of first monomers described later and one or more types of second monomers described below, and more preferably is a copolymer of copolymer components composed of these. It is preferable.

  The first monomer is a carboxylic acid or acid anhydride having one polymerizable unsaturated group in the molecule. Examples of the first monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, maleic acid half ester, and the like. Particularly preferred is (meth) acrylic acid. In this specification, (meth) acryl indicates acrylic and / or methacrylic. The same applies hereinafter.

  The second monomer is a monomer that is non-acidic and has at least one polymerizable unsaturated group in the molecule. Examples of the second monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth) acrylate. Tert-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, vinyl alcohol esters such as acetic acid Examples include vinyl, (meth) acrylonitrile, styrene, and styrene derivatives. Among these, methyl (meth) acrylate, n-butyl (meth) acrylate, styrene, 2-ethylhexyl (meth) acrylate, and benzyl (meth) acrylate are preferable from the viewpoint of improving the resolution and adhesion of the resist pattern. From the viewpoint of improving the resolution and adhesion of the resist pattern, styrene and benzyl (meth) acrylate are particularly preferable.

  Preferable examples of the combination of the polymerization components include methyl methacrylate / methacrylic acid / styrene.

  As a copolymerization ratio of the first monomer and the second monomer, out of 100% by mass of the copolymer component, the first monomer is 10% by mass to 60% by mass, and the second monomer The monomer is preferably 40% by mass to 90% by mass, more preferably the first monomer is 15% by mass to 35% by mass, and the second monomer is 65% by mass to 85%. % By mass.

  (A) The synthesis of the alkali-soluble polymer is carried out by diluting a mixture of the first monomer and the second monomer with a solvent such as acetone, methyl ethyl ketone, or isopropanol. It is preferable to carry out by adding an appropriate amount of a radical polymerization initiator such as butyronitrile and stirring with heating. In some cases, the synthesis is performed while a part of the mixture is dropped into the reaction solution. After completion of the reaction, a solvent may be further added to adjust to a desired concentration. As synthesis means, bulk polymerization, suspension polymerization, or emulsion polymerization may be used in addition to solution polymerization.

  (A) The ratio with respect to the total mass of the photosensitive resin composition of an alkali-soluble polymer is the range of 10 mass%-90 mass%, Preferably it is 30 mass%-70 mass%, More preferably, it is 40 mass%. -60 mass%. It is advantageous from the viewpoint of controlling the development time that the ratio of (A) the alkali-soluble polymer to the photosensitive resin composition is 90% by mass or less, while (A) the alkali-soluble polymer is high in the photosensitive resin composition. Setting the molecular ratio to 10% by mass or more is advantageous from the viewpoint of improving the edge fuse property.

<(B) Compound having an ethylenically unsaturated double bond>
(B) The compound having an ethylenically unsaturated double bond preferably contains a compound having a (meth) acryloyl group in the molecule from the viewpoint of curability and compatibility with (A) an alkali-soluble polymer.

  For example, a compound in which (meth) acrylic acid is added to one end of polyalkylene oxide, or (meth) acrylic acid is added to one end and the other end is converted to alkyl ether or allyl ether Can do.

  Examples of such a compound include, for example, phenoxyhexaethylene glycol mono (meth) acrylate, which is a (meth) acrylate of a compound obtained by adding polyethylene glycol to a phenyl group, or polypropylene glycol added with an average of 2 mol of propylene oxide and an average of 7 4-Normal nonylphenoxyheptaethylene glycol dipropylene glycol (meth) acrylate, which is a (meth) acrylate of a compound in which polyethylene glycol added with mol of ethylene oxide is added to nonylphenol, average with polypropylene glycol added with an average of 1 mol of propylene oxide 4-normal nonyl which is a (meth) acrylate of a compound obtained by adding polyethylene glycol to which 5 mol of ethylene oxide has been added to nonylphenol E Bruno carboxymethyl pentaethylene glycol monopropylene glycol (meth) acrylate. As such a compound, for example, 4-normal nonylphenoxyoctaethylene glycol (meth) acrylate (Toagosei Co., Ltd.), which is a (meth) acrylate of a compound obtained by adding polyethylene glycol with an average of 8 moles of ethylene oxide added to nonylphenol. And M-114).

  Examples of such a compound include a compound having a (meth) acryloyl group at both ends of an alkylene oxide chain, or (meth) at both ends of an alkylene oxide chain in which an ethylene oxide chain and a propylene oxide chain are bonded randomly or in blocks. Examples thereof include compounds having an acryloyl group.

  Examples of such a compound include tetraethylene glycol di (meth) acrylate, pentaethylene glycol di (meth) acrylate, hexaethylene glycol di (meth) acrylate, heptaethylene glycol di (meth) acrylate, octaethylene glycol di ( Poly (ethylene glycol) (meth) acrylates such as (meth) acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, and compounds having (meth) acryloyl groups at both ends of 12 mol ethylene oxide chain And polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, and the like. Examples of the polyalkylene oxide di (meth) acrylate compound containing an ethylene oxide group and a propylene oxide group in the compound include, for example, a glycol obtained by adding an average of 3 moles of ethylene oxide to both ends of polypropylene glycol added with an average of 12 moles of propylene oxide. And diglycolate of glycol obtained by adding an average of 15 moles of ethylene oxide to both ends of polypropylene glycol having an average of 18 moles of propylene oxide added thereto.

  A compound having (meth) acryloyl groups at both ends by modifying bisphenol A with alkylene oxide is preferable from the viewpoint of resolution and adhesion. Examples of the alkylene oxide modification include ethylene oxide modification, propylene oxide modification, butylene oxide modification, pentylene oxide modification, and hexylene oxide modification. A compound having (meth) acryloyl groups at both ends by modifying bisphenol A with ethylene oxide is preferred. As such a compound, for example, 2,2-bis (4-((meth) acryloxydiethoxy) phenyl) propane (NK ester BPE-200 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis (4-((meth) acryloxytriethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytetraethoxy) phenyl) propane, 2,2-bis (4-((meth) acrylic) Roxypentaethoxy) phenyl) propane (NK ester BPE-500 manufactured by Shin-Nakamura Chemical Co., Ltd.), 2,2-bis (4-((meth) acryloxyhexaethoxy) phenyl) propane, 2,2-bis ( 4-((meth) acryloxyheptaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxyoctaethoxy) phenyl) propane, 2 2-bis (4-((meth) acryloxynonaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydecaethoxy) phenyl) propane, 2,2-bis (4-(( (Meth) acryloxyundecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxydodecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxytridecaethoxy) ) Phenyl) propane, 2,2-bis (4-((meth) acryloxytetradecaethoxy) phenyl) propane, 2,2-bis (4-((meth) acryloxypentadecaethoxy) phenyl) propane, 2 2,2-bis (4-((meth) acryloxypolyether) such as 2-bis (4-((meth) acryloxyhexadecaethoxy) phenyl) propane ) Phenyl) propane. Further, di (meth) acrylate of polyalkylene glycol obtained by adding an average of 2 mol of propylene oxide and an average of 6 mol of ethylene oxide to both ends of bisphenol A, or an average of 2 mol of propylene oxide and an average of 15 mol to both ends of bisphenol A, respectively. Also preferred are compounds modified with ethylene oxide and propylene oxide, such as di (meth) acrylates of polyalkylene glycols with addition of ethylene oxide. The number of moles of ethylene oxide in the compound having (meth) acryloyl groups at both ends by modifying bisphenol A with alkylene oxide is from 10 moles to 30 moles from the viewpoint of improving resolution, adhesion and flexibility. Molar or less is preferable.

  For example, a compound having more than two (meth) acryloyl groups in one molecule uses a compound having three or more groups (for example, hydroxyl groups) to which an alkylene oxide group can be added in the molecule as a central skeleton. It can be obtained by adding an alkylene oxide group such as an ethylene oxide group, a propylene oxide group or a butylene oxide group to (meth) acrylate by reacting the resulting alcohol with (meth) acrylic acid. Examples of the compound that can be a central skeleton include glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and isocyanurate rings.

  Examples of the compound having more than two (meth) acryloyl groups in one molecule include, for example, trimethylolpropane ethylene oxide (EO) 3 mol-modified triacrylate, trimethylolpropane EO6 mol-modified triacrylate, trimethylolpropane EO9. Examples thereof include a mole-modified triacrylate and EO12 mole-modified triacrylate of trimethylolpropane. As such a compound, for example, EO 3 mol-modified triacrylate of glycerol (for example, A-GLY-3E manufactured by Shin-Nakamura Chemical Co., Ltd.), EO 9 mol-modified triacrylate of glycerol (for example, manufactured by Shin-Nakamura Chemical Co., Ltd.) A-GLY-9E), EO 6 mol of glycerin and propylene oxide (PO) 6 mol modified triacrylate (for example, A-GLY-0606PE manufactured by Shin-Nakamura Chemical Co., Ltd.), EO 9 mol PO9 mol modified triacrylate of glycerin (for example, Shin-Nakamura Chemical Co., Ltd. A-GLY-0909PE), etc., pentaerythritol 4EO-modified tetraacrylate (for example, SR-494 manufactured by Sartomer Japan), pentaerythritol 35EO-modified tetraacrylate (for example, Shin-Nakamura Chemical) NK Ester A manufactured by Kogyo Co., Ltd. Mention may be made of the M-35E) or the like.

  (B) The compound which has an ethylenically unsaturated double bond can contain suitably the compound etc. which are listed below other than said compound. For example, 1,6-hexanediol di (meth) acrylate, 1,4-cyclohexanediol di (meth) acrylate, 2-di (p-hydroxyphenyl) propanedi (meth) acrylate, 2,2-bis [(4- (Meth) acryloxypolypropyleneoxy) phenyl] propane, 2,2-bis [(4- (meth) acryloxypolybutyleneoxy) phenyl] propane, glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, Polyoxypropyltrimethylolpropane tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, trimethylolpropane triglycidyl ether tri (meth) acrylate, β-hydroxypropyl-β '-(acryloyloxy) propyl Examples thereof include talates, nonylphenoxypolypropylene glycol (meth) acrylate, nonylphenoxypolybutylene glycol (meth) acrylate, and polypropylene glycol mono (meth) acrylate. Furthermore, the following urethane compounds are also mentioned. For example, hexamethylene diisocyanate, tolylene diisocyanate or other diisocyanate compounds (for example, 2,2,4-trimethylhexamethylene diisocyanate) and compounds having a hydroxyl group and a (meth) acryl group in one molecule, such as 2- Examples include urethane compounds with hydroxypropyl acrylate and oligopropylene glycol monomethacrylate. Specifically, there is a reaction product of hexamethylene diisocyanate and oligopropylene glycol monomethacrylate (for example, Bremer PP1000 manufactured by NOF Corporation). Moreover, di- or tri (meth) acrylates of isocyanuric acid esters modified with polypropylene glycol or polycaprolactone are also included. Moreover, the urethane oligomer obtained by making the terminal of the urethane compound obtained as a polyadduct of diisocyanate and a polyol react with the compound which has an ethylenically unsaturated double bond and a hydroxyl group etc. can be mentioned, for example.

  (B) The ratio with respect to the total mass of the photosensitive resin composition of the compound which has an ethylenically unsaturated double bond is 5 mass%-70 mass%. Setting this ratio to 5% by mass or more is advantageous from the viewpoint of sensitivity, resolution, and adhesion, while setting this ratio to 70% by mass or less delays peeling of edge fuses and cured resist. It is advantageous from the viewpoint of suppressing the above, and it is more preferable to make this ratio 50% by mass or less.

<(C) Photopolymerization initiator>
(C) As a photoinitiator, although the compound generally used as a photoinitiator in the field | area of the photosensitive resin composition can be used, Especially, for example, a hexaaryl biimidazole compound, N-aryl-α- Amino acid compounds, quinones, aromatic ketones, acetophenones, acylphosphine oxides, benzoin or benzoin ethers, dialkyl ketals, thioxanthones, dialkylaminobenzoates, oxime esters, acridines, pyrazoline derivatives, N-aryl amino acid ester compounds, halogen compounds and the like can be mentioned.

  Examples of the hexaarylbiimidazole compound 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, 2,2'-bis- (2,3,4-trifluoro) Phenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,5-trifluorophenyl) -4,4 ′, 5 , 5′-Tetrakis- (3-methoxy Enyl) -biimidazole, 2,2′-bis- (2,3,6-trifluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2 '-Bis- (2,4,5-trifluorophenyl) -4,4', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,4, 6-trifluorophenyl) -4,4 ', 5,5'-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2'-bis- (2,3,4,5-tetrafluorophenyl)- 4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole, 2,2′-bis- (2,3,4,6-tetrafluorophenyl) -4,4 ′, 5 5'-tetrakis- (3-methoxyphenyl) -bi And midazole, 2,2′-bis- (2,3,4,5,6-pentafluorophenyl) -4,4 ′, 5,5′-tetrakis- (3-methoxyphenyl) -biimidazole and the like. It is done.

  Examples of the N-aryl-α-amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, N-ethyl-N-phenylglycine and the like. In particular, N-phenylglycine is preferable because of its high sensitizing effect.

  Examples of quinones include 2-ethylanthraquinone, octaethylanthraquinone, 1,2-benzanthraquinone, 2,3-benzanthraquinone, 2-phenylanthraquinone, 2,3-diphenylanthraquinone, 1-chloroanthraquinone, 2-chloro. Anthraquinone, 2-methylanthraquinone, 1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone, 9,10-phenanthraquinone, 2-methyl-1,4-naphthoquinone 2,3-dimethylanthraquinone, 3-chloro-2-methylanthraquinone and the like.

Examples of aromatic ketones include benzophenone, Michler's ketone [4,4′-bis (dimethylamino) benzophenone], 4,4′-bis (diethylamino) benzophenone, 4-methoxy-4′-dimethylaminobenzophenone, and the like. be able to.

  Examples of acetophenones include 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, and 1- (4 -Dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexyl phenylketone, 2-benzyl- And 2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholino-propanone-1. Examples of commercially available acetophenones include Irgacure-907, Irgacure-369, and Irgacure-379 manufactured by Ciba Specialty Chemicals.

  Examples of acylphosphine oxides include 2,4,6-trimethylbenzyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phosphine oxide, and bis (2,6-dimethoxybenzoyl) -2. 4,4-trimethyl-pentyl phosphine oxide and the like. Examples of commercially available acylphosphine oxides include Lucilin TPO manufactured by BASF and Irgacure-819 manufactured by Ciba Specialty Chemicals.

  Examples of benzoin or benzoin ethers include benzoin, benzoin ethyl ether, benzoin phenyl ether, methyl benzoin, and ethyl benzoin.

  Examples of dialkyl ketals include benzyl dimethyl ketal and benzyl diethyl ketal.

  Examples of thioxanthones include 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chlorothioxanthone, and the like.

  Examples of the dialkylaminobenzoates include ethyl dimethylaminobenzoate, ethyl diethylaminobenzoate, ethyl-p-dimethylaminobenzoate, 2-ethylhexyl-4- (dimethylamino) benzoate and the like.

  Examples of oxime esters include 1-phenyl-1,2-propanedione-2-O-benzoyloxime, 1-phenyl-1,2-propanedione-2- (O-ethoxycarbonyl) oxime, and the like. . Examples of commercially available oxime esters include CGI-325, Irgacure-OXE01, and Irgacure-OXE02 manufactured by Ciba Specialty Chemicals.

  Examples of acridines include 1,7-bis (9,9′-acridinyl) heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9- Ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-n-propylphenyl) acridine, 9- (4-n-butylphenyl) acridine, 9- ( 4-tert-butylphenyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-ethoxyphenyl) acridine, 9- (4-acetylphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine, 9- (4-bromophenyl) acridine Gin, 9- (3-methylphenyl) acridine, 9- (3-tert-butylphenyl) acridine, 9- (3-acetylphenyl) acridine, 9- (3-dimethylaminophenyl) acridine, 9- (3- Diethylaminophenyl) acridine, 9- (3-chlorophenyl) acridine, 9- (3-bromophenyl) acridine, 9- (2-pyridyl) acridine, 9- (3-pyridyl) acridine, 9- (4-pyridyl) acridine Etc. Among these, 1,7-bis (9,9'-acridinyl) heptane or 9-phenylacridine is preferable, and 9-phenylacridine is more preferable in terms of sensitivity, resolution, availability, and the like.

  Examples of the pyrazoline derivative include 1- (4-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4- tert-butyl-phenyl) -pyrazoline, 1,5-bis- (4-tert-butyl-phenyl) -3- (4-tert-butyl-styryl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-ethoxy-phenyl) -pyrazoline, 1-phenyl-3- (4-tert- Octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1,5-bis- (4-tert-octyl-phenyl) -3 (4-tert-octyl-styryl) -pyrazoline, 1- (4-dodecyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1-phenyl-3- (4-dodecyl-styryl) -5- (4 -Dodecyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-dodecyl-stynyl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4-tert-octyl-phenyl) ) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (4-tert-octyl-styryl) ) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4-dodecyl-phenyl) -3- (4-tert-butyl-styryl) -5 (4-tert-butyl-phenyl) -pyrazoline, 1- (4-tert-butyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4 -Dodecyl-phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4-tert-octyl-phenyl) -3- (4-dodecyl) -Styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (2,4-dibutyl-phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, etc. Is mentioned.

  Examples of the pyrazoline derivative include 1-phenyl-3- (3,5-di-tert-butyl-styryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline and 1-phenyl. -3- (2,6-di-tert-butyl-styryl) -5- (2,6-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2,5-di-tert- Butyl-styryl) -5- (2,5-di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (2,6-di-n-butyl-styryl) -5- (2,6- Di-n-butyl-phenyl) -pyrazoline, 1- (3,4-di-tert-butyl-phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (3,5-di-tert-butyl- Phenyl) -3-styryl- -Phenyl-pyrazoline, 1- (4-tert-butyl-phenyl) -3- (3,5-di-tert-butyl-phenyl) -5-phenyl-pyrazoline, 1- (3,5-di-tert- Butyl-phenyl) -3- (3,5-di-tert-butyl-styryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (5-tert-butyl) -Benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5 -(4-tert-butyl-phenyl) -pyrazoline, 1- (4- (4-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styrene) L) -5- (4-tert-butyl-phenyl) -pyrazoline, 1- (4- (5-tert-octyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1 -(4- (Benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4- (5-tert -Octyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4- (5-dodecyl-benzo) Oxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-stynyl)- 5- (4-dodecyl-phenyl) -pyrazoline, 1- (4- (5-tert-octyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4 -Tert-butyl-phenyl) -pyrazoline and the like.

  Furthermore, examples of the pyrazoline derivative include 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert- Octyl-phenyl) -pyrazoline, 1- (4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -Pyrazolin, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- ( 4- (5-dodecyl-benzoxazol-2-yl) phenyl) -3- (4-tert-octyl-styryl) -5- (4-tert-octyl-thio) Nyl) -pyrazoline, 1- (4- (5-tert-octyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1 -(4- (4,6-dibutyl-benzoxazol-2-yl) phenyl) -3- (4-dodecyl-styryl) -5- (4-dodecyl-phenyl) -pyrazoline, 1- (4- (benzo Oxazol-2-yl) phenyl) -3- (3,5-di-tert-butylstyryl) -5- (3,5-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoxazole) -2-yl) phenyl) -3- (2,6-di-tert-butyl-styryl) -5- (2,6-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzoo) Sazol-2-yl) phenyl) -3- (2,5-di-tert-butyl-styryl) -5- (2,5-di-tert-butyl-phenyl) -pyrazoline, 1- (4- (benzo Oxazol-2-yl) phenyl) -3- (2,6-di-n-butyl-styryl) -5- (2,6-di-n-butyl-phenyl) -pyrazoline, 1- (4- (4 , 6-Di-tert-butyl-benzoxazol-2-yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (5,7-di-tert-butyl-benzoxazol-2-yl) Yl) phenyl) -3-styryl-5-phenyl-pyrazoline, 1- (4- (5-tert-butyl-benzoxazol-2-yl) phenyl) -3- (3,5-di-tert-butyl- Styryl) -5- Phenyl-pyrazoline, 1- (4- (4,6-di-tert-butyl-benzoxazol-2-yl) phenyl) -3- (3,5-di-tert-butyl-styryl) -5- (3 , 5-Di-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-amino-phenyl) -pyrazoline, 1-phenyl-3- (4 -Tert-butyl-styryl) -5- (4-N-ethyl-phenyl) -pyrazoline and 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-N, N-diethyl- Phenyl) -pyrazoline and the like.

  Furthermore, examples of the pyrazoline derivative include 1-phenyl-3- (4-biphenyl) -5- (4-n-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- ( 4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-isobutyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- ( 4-n-pentyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-isopentyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- ( 4-neopentyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-hexyl-phenyl) -pyrazoline, 1-phenyl-3- (4-bif Nyl) -5- (4-heptyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-n-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4- Biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-nonyl-phenyl) -pyrazoline, 1-phenyl-3- (4- Biphenyl) -5- (4-decyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-undecyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) And -5- (4-dodecyl-phenyl) -pyrazoline.

  Among the pyrazoline derivatives listed above, 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl)-is preferable from the viewpoint of adhesion and rectangularity of the resist pattern. Pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline and 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) ) -Pyrazoline is preferred.

  Examples of ester compounds of N-aryl amino acids include N-phenylglycine methyl ester, N-phenylglycine ethyl ester, N-phenylglycine n-propyl ester, N-phenylglycine isopropyl ester, and N-phenylglycine. 1-butyl ester, N-phenylglycine 2-butyl ester, N-phenylglycine tertbutyl ester, N-phenylglycine pentyl ester, N-phenylglycine hexyl ester, N-phenylglycine pentyl ester, N -Phenylglycine octyl ester and the like.

  Examples of the halogen compound include amyl bromide, isoamyl bromide, isobutylene bromide, ethylene bromide, diphenylmethyl bromide, benzyl bromide, methylene bromide, tribromomethylphenyl sulfone, carbon tetrabromide, tris (2 , 3-Dibromopropyl) phosphate, trichloroacetamide, amyl iodide, isobutyl iodide, 1,1,1-trichloro-2,2-bis (p-chlorophenyl) ethane, chlorinated triazine compounds, diallyl iodonium compounds, and the like. In particular, tribromomethylphenylsulfone is preferred.

  The (C) photopolymerization initiators listed above may be used alone or in combination of two or more. Among these (C) photopolymerization initiators, hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds, quinones, acridines are used from the viewpoints of sensitivity and resolution of the photosensitive resin composition. And / or pyrazoline derivatives are preferably used, and hexaarylbiimidazole compounds, N-aryl-α-amino acid compounds and / or acridines are more preferably used.

  (C) The ratio with respect to the total mass of the photosensitive resin composition of a photoinitiator is 0.01 mass%-20 mass%. Setting this proportion to 0.01% by mass or more is advantageous from the viewpoint of obtaining sufficient sensitivity, and this proportion is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more. preferable. On the other hand, setting this ratio to 20% by mass or less is advantageous from the viewpoint of obtaining high resolution and suppressing the cohesiveness in the developer, and this ratio should be 10% by mass or less. preferable.

  Moreover, (C) When using the hexaaryl biimidazole compound as a photoinitiator, content of a hexa aryl biimidazole compound is 0.1 mass%-15 mass with respect to the total mass of the photosensitive resin composition. % Is preferred. The blending amount of 0.1% by mass or more is preferable from the viewpoint of obtaining sufficient sensitivity, the blending amount is more preferably 1% by mass or more, and particularly preferably 3% by mass or more. . On the other hand, setting the blending amount to 15% by mass or less is preferable from the viewpoint of obtaining high resolution and suppressing the cohesiveness in the developer, and controlling the blending amount to 10% by mass or less. Is more preferable, and it is particularly preferable that the content be 6% by mass or less.

  When (C) an N-aryl-α-amino acid compound is used as the photopolymerization initiator, the content of the N-aryl-α-amino acid compound is 0.001 with respect to the total mass of the photosensitive resin composition. The mass% to 5 mass% is preferable. Setting this amount to 0.001% by mass or more is preferable from the viewpoint of obtaining sufficient sensitivity, more preferably 0.01% by mass or more, and more preferably 0.1% by mass or more. It is particularly preferred. On the other hand, it is preferable to make this compounding amount 5% by mass or less from the viewpoint of obtaining high resolution and improving hue stability, and it is more preferable to make this compounding amount 1% by mass or less. It is particularly preferable that the content be 0.5% by mass or less.

  Moreover, (c) When using acridine as a photoinitiator, 0.01 mass%-5 mass% are preferable with respect to the total mass of photosensitive resin composition. Setting this amount to 0.01% by mass or more is preferable from the viewpoint of obtaining sufficient sensitivity, and it is more preferable to set this amount to 0.1% by mass or more, and to 0.2% by mass or more. It is particularly preferred. On the other hand, making this blending amount 5% by mass or less is preferable from the viewpoint of obtaining a rectangular resist shape and improving hue stability, and it is more preferable to make this blending amount 3% by mass or less. It is particularly preferable to make it 2% by mass or less.

<Compound having sulfide structure and compound having hindered phenol structure>
In the present embodiment, a compound having a sulfide structure and a compound having a hindered phenol structure are included in the photosensitive resin composition. Each of the sulfide structure and the hindered phenol structure may be contained, for example, in the components (A) to (C) described above, or may be contained in the component (D) described later, It may be a combination. As an aspect in which a compound having a sulfide structure and a compound having a hindered phenol structure exist in the photosensitive resin composition, (1) a compound having a sulfide structure and not having a hindered phenol structure and a hindered A mode in which a combination with a compound having a phenol structure and no sulfide structure exists, (2) a mode in which a compound having both a sulfide structure and a hindered phenol structure exists, and (3) a mode having a sulfide structure. And a combination of a compound having no hindered phenol structure and / or a compound having a hindered phenol structure and not having a sulfide structure and a compound having both a sulfide structure and a hindered phenol structure. . The presence of the compound having a sulfide structure and the compound having a hindered phenol structure in the photosensitive resin composition provides a photosensitive resin composition that gives excellent resolution.

｛式中、Ｒ¹及びＲ²は、各々独立に、置換されていてもよい、直鎖アルキル基、分岐アルキル基、アリール基、シクロヘキシル基、２価の連結基を介した直鎖アルキル基、２価の連結基を介した分岐アルキル基、２価の連結基を介したシクロヘキシル基又は２価の連結基を介したアリール基を表す。｝
中でも、Ｓ原子がアルキル基と結合していることが好ましい。また、から、Ｓ原子に結合している当該アルキル基には芳香族置換基が結合されていることが好ましい。 In the present embodiment, the compound having a sulfide structure is typically a compound represented by the following general formula (1).

{Wherein R ¹ and R ² are each independently a linear alkyl group, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group via a divalent linking group, which may be substituted, A branched alkyl group via a divalent linking group, a cyclohexyl group via a divalent linking group, or an aryl group via a divalent linking group is represented. }
Among these, it is preferable that the S atom is bonded to the alkyl group. In addition, it is preferable that an aromatic substituent is bonded to the alkyl group bonded to the S atom.

  The compound having a sulfide structure may be a compound having both a sulfide structure and a hindered phenol structure as described later.

｛式中、Ｒ³は、置換されていてもよい、炭素数が２以上の直鎖アルキル基、分岐アルキル基、アリール基、シクロヘキシル基、２価の連結基を介した直鎖アルキル基、２価の連結基を介した分岐アルキル基、２価の連結基を介したシクロヘキシル基又は２価の連結基を介したアリール基を表し、そしてＲ⁴、Ｒ⁵、Ｒ⁶及びＲ⁷は、各々独立に、水素、又は、置換されていてもよい、直鎖アルキル基、分岐アルキル基、アリール基、シクロヘキシル基、２価の連結基を介した直鎖アルキル基、２価の連結基を介した分岐アルキル基、２価の連結基を介したシクロヘキシル基若しくは２価の連結基を介したアリール基を表す。｝ In the present embodiment, the hindered phenol structure means a structure in which at least 2-position and / or 6-position of phenol is substituted with a bulky group. The compound having a hindered phenol structure is typically a compound represented by the following general formula (2).

{Wherein R ³ is a linear alkyl group having 2 or more carbon atoms, a branched alkyl group, an aryl group, a cyclohexyl group, a divalent linking group, which may be substituted; A branched alkyl group via a valent linking group, a cyclohexyl group via a divalent linking group, or an aryl group via a divalent linking group, and R ⁴ , R ⁵ , R ⁶ and R ⁷ are each Independently, hydrogen or optionally substituted linear alkyl group, branched alkyl group, aryl group, cyclohexyl group, linear alkyl group via divalent linking group, via divalent linking group It represents a branched alkyl group, a cyclohexyl group via a divalent linking group, or an aryl group via a divalent linking group. }

  In the present embodiment, when a compound having a sulfide structure and a compound having a hindered phenol structure are used in combination, details of the mechanism for improving the resolution of the photosensitive resin composition are not clear, but are considered as follows. That is, when the photosensitive resin layer is irradiated with light in the exposure process, the focal position may be shifted. In such a case, since the light is not sufficiently collected, weak light is emitted even outside the pattern position. As a result, the pattern tends not to be formed accurately. It is considered that when the sulfide structure and the hindered phenol structure are present in the photosensitive resin layer, the weak light is consumed by these structures, and the accurate transfer of the pattern shape is maintained.

｛式中、Ｒ⁸は、置換されていてもよい、炭素数が２以上の直鎖アルキル基、分岐アルキル基、アリール基、シクロヘキシル基、２価の連結基を介した直鎖アルキル基、２価の連結基を介した分岐アルキル基、２価の連結基を介したシクロヘキシル基又は２価の連結基を介したアリール基を表し、そしてＲ⁹、Ｒ¹⁰及びＲ¹¹は、各々独立に、水素、又は、置換されていてもよい、直鎖アルキル基、分岐アルキル基、アリール基、シクロヘキシル基、２価の連結基を介した直鎖アルキル基、２価の連結基を介した分岐アルキル基、２価の連結基を介したシクロヘキシル基若しくは２価の連結基を介したアリール基を表す。｝で表される化合物を含むことが特に好ましい。上記一般式（３）に関し、それぞれのアルキル基の好ましい炭素数、並びに、２価の連結基及び置換基の好ましい態様は、上記一般式（２）で前述したのと同様である。 The photosensitive resin composition has the following general formula (3) as a compound having a hindered phenol structure:

{Wherein R ⁸ is an optionally substituted linear alkyl group having 2 or more carbon atoms, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group via a divalent linking group, 2 A branched alkyl group via a valent linking group, a cyclohexyl group via a divalent linking group or an aryl group via a divalent linking group, and R ⁹ , R ¹⁰ and R ¹¹ are each independently Hydrogen or an optionally substituted linear alkyl group, branched alkyl group, aryl group, cyclohexyl group, linear alkyl group via a divalent linking group, branched alkyl group via a divalent linking group It represents a cyclohexyl group via a divalent linking group or an aryl group via a divalent linking group. } It is especially preferable that the compound represented by this is included. Regarding the general formula (3), the preferred carbon number of each alkyl group and the preferred embodiments of the divalent linking group and substituent are the same as those described above for the general formula (2).

  It is excellent in terms of improving the resolution of the photosensitive resin composition that the photosensitive resin composition contains a compound having a hindered phenol structure, and the compound represented by the general formula (3) is From the viewpoint of improving the resolution of the photosensitive resin composition, and from the viewpoint of suppressing a decrease in sensitivity of the photosensitive resin composition, it is particularly preferable.

The compound represented by the general formula (3) is R ⁸ in the general formula (3) from the viewpoint of improving the resolution of the photosensitive resin composition and suppressing the sensitivity reduction of the photosensitive resin composition. , R ⁹ , R ¹⁰ and R ¹¹ preferably have an aromatic ring. From the same viewpoint, the hydroxyl group concentration of the compound having a hindered phenol structure is preferably 0.10 mol / 100 g to 0.75 mol / 100 g.

  Examples of the compound having a hindered phenol structure include 4,4′-thiobis (6-tert-butyl-m-cresol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), and styrenation. Phenol (for example, Kawaguchi Chemical Industry Co., Ltd., Antage SP), tribenzylphenol (for example, Kawaguchi Chemical Industry Co., Ltd., TBP, phenol having 1 to 3 benzyl groups), 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], pentaerythris Lithyl tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxy Phenyl) propionate], octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-) Hydrocinnamamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, 1,3,5-trimethyl-2 4,6-tris (3,5-di -t- butyl-4-hydroxybenzyl) benzene, tris - (3,5-di -t- butyl-4-hydroxybenzyl) - isocyanurate.

  Examples of the compound represented by the general formula (3) include 4,4′-thiobis (6-tert-butyl-m-cresol) and 4,4′-butylidenebis (3-methyl-6-tert-butylphenol). And styrenated phenol (for example, manufactured by Kawaguchi Chemical Industry Co., Ltd., Antage SP), tribenzylphenol (for example, manufactured by Kawaguchi Chemical Industry Co., Ltd., TBP, phenol having 1 to 3 benzyl groups) and the like.

  The compound having a hindered phenol structure may be a compound having both a sulfide structure and a hindered phenol structure as described later.

  Preferable examples of the compound having both a sulfide structure and a hindered phenol structure include compounds in which the divalent linking group is —S— in the general formula (2) or (3). More specific preferred examples include 4,4′-thiobis (6-tert-butyl-m-cresol), bis [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionyloxy] ethyl] sulfide, 4,6-bis (octylthiomethyl) -o-cresol, 4,6-bis (dodecylthiomethyl) -o-cresol, and the like.

<(D) Additive>
In a preferred embodiment, the photosensitive resin composition includes (D) an additive containing a sulfide structure, a hindered phenol structure, or a combination thereof (hereinafter also referred to as (D) additive). (D) An additive can consist of 1 type, or 2 or more types of compounds. That is, (D) the additive is a compound having a sulfide structure and not having a hindered phenol structure, a compound having a hindered phenol structure and not having a sulfide structure, and both a sulfide structure and a hindered phenol structure. It consists of 1 or more types selected from the group which consists of a compound which has this. (D) More specifically, the additive is a compound as exemplified above with respect to the compound having a sulfide structure and the compound having a hindered phenol structure, and is included in the above-described components (A) to (C). You can choose from compounds that are not. In one embodiment, (D) the additive is a compound having a sulfide structure. In another embodiment, (D) the additive is a compound having a hindered phenol structure.

  The content of (D) additive is preferably 0.001% by mass to 10% by mass with respect to the total mass of the photosensitive resin composition. The content is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.1% by mass or more from the viewpoint of improvement in resolution. From the standpoint of hardly causing a decrease in property, it is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less.

  The ratio of the sulfide structure to 1 kg of the photosensitive resin composition is preferably 1 mmol / kg to 50 mmol / kg from the viewpoint of suppressing the narrowing of the space width due to the focal position shift. This ratio is more preferably 4 mmol / kg to 14 mmol / kg, and further preferably 5 mmol / kg to 10 mmol / kg.

  The ratio of the hindered phenol structure to 1 kg of the photosensitive resin composition is preferably 0.05 mmol / kg to 500 mmol / kg. This ratio is preferably 0.05 mmol / kg or more, more preferably 0.5 mmol / kg or more, further preferably 2.5 mmol / kg or more, further preferably 5 mmol / kg or more in terms of improving resolution. 25 mmol / kg or more is particularly preferable, and 35 mmol / kg or more is most preferable. On the other hand, this ratio is preferably 500 mmol / kg or less, more preferably 250 mmol / kg or less, and more preferably 150 mmol / kg, in that the effects of sensitivity reduction and resolution reduction due to the presence of the compound having a hindered phenol structure are less likely to occur. The following is more preferable, 100 mmol / kg or less is further preferable, and 75 mmol / kg or less is particularly preferable.

<Additional ingredients>
In this Embodiment, the photosensitive resin composition may contain the following additional components other than said (A)-(C) component and arbitrary (D) components, for example.

(Coloring substances and dyes)
In the present embodiment, the photosensitive resin composition may contain a coloring substance or a dye as desired.

  Examples of the coloring substance include fuchsin, phthalocyanine green, auramine base, paramadienta, crystal violet, methyl orange, Nile blue 2B, Victoria blue, malachite green (for example, Eisen (registered trademark) MALACHITE GREEN manufactured by Hodogaya Chemical Co., Ltd.), Examples thereof include Basic Blue 20 and Diamond Green (for example, Eizen (registered trademark) DIAMOND GREEN GH manufactured by Hodogaya Chemical Co., Ltd.). The content of the coloring substance in the photosensitive resin composition is preferably 0.001% by mass to 1% by mass when the total mass of the photosensitive resin composition is 100% by mass. Setting the content to 0.001% by mass or more is preferable from the viewpoint of improving the handleability of the photosensitive resin composition, while setting the content to 1% by mass or less is a photosensitive resin. It is preferable from the viewpoint of maintaining the storage stability of the composition.

  The photosensitive resin composition is preferable in terms of visibility because the exposed portion is colored by containing a dye (for example, leuco dye or fluoran dye), and when an inspection machine reads an alignment marker for exposure. The higher the contrast between the exposed part and the unexposed part, the easier it is to recognize the marker, which is advantageous.

  Examples of the leuco dye include tris (4-dimethylaminophenyl) methane [leuco crystal violet], bis (4-dimethylaminophenyl) phenylmethane [leucomalachite green], and the like. In particular, from the viewpoint of good contrast, it is preferable to use leuco crystal violet as the leuco dye. It is preferable that content of the leuco dye in the photosensitive resin composition is 0.1 mass%-10 mass% with respect to the total mass of the photosensitive resin composition. Setting the content to 0.1% by mass or more is preferable from the viewpoint of improving the contrast between the exposed part and the unexposed part, and it is more preferable to set the content to 0.2% by mass or more. It is particularly preferable to set it to 4% by mass or more. On the other hand, the content is preferably 10% by mass or less from the viewpoint of maintaining storage stability, the content is more preferably 5% by mass or less, and particularly preferably 2% by mass or less. preferable.

  Moreover, it is preferable from the viewpoint of optimizing adhesion and contrast that the leuco dye and the halogen compound described above with respect to the (C) photopolymerization initiator are used in combination in the photosensitive resin composition. When a leuco dye is used in combination with the halogen compound, the content of the halogen compound in the photosensitive resin composition is 0.01% by mass to 100% by mass when the total mass of the photosensitive resin composition is 100% by mass. 3% by mass is preferable from the viewpoint of maintaining the storage stability of the hue in the photosensitive layer.

(Other compounds)
Furthermore, the photosensitive resin composition further contains at least one compound selected from the group consisting of radical polymerization inhibitors, benzotriazoles, and carboxybenzotriazoles, in order to improve thermal stability and storage stability. May be.

  Examples of the radical polymerization inhibitor include p-methoxyphenol, hydroquinone, pyrogallol, naphthylamine, cuprous chloride, nitrosophenylhydroxyamine aluminum salt, diphenylnitrosamine and the like. In order not to impair the sensitivity of the photosensitive resin composition, a nitrosophenylhydroxyamine aluminum salt is preferred.

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

  Examples of carboxybenzotriazoles include 4-carboxy-1,2,3-benzotriazole, 5-carboxy-1,2,3-benzotriazole, and N- (N, N-di-2-ethylhexyl) aminomethylene. Examples thereof include carboxybenzotriazole, N- (N, N-di-2-hydroxyethyl) aminomethylenecarboxybenzotriazole, N- (N, N-di-2-ethylhexyl) aminoethylenecarboxybenzotriazole and the like.

  The total content of the radical polymerization inhibitor, benzotriazoles, and carboxybenzotriazoles is preferably 0.01% by mass to 3% by mass when the total mass of the photosensitive resin composition is 100% by mass. %, More preferably 0.05% by mass to 1% by mass. Setting the content to 0.01% by mass or more is preferable from the viewpoint of imparting storage stability to the photosensitive resin composition, while setting the content to 3% by mass or less improves sensitivity. It is preferable from the viewpoint of maintaining and suppressing decolorization of the dye.

  In the present embodiment, the photosensitive resin composition may further contain bisphenol A epoxy compounds. Examples of the bisphenol A epoxy compounds include compounds obtained by modifying bisphenol A with polypropylene glycol and epoxidizing the terminals.

  In the present embodiment, the photosensitive resin composition may further contain a plasticizer. Examples of the plasticizer include phthalic acid esters such as diethyl flate, o-toluenesulfonic acid amide, p-toluenesulfonic acid amide, tributyl citrate, triethyl citrate, acetyl triethyl citrate, and acetyl tricitrate tri-n-. And propyl, acetyl citrate tri-n-butyl, polyethylene glycol, polypropylene glycol, polyethylene glycol alkyl ether, and polypropylene glycol alkyl ether. Also, Adecanol SDX-1569, Adecanol SDX-1570, Adecanol SDX-1571, Adecanol SDX-479 (manufactured by Asahi Denka Co., Ltd.), New Pole BP-23P, New Pole BP-3P, New Pole BP-5P, New Pole Pole BPE-20T, New Pole BPE-60, New Pole BPE-100, New Pole BPE-180 (manufactured by Sanyo Chemical Co., Ltd.), Unior DB-400, Unior DAB-800, Unior DA-350F, Unior DA- Examples include compounds having a bisphenol skeleton such as 400, Uniol DA-700 (manufactured by Nippon Oil & Fats Co., Ltd.), BA-P4U glycol, BA-P8 glycol (manufactured by Nippon Emulsifier Co., Ltd.).

  The content of the plasticizer in the photosensitive resin composition is preferably 1% by mass to 50% by mass and more preferably 1% by mass to 30% by mass with respect to the total mass of the photosensitive resin composition. . Setting the content to 1% by mass or more is preferable from the viewpoint of suppressing delay in development time and imparting flexibility to the cured film, while making the content 50% by mass or less, This is preferable from the viewpoint of suppressing insufficient curing and cold flow.

<Solvent>
In a preferred embodiment, the photosensitive resin composition can be used in the state of a preparation obtained by adding a solvent thereto. Examples of the solvent include ketones typified by methyl ethyl ketone (MEK) and alcohols typified by methanol, ethanol and isopropanol. The solvent is added to the photosensitive resin composition in such an amount that the viscosity of the solution of the photosensitive resin composition to be applied on the support film (that is, the preparation liquid) is 500 mPa · s to 4000 mPa · s at 25 ° C. It is preferable.

<Photosensitive resin laminate>
The present embodiment also provides a photosensitive resin laminate including a support layer and a photosensitive resin layer made of the photosensitive resin composition of the present embodiment laminated on the support layer. The support layer is, for example, a support film. If necessary, the photosensitive resin laminate may further have a protective layer on the surface of the photosensitive resin layer opposite to the support layer side.

  The support film is preferably a transparent film that transmits light emitted from the exposure light source. Examples of such support films include polyethylene terephthalate film, polyvinyl alcohol film, polyvinyl chloride film, vinyl chloride copolymer film, polyvinylidene chloride film, vinylidene chloride copolymer film, polymethyl methacrylate copolymer film, Examples thereof include a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, and a cellulose derivative film. These films can be stretched if necessary, and preferably have a haze of 5 or less. The thinner the film is, the more advantageous it is to improve the image forming property and the economical efficiency, but a film having a thickness of 10 μm to 30 μm is preferably used in order to maintain the strength of the photosensitive resin laminate.

  An important characteristic of the protective layer used in the photosensitive resin laminate is that the protective layer is sufficiently smaller than the support layer (for example, a support film) in terms of adhesion to the photosensitive resin layer and can be easily peeled off. For example, a polyethylene film or a polypropylene film can be preferably used as the protective layer. Further, for example, a film having excellent peelability as described in JP-A-59-202457 can be used. The thickness of the protective layer is preferably 10 μm to 100 μm, more preferably 10 μm to 50 μm.

  When a polyethylene film is used as the protective layer, there is a gel called fish eye on the surface of the polyethylene film, which may be transferred to the photosensitive resin layer. When the fish eye is transferred to the photosensitive resin layer, air may be entrained during lamination to form voids, which may lead to defects in the resist pattern. From the viewpoint of preventing fish eyes, stretched polypropylene is more preferable as the material of the protective layer. A specific example is Alfane E-200A manufactured by Oji Paper Co., Ltd.

  Although the thickness of the photosensitive resin layer in the photosensitive resin laminate varies depending on the application, it is preferably 5 μm to 100 μm, more preferably 7 μm to 60 μm. The thinner the thickness, the higher the resolution, and the thicker the film strength. .

  The manufacturing method of the photosensitive resin laminated body is demonstrated. As a method for producing a photosensitive resin laminate by sequentially laminating a support layer (for example, a support film), a photosensitive resin layer, and, if necessary, a protective layer, a known method can be employed. For example, the photosensitive resin composition used for the photosensitive resin layer is mixed with a solvent that dissolves the photosensitive resin composition to form a uniform solution, which is first applied onto the support layer using a bar coater or roll coater, and then dried to form the support layer. A photosensitive resin layer made of a photosensitive resin composition can be laminated thereon. Next, if necessary, a photosensitive resin laminate can be produced by laminating a protective layer on the photosensitive resin layer.

<Method for producing resist pattern>
Next, the present embodiment also includes a lamination step of laminating the photosensitive resin laminate of the present embodiment on a substrate, an exposure step of exposing the photosensitive resin layer of the photosensitive resin laminate, and the photosensitivity. Provided is a method for producing a resist pattern, which includes a development step of developing and removing an unexposed portion of a resin layer.
An example of a method for producing a resist pattern using the photosensitive resin laminate of the present embodiment will be described. Examples of resist patterns include printed wiring boards, semiconductor elements, printing plates, liquid crystal display panels, flexible substrates, lead frame substrates, COF (chip on film) substrates, semiconductor package substrates, liquid crystal transparent electrodes, and liquid crystal TFTs. Patterns for wiring, PDP (plasma display panel) electrodes, and the like. As an example, a method for manufacturing a printed wiring board will be described as follows.

  In a preferred embodiment, the exposure step is performed by direct drawing of a drawing pattern. In the present embodiment, direct drawing is particularly advantageous when high-mix low-volume production is performed in a short delivery time or when position accuracy is required. A more detailed aspect of the exposure process will be described later.

A printed wiring board is manufactured through the following steps.
(1) Laminating step In this step, the photosensitive resin laminate is adhered to a substrate such as a copper clad laminate or a flexible substrate using a hot roll laminator while peeling off the protective layer of the photosensitive resin laminate. The heating temperature is usually 40 to 160 ° C.

(2) Exposure step In this step, a mask film having a desired wiring pattern is brought into close contact with the support and exposed using an active light source (for example, a UV lamp), or the desired wiring pattern is applied to the active light source. Exposure is performed by direct drawing with light from (for example, a semiconductor laser).

(3) Development step In this step, after the exposure step, the support on the photosensitive resin layer is peeled off, and then the unexposed portion is developed and removed using a developing solution of an alkaline aqueous solution. To form. As the alkaline aqueous solution, an aqueous solution of Na ₂ CO ₃ or K ₂ CO ₃ is usually used. The alkaline aqueous solution is appropriately selected according to the characteristics of the photosensitive resin layer, and a Na ₂ CO ₃ aqueous solution having a concentration of about 0.2% by mass to about 2% by mass and about 20 ° C. to about 40 ° C. is generally used. It is.

  Although a resist pattern can be obtained through each of the above steps, a heating step at about 100 ° C. to about 300 ° C. can be further performed in some cases. By carrying out this heating step, chemical resistance can be further improved. For heating, a hot air, infrared, or far infrared heating furnace can be used.

Furthermore, a conductor pattern can be formed using the method for producing a resist pattern of the present embodiment. The conductor pattern can be manufactured by, for example, the following steps (4) and (5) after manufacturing the resist pattern by the method of the present embodiment.
(4) Etching process or plating process In this process, the surface (for example, copper surface) of the base material exposed by the development in the development process is etched or plated to form a conductor pattern.
(5) Stripping Thereafter, the resist pattern is stripped from the substrate with an aqueous solution having alkalinity stronger than that of the developer. The alkaline aqueous solution for peeling is not particularly limited, but an aqueous solution of NaOH or KOH having a concentration of about 2% by mass to about 5% by mass and a temperature of about 40 to about 70 ° C. is generally used. A small amount of a water-soluble solvent can also be added to the stripping solution.

  The photosensitive resin laminate of the present embodiment is a conductive pattern such as a printed wiring board, a flexible substrate, a lead frame substrate, a COF substrate, a semiconductor package substrate, a liquid crystal transparent electrode, a liquid crystal TFT wiring, and a PDP electrode. It is the photosensitive resin laminated body suitable for manufacture of this.

  The various parameters described above are measured according to the measurement method in the examples described later or a method equivalent thereto unless otherwise specified.

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

<Acid equivalent>
An automatic titration apparatus (Hiranuma Sangyo Co., Ltd. Hiranuma automatic titration apparatus (COM-555)) was used, and a potentiometric titration method was performed using a 0.1 mol / L sodium hydroxide aqueous solution.

<Sensitivity evaluation>
First, a 0.4 mm-thick copper clad laminate on which 35 μm rolled copper foil is laminated is jetted using a grinding material (Nippon Carlit Co., Ltd., Sacradund R (registered trademark # 220)) at a spray pressure of 0.2 MPa. Scrub polished.

  Next, while peeling the polyethylene film of the photosensitive resin laminate, roll the photosensitive resin laminate on a copper clad laminate preheated to 60 ° C. with a hot roll laminator (Asahi Kasei Co., Ltd., AL-700). Lamination was performed at a temperature of 105 ° C. The air pressure was 0.35 MPa, and the laminating speed was 1.5 m / min.

  Next, the pattern in which an unexposed part becomes a line was exposed by 8W with the direct drawing exposure machine (The Orbotec Co., Ltd. product, Paragon-9000). In this exposure, the exposure was carried out with an exposure amount at which the maximum number of remaining film steps was 20 when exposure and development were performed using the above-mentioned stopher 41-step tablet as a mask. In addition, the three focal points are the substrate surface (expressed as ± 0 μm), 400 μm before the substrate (expressed as +400 μm), and 300 μm from the substrate (expressed as −300 μm). And exposed.

Further, after the polyethylene terephthalate film is peeled off, a 1 mass% Na ₂ CO ₃ aqueous solution at 30 ° C. is sprayed for a predetermined time using an alkali developing machine (manufactured by Fuji Kiko Co., Ltd., a dry film developing machine). The unexposed portion of the layer was dissolved and removed in a time twice as long as the minimum development time. At this time, the minimum time required for completely dissolving the photosensitive resin layer in the unexposed portion was defined as the minimum development time. The actual development time was twice as long as the minimum development time to obtain a cured resist pattern.

Thereafter, the space width of the unexposed portion at a mask width of 50 μm was measured.

<Weight average molecular weight>
Gel Permeation Chromatography (GPC) manufactured by JASCO Corporation [Pump: Gulliver, PU-1580 type, Column: Shodex (trademark) manufactured by Showa Denko KK (KF-807, KF-806M, KF-806M, KF-802.5) 4 in series, mobile phase solvent: tetrahydrofuran, polystyrene standard sample (use of calibration curve by Shodex STANDARD SM-105 manufactured by Showa Denko KK) was used to determine the weight average molecular weight as polystyrene.

[Examples 1 to 4 (Examples 1, 3 and 4 are reference examples) and Comparative Examples 1 and 2]
A photosensitive resin composition obtained by sufficiently stirring and mixing the photosensitive resin composition and the solvent having the composition shown in Tables 1 and 2 (where the numbers of the respective components indicate the blending amount (part by mass) as a solid content). A preparation was obtained. A polyethylene terephthalate film having a thickness of 16 μm is prepared as a support, and the photosensitive resin composition mixture is uniformly applied to the surface of the film using a bar coater, and dried in a 95 ° C. drier for 3 minutes. A photosensitive resin layer was formed. The thickness of the photosensitive resin layer was 29 μm.

  Next, a 19 μm thick polyethylene film was bonded as a protective layer on the surface of the photosensitive resin layer on which the polyethylene terephthalate film was not laminated to obtain a photosensitive resin laminate. Various evaluation was performed about the obtained photosensitive resin laminated body. The results are shown in Table 1.

From the results of Tables 1 and 2, the following contents can be read.
By using the photosensitive resin composition of the present embodiment in comparison with the examples and the comparative examples, it is possible to suppress the tendency of the space width to be narrowed when the focal position is shifted.

  The photosensitive resin laminate of the present embodiment has a high resolution, so that a printed wiring board, a flexible substrate, a lead frame substrate, a COF (chip on film) substrate, a semiconductor package substrate, a transparent electrode for liquid crystal It can be used for the production of conductive patterns such as liquid crystal TFT wiring and PDP (plasma display panel) electrodes.

Claims (9)

below:
(A) Alkali-soluble polymer: 10% by mass to 90% by mass;
(B) Compound having ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) Photopolymerization initiator: 0.01% by mass to 20% by mass;
A photosensitive resin composition comprising:
The (A) alkali-soluble polymer has an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000,
A compound having a sulfide structure and a compound having a hindered phenol structure exist in the photosensitive resin composition,
In the photosensitive resin composition, the compound having the hindered phenol structure is represented by the following general formula (3):

{Wherein R ⁸ is an optionally substituted linear alkyl group having 2 or more carbon atoms, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group via a divalent linking group, 2 A branched alkyl group via a valent linking group, a cyclohexyl group via a divalent linking group or an aryl group via a divalent linking group, and R ⁹ , R ¹⁰ and R ¹¹ are each independently Hydrogen or an optionally substituted linear alkyl group, branched alkyl group, aryl group, cyclohexyl group, linear alkyl group via a divalent linking group, branched alkyl group via a divalent linking group It represents a cyclohexyl group via a divalent linking group or an aryl group via a divalent linking group. Look containing a compound represented by},
The amount of sulfide groups contained in 1 kg of the photosensitive resin composition is 4 mmol / g to 10 mmol / kg (provided that the amount of sulfide groups contained in 1 kg of the photosensitive resin composition is 5.5 mmol / kg). A photosensitive resin composition, excluding cases) . below:
(A) Alkali-soluble polymer: 10% by mass to 90% by mass;
(B) Compound having ethylenically unsaturated double bond: 5% by mass to 70% by mass; and (C) Photopolymerization initiator: 0.01% by mass to 20% by mass;
A photosensitive resin composition comprising:
The (A) alkali-soluble polymer has an acid equivalent of 100 to 600 and a weight average molecular weight of 5,000 to 500,000,
A compound having a sulfide structure and a compound having a hindered phenol structure exist in the photosensitive resin composition,
In the photosensitive resin composition, the compound having the hindered phenol structure is represented by the following general formula (3):

{Wherein R ⁸ is an optionally substituted linear alkyl group having 2 or more carbon atoms, a branched alkyl group, an aryl group, a cyclohexyl group, a linear alkyl group via a divalent linking group, 2 A branched alkyl group via a valent linking group, a cyclohexyl group via a divalent linking group or an aryl group via a divalent linking group, and R ⁹ , R ¹⁰ and R ¹¹ are each independently Hydrogen or an optionally substituted linear alkyl group, branched alkyl group, aryl group, cyclohexyl group, linear alkyl group via a divalent linking group, branched alkyl group via a divalent linking group It represents a cyclohexyl group via a divalent linking group or an aryl group via a divalent linking group. Look containing a compound represented by},
The amount of sulfide groups contained per kg in the photosensitive resin composition is 4 mmol / kg to 10 mmol / kg,
The (B) compound having an ethylenically unsaturated double bond is a photosensitive resin composition comprising a compound having (meth) acryloyl groups at both ends by modifying bisphenol A with alkylene oxide . (D) Additive containing sulfide structure or hindered phenol structure or a combination thereof: 0.001% by mass to 10% by mass;
The photosensitive resin composition according to claim 1 or 2 , further comprising: The photosensitive resin composition according to claim 3 , wherein the (D) additive is a compound having a sulfide structure. The photosensitive resin composition of Claim 3 or 4 whose said (D) additive is a compound which has a hindered phenol structure. The hindered phenol group amount contained per 1kg of the photosensitive resin composition is not more than 35 mmol / kg or more 500 mmol / kg, the photosensitive resin composition according to any one of claims 1 to 5.   The photosensitive resin laminated body containing a support layer and the photosensitive resin layer which consists of a photosensitive resin composition of any one of Claims 1-6 laminated | stacked on this support layer.   A lamination step of laminating the photosensitive resin laminate according to claim 7 on a substrate, an exposure step of exposing a photosensitive resin layer of the photosensitive resin laminate, and developing and removing an unexposed portion of the photosensitive resin layer A method for producing a resist pattern, comprising a developing step.   The method for producing a resist pattern according to claim 8, wherein the exposure step is performed by direct drawing of a drawing pattern.