JP2017173734A - Photosensitive resin composition and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive resin composition having excellent curability, solvent resistance after curing, and heat resistance, and provide a cured product formed from the photosensitive resin composition, and a color filter and a display device prepared with the cured product.SOLUTION: A photosensitive resin composition comprises (A) photo-radical-polymerizable compound, (B) alkali-soluble resin of a specific structure, (C) photoradical polymerization initiator, (D) photoacid generator, and (E) colorant.SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition, a cured product obtained by curing the photosensitive resin composition, and a color filter. More specifically, as a so-called resist, it is used in the field of various electronic information materials, especially color filter pixels, overcoats, used in color liquid crystal display panels, color imaging tube elements, organic EL display panels, etc. in the field of electronic information materials. The present invention relates to a photosensitive resin composition that can be suitably used for production of a photolitho spacer, and a cured product thereof.

  The photosensitive resin composition changes its shape by applying energy to the coated film by light or heat. For example, the part exposed to light is cured and the other part is soluble. It has something. Utilizing such characteristics, it is used to manufacture optical members for displays and circuit boards of other electronic devices, and the importance of the usefulness increases with the development of so-called IT technology. Industrial material. One important member in which such a resin composition is used is a color filter. The color filter is an indispensable member for a color liquid crystal display device and a color image pickup tube element, and has a fine colored resin layer for separating colors. Various types of photosensitive resin compositions for forming color filters have been proposed, but the current mainstream is to use an acrylic photosensitive resin composition as an alkali development type resist. Usually, an alkali-soluble resin is included as an essential component as a component that affects the plate-making characteristics in processing.

  The photosensitive resin composition is a material used in various industrial fields. However, in the field of electronic information materials, for example, in the case of color filter applications, it has good curability and has a high development rate with respect to alkali. It has excellent basic performance that contributes to plate making performance when making color filters, such as shape and adhesion performance, and basic performance that contributes to reliability and spectral characteristics of color filters, such as solvent resistance, heat resistance, and transparency. It will be required. In other words, the curable resin composition has a great influence on the plate-making performance when producing a color filter and the performance of the color filter itself, and development research for satisfying and improving these characteristics has been actively conducted. It is where you are.

  Regarding a photosensitive resin composition for a color filter, as a composition in which a cationic curable compound such as an oxiranyl group or an oxetanyl group and a photoacid generator are combined, for example, a resin having a urethane bond, a polyfunctional acrylate, an epoxy resin, A photosensitive resin composition comprising a radical polymerization initiator and a photoacid generator (see Patent Document 1), a colorant, an alkali-soluble resin, an oxiranyl group or an oxetanyl group, and one ethylenically unsaturated bond A radiation-sensitive composition for forming a colored layer of a color filter, comprising a polymerizable monomer having a Q value of 0.2 to 1.2, a photo radical generator, and a photo acid generator (Patent) Reference 2) is disclosed.

JP 2000-298339 A Japanese Patent No. 5338333

  As described above, the photosensitive resin composition is required to have various physical properties such as curability, solvent resistance after curing, adhesion to a substrate (also referred to as a base material), heat resistance, and transparency. The cured product is also required to stably exhibit transparency, solvent resistance, adhesion, heat resistance, and the like. In recent years, with the advancement of technologies for display devices and the like, there has been a strong demand for higher performance for each member used. For example, in color filter applications, a high level of resistance is required after curing. Solvent and transparency are required. However, in the current situation, conventional resin compositions cannot sufficiently meet these demands. For example, the resin compositions described in Patent Documents 1 and 2 cannot be said to have sufficient curability and heat resistance, and it is difficult to obtain a cured product having high solvent resistance and transparency. There was room for improvement in order to improve the composition and to stably exhibit high solvent resistance, transparency, heat resistance and the like.

  The present invention has been made in view of the above situation, and can stably exhibit various physical properties such as curability, solvent resistance after curing, adhesion to a substrate (base material), heat resistance and transparency, It aims at providing the photosensitive resin composition useful for various uses, such as a color filter. Another object of the present invention is to provide a cured product formed from such a photosensitive resin composition, and a color filter and a display device using the cured product.

  The present inventor has made various studies on photosensitive resin compositions useful for various applications such as color filters. As a result, even in a system in which the amount of a cationic curable compound such as epoxy is not high, a specific alkali-soluble resin can It was found that a resin composition containing a radical initiator and a photoacid generator as essential elements dramatically improves the solvent resistance after curing, and a cured product capable of expressing high transparency can be obtained. The invention has been reached.

Therefore, the photosensitive resin composition of the present invention comprises (A) a photo-radically polymerizable compound, (B) an alkali-soluble resin, (C) a photo-radical polymerization initiator, (D) a photo-acid generator, and (E) coloring. And (B) the alkali-soluble resin has a structural unit represented by the following formulas (a), (b) and (c), or the following formulas (a), (b) and (d): It has the structural unit represented by these.

[In the above formulas (a), (b), (c) and (d), R ¹ and R ³ each independently represents a hydrogen atom or a methyl group. In the above formula (a), R ² is an alkyl group optionally substituted with a functional group other than the primary hydroxy group, an alicyclic group, a group containing an aromatic ring optionally substituted with a functional group, or ether A functional group having a bond is represented. Each Y in the above formulas (a), (b), (c) and (d) independently represents a carboxylate group (—COO—) or (—OCO—), a phosphate group (— PO ₃ —) or (—OPO ₂ —), a sulfonic acid ester group (—SO ₃ —) or (—OSO ₂ —), or a phenylene group. Z in the formula (c) and X in the formula (d) each independently represent a divalent hydrocarbon group which may have a substituent. ]

  The (B) alkali-soluble resin further includes a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer, an N-substituted maleimide monomer, and an α- (unsaturated alkoxyalkyl) acrylate monomer. It is preferable to have a structural unit derived from at least one monomer selected from the group consisting of bodies.

Moreover, the hardened | cured material of this invention hardens the said photosensitive resin composition.
Moreover, the color filter of this invention has the said hardened | cured material on a board | substrate.
Furthermore, the liquid crystal display device of the present invention is equipped with the color filter.
Furthermore, the organic EL display of the present invention is equipped with the color filter.

  The photosensitive resin composition of the present invention has the above-described configuration, and can provide a cured product excellent in various physical properties such as solvent resistance and transparency after curing. When a cured resin layer obtained from such a photosensitive resin composition is used for a color filter, a display device having high display quality with high luminance and color purity and no color unevenness can be provided.

[Photosensitive resin composition]
The photosensitive resin composition of the present invention comprises (A) a photopolymerizable compound, (B) an alkali-soluble resin, (C) a photoradical polymerization initiator, (D) a photoacid generator, and (E) a colorant. Contains. The (B) alkali-soluble resin has structural units represented by the following formulas (a), (b) and (c), or is represented by the following formulas (a), (b) and (d). It has a structural unit.

In the above formulas (a), (b), (c) and (d), each R ¹ and R ³ each independently represents a hydrogen atom or a methyl group. In the above formula (a), R ² is an alkyl group optionally substituted with a functional group other than the primary hydroxy group, an alicyclic group, a group containing an aromatic ring optionally substituted with a functional group, or ether A functional group having a bond is represented. Each Y in the above formulas (a), (b), (c) and (d) independently represents a carboxylate group (—COO—) or (—OCO—), a phosphate group (— PO ₃ —) or (—OPO ₂ —), a sulfonic acid ester group (—SO ₃ —) or (—OSO ₂ —), or a phenylene group. Z in the formula (c) and X in the formula (d) each independently represent a divalent hydrocarbon group which may have a substituent.

  In the following, (A) the photoradical polymerizable compound is referred to as “compound (A) or (A) component”, (B) the alkali-soluble resin is referred to as “(B) component”, and (C) the photoradical polymerization initiator is used. The “(C) component”, the (D) photoacid generator may be referred to as “(D) component”, and the (E) colorant may be referred to as “(E) component”. In the present specification, “(meth) acrylic acid” is a notation expressing both methacrylic acid and acrylic acid. Each component may contain 1 type each, and may contain 2 or more types. Moreover, the other component may be included.

(A) Photoradical polymerizable compound <Polyfunctional compound>
The (A) radically polymerizable compound contained in the photosensitive resin composition of the present invention is preferably a bifunctional or higher polyfunctional compound (also simply referred to as “polyfunctional compound”). A polyfunctional compound is a compound having two or more functional groups in one molecule. By including such a compound, the photosensitive resin composition becomes excellent in photosensitivity and curability, and it becomes possible to obtain a cured film with extremely high hardness. The two or more functional groups may be the same functional group or different functional groups.

  The number of functions of the polyfunctional compound is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more. Further, from the viewpoint of further suppressing curing shrinkage, the functional number is preferably 10 or less, more preferably 8 or less. The molecular weight of the polyfunctional compound is not particularly limited, but is preferably 2000 or less, for example, from the viewpoint of handling.

  Examples of the functional group include a vinyl group, an allyl group, a (meth) acryloyl group, an epoxy group, an isocyanato group, a hydroxy group, an acid anhydride group, and an oxazoline group. Among these, a (meth) acryloyl group is preferable. That is, the polyfunctional compound is preferably a compound having at least one (meth) acryloyl group in one molecule, such as a polyfunctional (meth) acrylate compound or a polyfunctional urethane (meth) acrylate compound. It is preferable to use a (meth) acryloyl group-containing isocyanurate compound or the like. More preferably, it is a compound having two or more (meth) acryloyl groups in one molecule (hereinafter, also referred to as “polyfunctional (meth) acrylate compound”), and thereby has higher hardness and higher transparency. A cured product can be obtained.

  (A) The photo-radically polymerizable compound is more preferably a compound having two or more (meth) acryloyl groups in one molecule. The photoradical polymerizable compound is a low molecular compound having a radical polymerizable unsaturated group that is polymerized by irradiation with active energy rays such as free radicals, electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.), electron beams, etc. The photosensitive resin composition can be made more excellent in curability. The radical photopolymerizable compound can be classified into a monofunctional radical photopolymerizable compound having one radical polymerizable unsaturated group in the same molecule and a multifunctional radical photopolymerizable compound having two or more. Preferably, it is a polyfunctional photoradically polymerizable compound having two or more.

  The content of the (A) radically polymerizable compound may be appropriately set according to the purpose and use in addition to the type of compound and alkali-soluble resin to be used. For example, from the viewpoint of superior developability and plate making properties The total solid content of the photosensitive resin composition is preferably 5 to 50% by mass based on 100% by mass. More preferably, it is 10-40 mass%, More preferably, it is 10-30 mass%.

  Among the above photoradical polymerizable compounds, a polyfunctional photoradical polymerizable compound is preferable from the viewpoint of curability. Furthermore, among the above-mentioned polyfunctional photoradical polymerizable compounds, polyfunctional (meth) acrylates, polyfunctional urethane (meth) acrylates, (meth) acryloyl group-containing isocyanates due to reactivity, economy, availability, and the like. Polyfunctional monomers having a (meth) acryloyl group such as nurates are more preferable. More preferred are dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and trimethylolpropane tri (meth) acrylate.

Examples of the polyfunctional monomer having the (meth) acryloyl group are KAYARAD R-526, NPGDA, PEG400DA, MANDA, R-167, HX-220, HX-620, R-551, R-. 712, R-604, R-684, GPO-303, TMPTA, THE-330, TPA-320, TPA-330, PET-30, T-1420 (T), DPHA, DPHA-2C, D-310, D -330, DPCA-20, DPCA-30, DPCA-60, DPCA-120, DN-0075 (manufactured by Nippon Kayaku Co., Ltd.); Aronix M-203S, M-208, M-211B, M-215, M -220, M-225, M-270, M-240, M-309, M-310, M-321, M-350, M-360, M- 370, M-313, M-315, M-325, M-327, M-306, M-305, M-451, M-450, M-408, M-403, M-400, M-402, M-404, M-406, M-405, M-510, M-520 (above, manufactured by Toagosei Co., Ltd.); Light acrylate 3EG-A, 4EG-A, 9EG-A, DCP-A, BP-4EA, BP-4PA, HPP-A, PTMGA-250, G201PTMP-A, TMP-6EO-3A, TMP-3EO-A (manufactured by Kyoeisha Chemical Co., Ltd.), light esters EG, 2EG, 3EG, 4EG, 9EG, G101P, G201P, BP-2EM, BP-6EM, TMP (above, manufactured by Kyoeisha Chemical Co., Ltd.), Biscoat 295, 300, 360, GPT, 3PA, 400 (above, Osaka Organic Chemical Industry Co., Ltd.) ), And the like.
Among these, TMPTA and DPHA are preferably used.
Below, the polyfunctional (meth) acrylate compound suitable as a polyfunctional compound used by this invention and another polyfunctional compound are further demonstrated.

-Multifunctional (meth) acrylate compound-
The number of (meth) acryloyl groups possessed by the polyfunctional (meth) acrylate compound is preferably 3 or more. Thus, it is preferable that the polyfunctional compound contains a trifunctional or higher polyfunctional (meth) acrylate compound, whereby the photosensitivity and curability are further improved, and the hardness and transparency can be further improved. it can. More preferably, it is 4 or more, More preferably, it is 5 or more. Further, from the viewpoint of further suppressing curing shrinkage, it is preferably 10 or less, more preferably 8 or less, and still more preferably 6 or less.

The (meth) acryloyl group possessed by the polyfunctional (meth) acrylate compound means a methacryloyl group and / or an acryloyl group, but an acryloyl group is preferred from the viewpoint of better reactivity. That is, the polyfunctional (meth) acrylate compound is particularly preferably a polyfunctional acrylate compound having two or more acryloyl groups.
Although the molecular weight of the said polyfunctional (meth) acrylate compound is not specifically limited, For example, 2000 or less is suitable from a viewpoint of handling. More preferably, it is 1000 or less. Moreover, 100 or more are suitable.

Although it does not specifically limit as said polyfunctional (meth) acrylate compound, For example, the following compound etc. are mentioned.
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, hexanediol di (meth) acrylate, cyclohexanedimethanol Bifunctional (meth) acrylate compounds such as di (meth) acrylate, bisphenol A alkylene oxide di (meth) acrylate, bisphenol F alkylene oxide di (meth) acrylate;
Trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, tripentaerythritol hepta (meth) acrylate, tripentaerythritol octa (meth) acrylate, ethylene oxide-added trimethylolpropane tri (meth) acrylate, ethylene oxide-added ditrimethylolpropane tetra (meth) acrylate, ethylene oxide Addition pentaerythritol tetra (meth) acrylate, ethylene oxide addition dipe Taerythritol hexa (meth) acrylate, propylene oxide-added trimethylolpropane tri (meth) acrylate, propylene oxide-added ditrimethylolpropane tetra (meth) acrylate, propylene oxide-added pentaerythritol tetra (meth) acrylate, propylene oxide-added dipentaerythritol hexa (Meth) acrylate, ε-caprolactone-added trimethylolpropane tri (meth) acrylate, ε-caprolactone-added ditrimethylolpropane tetra (meth) acrylate, ε-caprolactone-added pentaerythritol tetra (meth) acrylate, ε-caprolactone-added dipentaerythritol Trifunctional or more polyfunctional (meth) acrylate compounds such as hexa (meth) acrylate;

-Other polyfunctional compounds-
Examples of the polyfunctional compound include polyfunctional vinyl ether compounds, vinyl ether group-containing (meth) acrylate compounds, polyfunctional allyl ether compounds, allyl group-containing (meth) acrylate compounds, (meth) acryloyl group-containing isocyanurate compounds, polyfunctional compounds. An allyl group-containing isocyanurate compound, a polyfunctional urethane (meth) acrylate compound, a polyfunctional aromatic vinyl compound, or the like can also be used.

  Examples of the polyfunctional vinyl ether compound include ethylene glycol divinyl ether, diethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, and bisphenol F alkylene oxide. Divinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether, dipentaerythritol hexavinyl ether, ethylene oxide-added trimethylol proppant Vinyl ethers, ethylene oxide-added ditrimethylolpropane tetravinyl ether, ethylene oxide adduct of pentaerythritol tetravinyl ether, ethylene oxide adduct of dipentaerythritol hexavinyl ether.

  Examples of the vinyl ether group-containing (meth) acrylate compound include 2-vinyloxyethyl (meth) acrylate, 3-vinyloxypropyl (meth) acrylate, 1-methyl-2-vinyloxyethyl (meth) acrylate, (meth) 2-vinyloxypropyl acrylate, 4-vinyloxybutyl (meth) acrylate, 4-vinyloxycyclohexyl (meth) acrylate, 5-vinyloxypentyl (meth) acrylate, 6-vinyloxyhexyl (meth) acrylate, (Meth) acrylic acid 4-vinyloxymethylcyclohexylmethyl, (meth) acrylic acid p-vinyloxymethylphenylmethyl, (meth) acrylic acid 2- (vinyloxyethoxy) ethyl, (meth) acrylic acid 2- (vinyloxy) And ethoxyethoxyethoxy) ethyl.

  Examples of the polyfunctional allyl ether compound include ethylene glycol diallyl ether, diethylene glycol diallyl ether, polyethylene glycol diallyl ether, propylene glycol diallyl ether, butylene glycol diallyl ether, hexanediol diallyl ether, bisphenol A alkylene oxide diallyl ether, and bisphenol F alkylene. Oxide diallyl ether, trimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, glycerol triallyl ether, pentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, ethylene oxide-added trimethylol proppant Allyl ether, ethylene oxide-added ditrimethylolpropane tetra allyl ether, ethylene oxide adduct of pentaerythritol tetra-allyl ether, ethylene oxide adduct of dipentaerythritol hexa-allyl ether.

  Examples of the allyl group-containing (meth) acrylate compound include allyl (meth) acrylate.

  Examples of the (meth) acryloyl group-containing isocyanurate compound include tri (acryloyloxyethyl) isocyanurate, tri (methacryloyloxyethyl) isocyanurate, alkylene oxide-added tri (acryloyloxyethyl) isocyanurate, alkylene oxide-added tri ( Methacryloyloxyethyl) isocyanurate and the like.

  Examples of the allyl group-containing isocyanurate compound include triallyl isocyanurate.

  Examples of the polyfunctional urethane (meth) acrylate compound include polyfunctional isocyanates such as tolylene diisocyanate, isophorone diisocyanate, and xylylene diisocyanate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. And the like obtained by a reaction with a hydroxy group-containing (meth) acrylic acid ester.

  Examples of the polyfunctional aromatic vinyl compound include divinylbenzene.

<Polymerizable monomer other than polyfunctional compound>
The polymerizable monomer other than the polyfunctional compound is also a compound other than the polyfunctional compound described above, and active energy rays such as free radicals, electromagnetic waves (for example, infrared rays, ultraviolet rays, X-rays), and electron beams. A low molecular weight compound having a polymerizable unsaturated bond (also referred to as a polymerizable unsaturated group) that can be polymerized by irradiation or the like can be used as the (A) photoradical polymerizable compound. As said polymerizable monomer, the monofunctional compound (polymerizable monomer) which has one polymerizable unsaturated group in a molecule | numerator is mentioned, for example.

  Examples of the monofunctional polymerizable monomer include, for example, N-substituted maleimide and unsubstituted among the compounds exemplified as other monomers preferably contained in the monomer component of the (meth) acrylate polymer. Maleimides and (meth) acrylic esters; (meth) acrylamides; unsaturated monocarboxylic acids; unsaturated polycarboxylic acids; unsaturated monocarboxylic acids in which the chain between the unsaturated group and the carboxyl group is extended; Saturated acid anhydrides; aromatic vinyls; conjugated dienes; vinyl esters; vinyl ethers; N-vinyl compounds;

(B) Alkali-soluble resin The (B) alkali-soluble resin contained in the photosensitive resin composition of the present invention has structural units represented by the following formulas (a), (b) and (c), or It is a polymer having structural units represented by the formulas (a), (b) and (d). (B) The alkali-soluble resin may have structural units represented by the following formulas (a), (b), (c), and (d).

In the above formulas (a), (b), (c) and (d), each R ¹ and R ³ each independently represents a hydrogen atom or a methyl group. In the above formula (a), R ² is an alkyl group optionally substituted with a functional group other than the primary hydroxy group, an alicyclic group, a group containing an aromatic ring optionally substituted with a functional group, or ether A functional group having a bond is represented.

Examples of the alkyl group that may be substituted with a functional group other than the primary hydroxy group in R ² include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, s- Butyl group, t-butyl group, n-amyl group, s-amyl group, t-amyl group, n-hexyl group, 2-ethylhexyl group, isodecyl group, tridecyl group, octyl group, isooctyl group, lauryl group, stearyl group , 2-hydroxypropyl group, 2-hydroxybutyl group, 3-hydroxybutyl group, N, N-dimethylaminoethyl group, etc. An alkyl group is mentioned.
Examples of the alicyclic group in R ² include a cyclohexyl group, a cyclohexylmethyl group, an adamantyl group, a tricyclodecanyl group, and an isobornyl group.
Examples of the group containing an aromatic ring that may be substituted with the functional group in R ² include a benzyl group, a phenyl group, a phenoxyethyl group, and a phenylphenol group.
Examples of the functional group having an ether bond in R ² include a 2-methoxyethyl group, a 2-ethoxyethyl group, a tetrahydrofurfuryl group, a tetrahydropyranyl group, and the like.
As the R ^2, an alkyl group or an alicyclic group which is not substituted with a functional group are preferred in view of developing property.

Each Y in the above formulas (a), (b), (c) and (d) independently represents a carboxylate group (—COO—) or (—OCO—), a phosphate group (— PO ₃ —) or (—OPO ₂ —), a sulfonic acid ester group (—SO ₃ —) or (—OSO ₂ —), or a phenylene group. Y is preferably a carboxylic acid ester group (—COO—).

  Z in the formula (c) represents a divalent hydrocarbon group which may have a substituent, and a group having an alkylene group which may be substituted with a functional group is preferable. Examples of the alkylene group which may be substituted with the functional group include a linear, branched or cyclic alkylene group, such as a methylene group, an ethylene group, an n-propylene group, an i-propylene group, and an n-butylene group. , S-butylene group, t-butylene group, 2-hydroxyethylene group, 2-hydroxypropylene group, 3-hydroxypropylene group, 2-hydroxybutylene group, 3-hydroxybutylene group, 4-hydroxybutylene group, 2-methoxy Examples include an alkylene group having 1 to 4 carbon atoms which may be substituted with a hydroxy group or an alkoxy group, such as an ethylene group and a 2-ethoxyethylene group. Among these, a C2-C4 alkylene group having a secondary hydroxy group is particularly preferable.

The aforementioned Z, carboxylic acid ester group (-COO-) or (-OCO-), phosphoric acid ester group (-PO ₃ -) or (-OPO ₂ -), sulfonate group (-SO ₃ -) or (—OSO ₂ —) or a phenylene group may be contained.
As said Z, a C2-C4 alkylene group which has a secondary hydroxy group is preferable.

X in the formula (d) represents a divalent hydrocarbon group which may have a substituent, an alkylene group which may be substituted with a functional group, or an arylene which may be substituted with a functional group. Or a divalent hydrocarbon group having an alicyclic structure is preferred, an alkylene group which may be substituted with a functional group or an arylene group which may be substituted with a functional group is more preferred, and is substituted with a functional group An alkylene group which may be further preferred.
Examples of the alkylene group which may be substituted with a particularly preferable functional group include a linear, branched or cyclic alkylene group, such as a methylene group, an ethylene group, an n-propylene group, an i-propylene group, and an n-butylene. Groups having 1 to 4 carbon atoms such as a group, s-butylene group and t-butylene group, and groups in which these groups are substituted with a functional group such as a hydroxy group. Examples of the alicyclic structure include a cyclohexane skeleton, an adamantane skeleton, and a norbornene skeleton.

  The total content of the structural units represented by the above formulas (a), (b) and (c) and the total content of the structural units represented by the above formulas (a), (b) and (d) are as follows: In (B) 100% by mass of the alkali-soluble resin, for example, it is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more.

Examples of the (B) alkali-soluble resin include a polymer (also referred to as a base polymer) obtained by polymerizing a monomer component containing a monomer having an acid group and a polymerizable double bond, and will be described later. Thus, a polymer obtained by reacting the base polymer with a compound having a functional group capable of bonding to an acid group and a polymerizable double bond (“polymer having a double bond in a side chain” or “side chain”) It is also preferably referred to as “double bond-containing polymer”. The latter side chain double bond-containing polymer is more preferable.
In addition, each monomer used can use 1 type (s) or 2 or more types, respectively.

Examples of the monomer having an acid group and a polymerizable double bond include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, cinnamic acid, and vinyl benzoic acid; maleic acid, fumaric acid, and itacon. Unsaturated polyvalent carboxylic acids such as acid, citraconic acid, and mesaconic acid; a chain between unsaturated groups such as mono (2-acryloyloxyethyl) succinate and mono (2-methacryloyloxyethyl) succinate and carboxyl groups Unsaturated monocarboxylic acids extended; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; phosphate group-containing unsaturated compounds such as light ester P-1M (manufactured by Kyoeisha Chemical); . Among these, it is preferable to use carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated acid anhydrides) from the viewpoints of versatility and availability. More preferably, unsaturated monocarboxylic acids are preferably used in terms of reactivity, alkali solubility, etc., more preferably (meth) acrylic acid (that is, acrylic acid and / or methacrylic acid), and among these, particularly preferable Is methacrylic acid.
(Meth) acrylic acid is a monomer that provides the structural unit represented by the above formula (b).

  The content ratio of the monomer having an acid group and a polymerizable double bond is preferably, for example, 5% by mass or more in 100% by mass of all the components for synthesizing the base polymer. Thereby, the solubility with respect to an alkali becomes more sufficient, for example, it becomes a curable resin composition further useful for the use for which developability is required. More preferably, it is 10 mass% or more, More preferably, it is 15 mass% or more. Moreover, it is preferable that it is 95 mass% or less at the point which can maintain the outstanding external appearance, adhesiveness, etc. of the hardened | cured material more after post-baking, for example. More preferably, it is 90 mass% or less.

  Although it does not specifically limit as said acid value (AV) of said (B) alkali-soluble resin, For example, it is suitable that it is 20 mgKOH / g or more and less than 300 mgKOH / g. Thereby, more sufficient alkali solubility is expressed, and it becomes possible to obtain a cured product having better developability. The lower limit of the acid value is more preferably 30 mgKOH / g or more, and still more preferably 40 mgKOH / g or more. Moreover, 250 mgKOH / g or less is more preferable, More preferably, it is 200 mgKOH / g or less.

The acid value is determined by measuring the acid value of the polymer solution with an automatic titrator (trade name “COM-555”, manufactured by Hiranuma Sangyo Co., Ltd.) using, for example, a 0.1 N aqueous KOH solution as a titrant. The acid value per solid content can be calculated from the acid value of the solution and the solid content of the solution. The solid content of the polymer solution can be determined as follows.
About 0.3 g of the polymer solution is weighed into an aluminum cup, dissolved by adding about 1 g of acetone, and then naturally dried at room temperature. Then, using a hot air dryer (trade name “PHH-101” manufactured by Espec Corp.), after drying at 140 ° C. for 3 hours, it is allowed to cool in a desiccator and the mass is measured. From the mass reduction amount, the solid content concentration of the polymer solution is calculated.

The (B) alkali-soluble resin preferably has a weight average molecular weight of 2000 to 200,000. When the molecular weight is within this range, better developability can be exhibited. From the viewpoint of further improving the solvent resistance, it is more preferably 3000 or more, particularly preferably 5000 or more. Further, from the viewpoint of viscosity and the like, it is more preferably 100,000 or less, particularly preferably 50,000 or less. When the alkali-soluble tree has a high molecular weight, the higher the acid value tends to be developed, and when the alkali-soluble tree has a low molecular weight, the hardness of the coating film tends not to be sufficient. .
The weight average molecular weight is determined, for example, by a GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corp.) and column TSKgel SuperHZM-M (manufactured by Tosoh Corp.) using polystyrene as a standard substance and eluent as polystyrene. Can do.

  Moreover, as a monomer which synthesize | combines the said (B) alkali-soluble resin, (meth) acrylic acid ester monomer (a) is used as a monomer which gives the structural unit represented by the said Formula (a). It is preferable to do.

  Specific examples of the (meth) acrylate monomer (a) include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, (meth) I-propyl acrylate, n-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, n-amyl (meth) acrylate, s-amyl (meth) acrylate T-amyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isodecyl (meth) acrylate, tridecyl (meth) acrylate, octyl (meth) acrylate, ( Isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, (meta 2-hydroxybutyl acrylate, 3-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, (meth) acrylic acid ester monomers having an alkyl group optionally substituted with a functional group such as methyl α-hydroxymethyl acrylate and ethyl α-hydroxymethyl acrylate; cyclohexyl (meth) acrylate, (meta (Meth) acrylate monomer having an alicyclic group such as cyclohexylmethyl acrylate, isobornyl (meth) acrylate, adamantyl (meth) acrylate, tricyclodecanyl (meth) acrylate; (meth) Benzyl acrylate, phenyl (meth) acrylate, (meth) acrylic acid Kishiechiru, such as alkoxylated phenylphenol (meth) acrylate, having a group containing an aromatic ring which may be substituted with a functional group (meth) acrylate monomer. These monomers can be used alone or in combination of two or more.

  Examples of commercially available products of these compounds include MMDOL30, MEDOL30, MIBDOL30, CHDOL30, MEDOL10, MIBDOL10, MIBDOL10, CHDOL10, Biscote 150, Biscote 160 (above, manufactured by Osaka Organic Chemical Industry Co., Ltd.), ACMO (manufactured by Kojin Co., Ltd.). A-LEN-10 (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like.

Among them, in terms of excellent heat resistance, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, alkoxylated phenylphenol (meta ) Acrylate is preferred. More preferably, in terms of excellent heat resistance, adhesion, and developability, methyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and / or alkoxylated phenylphenol (meth) acrylate Is preferably used.
The monomer component used to obtain the base polymer is further methyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, and alkoxylated phenylphenol (meth). A form containing at least one (meth) acrylic acid ester monomer selected from the group consisting of acrylates is also a preferred form of the present invention.

  Moreover, as a monomer which synthesize | combines the said (B) alkali-soluble resin, (meth) acrylic acid ester type monomer (d) is given as a monomer which gives the structural unit represented by the said Formula (d). It is preferable to use it. Examples of the (meth) acrylic acid ester monomer (d) include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, methacrylic acid 2 , 3-dihydroxypropyl, 3-hydroxy-1-adamantyl-methacrylate and the like. These monomers can be used alone or in combination of two or more.

  Moreover, as a monomer which synthesize | combines the said (B) alkali-soluble resin, the said (meth) acrylic acid ester type monomer (a), the said (meth) acrylic acid ester type monomer (d), dialkyl- 2,2 ′-(oxydimethylene) diacrylate monomers and (meth) acrylate monomers other than α- (unsaturated alkoxyalkyl) acrylate [other (meth) acrylate esters May be used. Examples of the other (meth) acrylic acid ester monomers include, for example, tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, (meth) acrylic β -Ethylglycidyl, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, 1,4-dioxaspiro [4,5] dec-2-ylmethacrylic acid, (meth) acryloylmorpholine, tetrahydrofurfuryl acrylate, 4 -(Meth) acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4- (meth) acryloyloxymethyl-2-methyl-2-isobutyl-1,3-dioxolane, 4- (meth) Acryloyloxymethyl-2-methyl-2-cyclohexyl-1,3-dioxolane 4- (meth) acryloyloxymethyl-2,2-dimethyl-1,3-dioxolane, and the like. These monomers can be used alone or in combination of two or more. The amount of the other (meth) acrylic acid ester monomer used is preferably less than 40% by mass, more preferably less than 30% by mass, even more preferably less than 20% by mass in 100% by mass of the base polymer component. Less than 5% by weight is particularly preferred, and less than 5% by weight is most preferred. The other (meth) acrylic acid ester monomers may not be used.

  The (B) alkali-soluble resin is preferably a polymer having a ring structure in the main chain. When a polymer having a ring structure in the main chain is used as the alkali-soluble resin, it is excellent in heat resistance, surface hardness, and adhesion, and for example, various changes with time after post-bake (heat treatment) are further suppressed. A cured product capable of expressing the physical properties more stably can be obtained.

  Here, when the (B) alkali-soluble resin is a polymer having a ring structure in the main chain, the monomer component forming the base polymer together with a monomer having an acid group and a polymerizable double bond It is preferable that one or more monomers that can introduce a ring structure into the main chain skeleton of the polymer are contained. That is, the alkali-soluble resin is obtained by polymerizing a monomer component including a monomer having an acid group and a polymerizable double bond and a monomer capable of introducing a ring structure into the main chain skeleton of the polymer. Polymer obtained (base polymer) and polymer obtained by reacting the base polymer with a compound having a functional group capable of binding to an acid group and a polymerizable double bond (polymer containing a side chain double bond) It is preferable that

  Examples of the monomer that can preferably introduce a ring structure into the main chain skeleton of the alkali-soluble resin (B) include, for example, a monomer having a double bond-containing ring structure in the molecule, and a ring formed by cyclopolymerization. Examples include monomers that form a polymer having a structure in the main chain, and it is preferable to use one or more of these. Such monomers include N-substituted or unsubstituted maleimide monomers, dialkyl-2,2 ′-(oxydimethylene) diacrylate monomers, and α- (unsaturated alkoxyalkyl) acrylates. It is preferable to use at least one selected from the group consisting of Thus, the alkali-soluble resin is an N-substituted or unsubstituted maleimide monomer unit, dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer unit, and / or α- (unsaturated). A form that is a polymer having a structural unit having a ring structure in the main chain such as an alkoxyalkyl) acrylate monomer unit is one of the preferred forms of the present invention.

In particular, resins containing N-substituted maleimide monomer units and / or dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer units are heat resistant, inorganic compound dispersible, hardness It becomes possible to give a cured film with improved and the like.
The resin (polymer) containing the above-mentioned monomer unit means a resin containing a structural unit derived from the monomer by, for example, a monomer polymerization reaction or a crosslinking reaction.

  In the monomer component, examples of the N-substituted maleimide monomer include N-cyclohexylmaleimide, N-phenylmaleimide, N-methylmaleimide, N-ethylmaleimide, N-isopropylmaleimide, and Nt-butylmaleimide. , N-dodecylmaleimide, N-benzylmaleimide, N-naphthylmaleimide and the like, and one or more of these can be used. Among these, N-cyclohexylmaleimide, N-phenylmaleimide, and N-benzylmaleimide are preferable, and N-benzylmaleimide is particularly preferable because of less coloring and excellent dispersibility of the inorganic compound.

  As described above, (B) the alkali-soluble resin is a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer, an N-substituted or unsubstituted maleimide monomer, and α- (unsaturated alkoxyalkyl). Having a structural unit derived from at least one monomer selected from the group consisting of acrylate monomers is a preferred embodiment of the present invention.

  Examples of the N-benzylmaleimide include benzylmaleimide; alkyl-substituted benzylmaleimide such as p-methylbenzylmaleimide and p-butylbenzylmaleimide; phenolic hydroxy group-substituted benzylmaleimide such as p-hydroxybenzylmaleimide; o-chlorobenzyl And halogen-substituted benzyl maleimides such as maleimide, o-dichlorobenzyl maleimide, and p-dichlorobenzyl maleimide.

  Examples of the dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer include, for example, dimethyl-2,2 ′-[, from the viewpoints of little coloring, dispersibility, industrial availability, and the like. It is preferable to use oxybis (methylene)] bis-2-propenoate or the like.

  Examples of the α- (unsaturated alkoxyalkyl) acrylate include α-allyloxymethyl acrylic acid, α-allyloxymethyl acrylate methyl, α-allyloxymethyl ethyl acrylate, α-allyloxymethyl acrylate n- Propyl, α-allyloxymethyl acrylate i-propyl, α-allyloxymethyl acrylate n-butyl, α-allyloxymethyl acrylate s-butyl, α-allyloxymethyl acrylate t-butyl, α-allyloxy N-amyl methyl acrylate, s-amyl α-allyloxymethyl acrylate, t-amyl α-allyloxymethyl acrylate, neopentyl α-allyloxymethyl acrylate, n-hexyl α-allyloxymethyl acrylate, α -Allyloxymethyl acrylate s-hexyl, α Allyloxymethyl acrylate n-heptyl, α-allyloxymethyl acrylate n-octyl, α-allyloxymethyl acrylate s-octyl, α-allyloxymethyl acrylate t-octyl, α-allyloxymethyl acrylate 2 -Ethylhexyl, α-allyloxymethyl acrylate capryl, α-allyloxymethyl acrylate nonyl, α-allyloxymethyl acrylate decyl, α-allyloxymethyl acrylate undecyl, α-allyloxymethyl acrylate, α-allyloxymethyl acrylate Tridecyl allyloxymethyl acrylate, myristyl α-allyloxymethyl acrylate, pentadecyl α-allyloxymethyl acrylate, cetyl α-allyloxymethyl acrylate, heptadecyl α-allyloxymethyl acrylate, α-allyloxy Chain saturated hydrocarbon group-containing α such as stearyl methyl acrylate, nonadecyl α-allyloxymethyl acrylate, eicosyl α-allyloxymethyl acrylate, seryl α-allyloxymethyl acrylate, melyl α-allyloxymethyl acrylate -(Allyloxymethyl) acrylate is preferred. Among them, methyl α-allyloxymethyl acrylate (also referred to as “α- (allyloxymethyl) methyl acrylate”) is particularly preferable. The α- (unsaturated alkoxyalkyl) acrylate can be produced, for example, by a production method disclosed in International Publication No. 2010/114077.

  The content ratio of the monomers that can preferably introduce a ring structure into the main chain skeleton of the (B) alkali-soluble resin (the ratio of the total when two or more are used) is, for example, the base polymer component (base polymer Monomer component to be formed) It is preferably 1 to 50% by mass with respect to 100% by mass. Within this range, it becomes possible to obtain a cured film with improved heat resistance, surface hardness, etc., and when the photosensitive resin composition further contains inorganic fine particles, the cured film is also excellent in dispersibility. Can be obtained. Among them, the content ratio of N-substituted or unsubstituted maleimide monomer, dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer, and / or α- (unsaturated alkoxyalkyl) acrylate ( When using 2 or more types, it is preferable that the total ratio) is 1-40 mass% with respect to 100 mass% of the said base polymer component (monomer component which forms a base polymer). When the addition amount of the N-substituted or unsubstituted maleimide monomer is further increased, a cured product that is superior in terms of hardness can be obtained, and a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer By using the body, a cured product that is more excellent in terms of heat-resistant colorability can be obtained. However, if the content of the N-substituted or unsubstituted maleimide monomer is too large, the development speed may not be more appropriate. More preferably, it is 2-40 mass% as said content rate, More preferably, it is 3-35 mass%.

  In addition to the above-mentioned monomer having an acid group and a polymerizable double bond, and a monomer capable of introducing a ring structure into the main chain skeleton of the polymer, the above monomer component also includes other radical polymerization. It may contain a functional monomer (also referred to as “other monomer”). As another monomer, 1 type (s) or 2 or more types, such as another aromatic vinyl-type monomer which does not correspond to the monomer mentioned above, can be used.

  Examples of the aromatic vinyl monomer include styrene, vinyl toluene, α-methyl styrene, methoxy styrene, and the like. Of these, styrene and vinyltoluene are preferable from the viewpoint of heat resistance coloring property and heat decomposition property of the resin.

  Content ratio of the (meth) acrylic acid ester monomer (a) and / or the (meth) acrylic acid ester monomer (d) and / or aromatic vinyl monomer (when two or more are used) Is preferably 1 to 90% by mass with respect to 100% by mass of the base polymer component. When it is in this range, a cured product that is more excellent in heat-resistant colorability, inorganic compound dispersibility, and alkali solubility can be obtained. More preferably, it is 5-75 mass%, More preferably, it is 10-70 mass%.

  Moreover, the said (meth) acrylic acid ester monomer (d) content rate (when using 2 or more types) is 5-50 mass% with respect to 100 mass% of said base polymer components, for example. Preferably it is.

As said other monomer, 1 type (s) or 2 or more types, such as the following compound, can also be used, for example, The content rate shall be 20 mass% or less in 100 mass% of said base polymer components. Is preferred.
(Meth) acrylamides such as N, N-dimethyl (meth) acrylamide and N-methylol (meth) acrylamide; heavy materials such as polystyrene, polymethyl (meth) acrylate, polyethylene oxide, polypropylene oxide, polysiloxane, polycaprolactone and polycaprolactam Macromonomers having a (meth) acryloyl group at one end of the combined molecular chain; conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate Class: methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether , Methoxyethyl vinyl ether, ethoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether, 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, and other vinyl ethers; N-vinylpyrrolidone, N-vinylcaprolactam, N-vinylimidazole N-vinyl compounds such as N-vinylmorpholine and N-vinylacetamide; unsaturated isocyanates such as isocyanatoethyl (meth) acrylate and allyl isocyanate;

  Monomer having acid group and polymerizable double bond, monomer capable of introducing ring structure into main chain skeleton of polymer, (meth) acrylic acid ester monomer (a), (meth) acrylic The total content of the acid ester monomer (d) and the aromatic vinyl monomer is, for example, 70% by mass or more with respect to 100% by mass of all monomer components for polymerizing the base polymer. More preferably, it is 80 mass% or more, More preferably, it is 90 mass% or more. By polymerizing such a monomer component to (B) an alkali-soluble resin, (A) a photoradical polymerizable compound, (C) a photoradical polymerization initiator, (D) a photoacid generator, and ( E) When a photosensitive resin composition is prepared together with a colorant, a cured product excellent in various physical properties such as solvent resistance and transparency after curing can be provided.

  In the (B) alkali-soluble resin, as a method for polymerizing the monomer component, a commonly used technique such as bulk polymerization, solution polymerization, emulsion polymerization or the like can be used, and it may be appropriately selected according to the purpose and application. That's fine. Among these, solution polymerization is preferred because it is industrially advantageous and structural adjustments such as molecular weight are easy. The polymerization mechanism of the monomer component may be a polymerization method based on a mechanism such as radical polymerization, anionic polymerization, cationic polymerization, or coordination polymerization, but the polymerization method based on the radical polymerization mechanism is industrial. Is also preferable.

  The polymerization initiating method in the above polymerization reaction may be performed by supplying energy necessary for initiating polymerization from an active energy source such as heat, electromagnetic waves (infrared rays, ultraviolet rays, X-rays, etc.), electron beams, etc. If an agent is used in combination, the energy required for initiation of polymerization can be greatly reduced, and reaction control is facilitated, which is preferable. The molecular weight of the polymer obtained by polymerizing the monomer components can be controlled by adjusting the amount and type of the polymerization initiator, the polymerization temperature, the type and amount of the chain transfer agent, and the like.

  When the monomer component is polymerized by a solution polymerization method, the solvent used for the polymerization is not particularly limited as long as it is inert to the polymerization reaction, and the polymerization mechanism and the type of monomer used. May be appropriately set according to the polymerization conditions such as the amount, polymerization temperature, polymerization concentration, etc., but when a solvent is used as a diluent or the like later in the photosensitive resin composition, the solvent containing the solvent is used. It is efficient and preferable to use for solution polymerization of monomer components.

As said solvent, the following compound etc. are mentioned suitably, for example, These 1 type (s) or 2 or more types can be used.
Monoalcohols such as methanol, ethanol, isopropanol, n-butanol, s-butanol; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene Glycol monoethers such as glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, 3-methoxybutanol; ethylene glycol dimethyl ether, ethylene glycol Jie Glycol ethers such as ether ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol mono Butyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, Esters of glycol monoethers such as propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate; methyl acetate, ethyl acetate, propyl acetate , Isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3 -Alkyl esters such as ethyl ethoxypropionate, methyl acetoacetate, ethyl acetoacetate; acetone, methyl ethyl ketone, methyl isobutyrate Ketones such as ruketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; aliphatic hydrocarbons such as hexane, cyclohexane and octane; amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone ;etc.

  Among these solvents, propylene glycol monomethyl ether, propylene are used because of the solubility of the resulting polymer, surface smoothness when forming a coating film, little influence on the human body and the environment, and industrial availability. It is more preferable to use glycol monomethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether, or ethyl lactate.

As the usage-amount of the said solvent, it is suitable that it is 50-1000 mass parts with respect to 100 mass parts of said base polymer components. More preferably, it is 100-500 mass parts.
When the monomer component is polymerized by a radical polymerization mechanism, it is industrially advantageous and preferable to use a polymerization initiator that generates radicals by heat. Such a polymerization initiator is not particularly limited as long as it generates radicals by supplying thermal energy. Depending on the polymerization conditions such as polymerization temperature, solvent, type of monomer to be polymerized, etc. And may be selected as appropriate. Moreover, you may use together reducing agents, such as transition metal salt and amines, with a polymerization initiator.

Examples of the polymerization initiator include cumene hydroperoxide, diisopropylbenzene hydroperoxide, di-t-butyl peroxide, lauroyl peroxide, benzoyl peroxide, t-butylperoxyisopropyl carbonate, and t-butylperoxy- 2-ethylhexanoate, azobisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), dimethyl 2,2′-azobis ( 2-methylpropionate), hydrogen peroxide, persulfate, etc., which are usually used as polymerization initiators, such as peroxides and azo compounds, may be used alone or in combination of two or more. May be.
The amount of the polymerization initiator used may be appropriately set according to the type and amount of the monomer used, the polymerization conditions such as the polymerization temperature and the polymerization concentration, the molecular weight of the target polymer, etc., and is particularly limited. It is not a thing. For example, in order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, the content is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the base polymer component. More preferably, it is 0.5-15 mass parts.

In the above polymerization, a chain transfer agent usually used may be used as necessary. Preferably, a polymerization initiator and a chain transfer agent are used in combination. In addition, when a chain transfer agent is used at the time of superposition | polymerization, it exists in the tendency which can suppress the increase in molecular weight distribution or gelatinization.
Examples of the chain transfer agent include mercaptocarboxylic acids such as mercaptoacetic acid and 3-mercaptopropionic acid; methyl mercaptoacetate, methyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, and n-mercaptopropionic acid n- Octyl, methoxybutyl 3-mercaptopropionate, stearyl 3-mercaptopropionate, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3- Mercaptocarboxylic esters such as mercaptopropionate); alkyl mercapts such as ethyl mercaptan, t-butyl mercaptan, n-dodecyl mercaptan, 1,2-dimercaptoethane Mercapto alcohols such as 2-mercaptoethanol and 4-mercapto-1-butanol; Aromatic mercaptans such as benzenethiol, m-toluenethiol, p-toluenethiol and 2-naphthalenethiol; Tris [(3- Mercaptopropionyloxy) -ethyl] isocyanurate and other mercaptoisocyanurates; 2-hydroxyethyl disulfide and diethyl sulfides such as tetraethyl thiuram disulfide; dithiocarbamates such as benzyldiethyldithiocarbamate; α-methylstyrene dimer Body dimers; alkyl halides such as carbon tetrabromide. These may be used alone or in combination of two or more.
Among these, mercaptocarboxylic acids, mercaptocarboxylic esters, alkyl mercaptans, mercapto alcohols, aromatic mercaptans, mercaptoisocyanurates, in terms of availability, ability to prevent crosslinking, and low degree of polymerization rate reduction. It is preferable to use a compound having a mercapto group such as More preferred are alkyl mercaptans, mercaptocarboxylic acids, mercaptocarboxylic acid esters, and still more preferred are n-dodecyl mercaptan and mercaptopropionic acid.
The amount of the chain transfer agent used is not particularly limited as long as it is appropriately set according to the type and amount of the monomer to be used, polymerization conditions such as polymerization temperature and polymerization concentration, and the molecular weight of the target polymer. In order to obtain a polymer having a weight average molecular weight of several thousand to several tens of thousands, the content is preferably 0.1 to 20 parts by mass with respect to 100 parts by mass of the base polymer component. More preferably, it is 0.5-15 mass parts.

  Regarding the polymerization conditions, the polymerization temperature may be appropriately set according to the type and amount of the monomer to be used, the type and amount of the polymerization initiator, and is preferably 50 to 150 ° C, for example, 70 to 120 ° C. is more preferable. Also, the polymerization time can be appropriately set similarly, but for example, 1 to 8 hours is preferable.

  The (B) alkali-soluble resin is also preferably a polymer having a double bond in the side chain. Specifically, a polymer (base polymer) obtained by polymerizing the above monomer components and a compound obtained by reacting a compound having a functional group capable of binding to an acid group and a polymerizable double bond. It is preferably a polymer (also referred to as a side chain double bond-containing polymer). Thereby, the sclerosis | hardenability of the said photosensitive resin composition is improved more, and the hardened | cured material excellent in adhesiveness with a board | substrate etc. and surface hardness can be obtained. Thus, the form in which the alkali-soluble resin is a polymer having a double bond in the side chain is one of the preferred forms of the present invention.

  In the compound having a functional group capable of binding to the acid group and a polymerizable double bond, examples of the polymerizable double bond include (meth) acryloyl group, vinyl group, allyl group, methallyl group, and the like. A compound having one or more of these compounds is suitable. Of these, a (meth) acryloyl group is preferable in terms of reactivity. In addition, examples of the functional group that can be bonded to the acid group include a hydroxy group, an epoxy group, an oxetanyl group, an isocyanate group, and the like, and those having one or more of these compounds are preferable. Of these, epoxy groups (including glycidyl groups) are preferred from the viewpoint of the speed of the modification treatment reaction, heat resistance, and dispersibility.

  Examples of the compound having a functional group capable of binding to the acid group and a polymerizable double bond include glycidyl (meth) acrylate, β-methylglycidyl (meth) acrylate, β-ethylglycidyl (meth) acrylate, Examples thereof include vinyl benzyl glycidyl ether, allyl glycidyl ether, (meth) acrylic acid (3,4-epoxycyclohexyl) methyl, vinylcyclohexene oxide, and the like, and one or more of these can be used. Among these, it is preferable to use a compound (monomer) having an epoxy group and a (meth) acryloyl group. By reacting the base polymer with glycidyl (meth) acrylate, a structural unit represented by the above formula (c) is formed in the alkali-soluble resin.

  The amount of the compound having a functional group capable of binding to the acid group and a polymerizable double bond is, for example, 1 to 100 parts by mass of the base polymer component (total amount of monomer components constituting the base polymer). The amount is preferably 50 parts by mass. More preferably, it is 5-45 mass parts.

  As a method for obtaining the side chain double bond-containing polymer, for example, when reacting the base polymer component with a compound having a functional group capable of binding to an acid group and a polymerizable double bond, the base polymer A method in which the amount of the acid group (preferably carboxyl group) of the component is larger than the amount of the compound having a functional group capable of binding to the acid group and a polymerizable double bond; the base polymer component and the acid group And a method of reacting a compound having a polybasic acid anhydride group after reacting with a compound having a functional group and a polymerizable double bond.

  The step of reacting the base polymer component (preferably a polymer having a carboxyl group) with a compound having a functional group capable of binding to an acid group and a polymerizable double bond ensures a good reaction rate and is a gel. In order to prevent the formation, it is preferably carried out in a temperature range of 50 to 160 ° C. More preferably, it is 70-140 degreeC, More preferably, it is 90-130 degreeC. Moreover, in order to improve reaction rate, the basic catalyst and acidic catalyst for esterification or transesterification normally used can be used as a catalyst. Among them, it is preferable to use a basic catalyst because side reactions are reduced.

  Examples of the basic catalyst include tertiary amines such as dimethylbenzylamine, triethylamine, tri-n-octylamine, and tetramethylethylenediamine; tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, and n-dodecyltrimethyl. Quaternary ammonium salts such as ammonium chloride; urea compounds such as tetramethylurea; alkylguanidines such as tetramethylguanidine; amide compounds such as dimethylformamide and dimethylacetamide; tertiary phosphines such as triphenylphosphine and tributylphosphine; tetraphenylphosphonium Quaternary phosphonium salts such as bromide and benzyltriphenylphosphonium bromide; It is possible to have. Of these, dimethylbenzylamine, triethylamine, tetramethylurea, and triphenylphosphine are preferable in terms of reactivity, handling properties, and halogen-free properties.

  The catalyst is used in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass as a total of the base polymer component and the compound having a functional group capable of binding to an acid group and a polymerizable double bond group. It is preferable. More preferably, it is 0.1-3 mass parts.

  The step of reacting the base polymer component with a compound having a functional group capable of binding to an acid group and a polymerizable double bond also adds a polymerization inhibitor to prevent gelation, It is preferably carried out in the presence. As the molecular oxygen-containing gas, air or oxygen gas diluted with an inert gas such as nitrogen is usually used and blown into the reaction vessel.

  As the polymerization inhibitor, a commonly used polymerization inhibitor for radically polymerizable monomers can be used. For example, hydroquinone, methylhydroquinone, trimethylhydroquinone, t-butylhydroquinone, methoquinone, 6-t-butyl. -2,4-xylenol, 2,6-di-t-butylphenol, 2,6-di-t-butyl-4-methoxyphenol, 2,2'-methylenebis (4-methyl-6-t-butylphenol), etc. Phenolic inhibitors, organic acid copper salts, phenothiazines and the like, and one or more of these can be used. Among them, a phenol-based inhibitor is preferable in terms of low coloration and ability to prevent polymerization, and 2,2′-methylenebis (4-methyl-6-tert-butylphenol), methoquinone, 6-t- Butyl-2,4-xylenol and 2,6-di-t-butylphenol are more preferable.

  The amount of the polymerization inhibitor used is a functional group capable of bonding to the base polymer component and the acid group from the viewpoint of ensuring a sufficient polymerization preventing effect and curability when used as a photosensitive resin composition. And it is preferable that it is 0.001-1 mass part with respect to 100 mass parts of total amounts with the compound which has a polymerizable double bond. More preferably, it is 0.01-0.5 mass part.

  Examples of the compound having a polybasic acid anhydride group include succinic anhydride, dodecenyl succinic acid, pentadecenyl succinic acid, octadecenyl succinic acid, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride. Acid, methylhexahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, maleic anhydride, itaconic anhydride, phthalic anhydride, glutaric anhydride, phthalic anhydride, trimellitic anhydride, anhydrous Examples include pyromellitic acid, and one or more of these can be used.

(B) Double bond equivalent of alkali-soluble resin The side chain double bond-containing polymer preferably has a double bond equivalent of 100 to 5000 g / mol. By setting it as such a range, it is expected that the sufficient storage stability of the polymer and the good plate-making characteristics in the sensitivity and pattern shape of the curable resin composition of the present invention will be compatible at a higher level. it can. Especially preferably, it is 200 or more. Moreover, 2500 g / mol or less is particularly preferable.

  The double bond equivalent is the mass (g) of the solid content of the polymer solution per 1 mol of the double bond of the polymer. The mass of the solid content of the polymer solution here means the mass of the base polymer component, the mass of the compound having a functional group capable of binding to an acid group and a polymerizable double bond group, and the mass of a chain transfer agent. And a thermal polymerization initiator. It can be determined by dividing the mass of the solid content of the polymer solution by the double bond amount of the polymer. The double bond amount of the polymer can be determined from the amount of the charged acid group and the compound having a functional group capable of bonding and a polymerizable double bond.

  The (B) alkali-soluble resin is a structural unit having an acid group [for example, a structural unit represented by the above formula (b)] and a structural unit having an ester [for example, a structural unit represented by the above formula (a). And a structural unit having a double bond [for example, a structural unit represented by the above formula (c)] and / or a structural unit having a hydroxy group [for example, represented by the above formula (d). Constituent unit]. The content of each structural unit is preferably 5 to 50% by weight of a structural unit having an acid group, 1 to 90% by weight of a structural unit having an ester, and a double bond with respect to 100% by weight of the (B) alkali-soluble resin. The structural unit is 5 to 80% by mass, and the structural unit having a hydroxy group is 5 to 50% by mass.

  The (B) alkali-soluble resin may further contain a structural unit having a ring structure in the main chain as described above. The content of the structural unit having a ring structure in the main chain is preferably 1 to 50% by mass with respect to 100% by mass of the (B) alkali-soluble resin.

  (B) It is preferable that the content rate of alkali-soluble resin is 10 mass% or more with respect to 100 mass% of solid content total amount of the photosensitive resin composition, and it is preferable that it is 50 mass% or less. By being in such a range, it becomes possible to show the effect of the present invention more remarkably. More preferably, it is 15-45 mass%. The “total solid content” means all components other than the solvent.

(C) Photoradical polymerization initiator The photosensitive resin composition of this invention contains a photoradical polymerization initiator as (C) component. Thereby, it becomes possible to further improve the sensitivity and curability of the photosensitive resin composition.
As said (C) photoradical polymerization initiator, it is what generates a polymerization start radical by irradiation of active energy rays, such as electromagnetic waves and an electron beam, and what is used normally can use 1 type, or 2 or more types. it can. Moreover, you may use together 1 type (s) or 2 or more types of photosensitizers, radical photopolymerization promoters, etc. as needed. Even if a photosensitizer and / or a radical photopolymerization accelerator are not used in combination, the effects of the present invention can be sufficiently exerted, but when used together, sensitivity and curability are further improved.

Specific examples of the (C) photoradical polymerization initiator include the following compounds.
2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2 -Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl}- 2-methylpropan-1-one, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) Nyl] -1-butanone and other alkylphenone compounds; benzophenone, 4,4′-bis (dimethylamino) benzophenone, benzophenone compounds such as 2-carboxybenzophenone, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin Benzoin compounds such as isobutyl ether; thioxanthone compounds such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone;
2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4 Halomethylated triazine compounds such as -ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) -s-triazine; 2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxa Halomethylated oxadiazole compounds such as diazole, 4-oxadiazole, 2-trichloromethyl-5-furyl-1,3,4-oxadiazole; 2,2 '-Bis (2-chlorophenyl) -4,4', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5 , 5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′- Biimidazole compounds such as biimidazole; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2- Oxime ester compounds such as methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime); bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6 -Difluoro-3- (1H-pyrrol-1-y ) - phenyl) titanocene compounds such as titanium; p-dimethylaminobenzoic acid, p- benzoic acid ester compounds such as diethyl benzoate; acridine compounds such as 9-phenyl acridine or the like.

  Examples of the photosensitizer and photoradical polymerization accelerator that may be used in combination with the above (C) photoradical polymerization initiator include, for example, dye compounds such as xanthene dyes, coumarin dyes, 3-ketocoumarin compounds, and pyromethene dyes; Dialkylaminobenzene compounds such as ethyl 4-dimethylaminobenzoate and 2-ethylhexyl 4-dimethylaminobenzoate; mercaptan hydrogen donors such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole Is mentioned.

  The content of the (C) radical photopolymerization initiator may be appropriately set according to the purpose, use, etc., and is not particularly limited, but is 0.5% with respect to 100 parts by mass of the total solid content of the photosensitive resin composition. It is preferable that the amount is not less than part by mass. Thereby, the hardened | cured material excellent by adhesiveness can be obtained, and peeling is suppressed more fully even after high temperature exposure. Further, in consideration of the balance between the influence of the decomposition product of the photopolymerization initiator, economy, and the like, it is preferably 20 parts by mass or less. The lower limit value is more preferably 1 part by mass or more, further preferably 2 parts by mass or more, and the upper limit value is more preferably 15 parts by mass or less.

  Moreover, (C) radical photopolymerization initiator is preferably 0.1 to 100 parts by weight, particularly 0.5 to 50 parts by weight with respect to 100 parts by weight of (A) radical photopolymerizable compound. preferable. If the amount is less than 0.1 parts by mass, the desired effect may not be obtained. If the amount exceeds 100 parts by mass, the initiator decomposition product may have an adverse effect.

  The photosensitizer and the photoradical polymerization accelerator may not be used as described above. However, in the case of using the photosensitizer, from the viewpoint of balance between curability, influence of decomposition products, and economy. It is preferable that it is 0.001-20 mass% with respect to 100 mass% of solid content total amount of a composition. More preferably, it is 0.01-15 mass%, More preferably, it is 0.05-10 mass%.

(D) Photoacid generator The photosensitive resin composition of the present invention contains (D) a photoacid generator. (D) The photoacid generator generates radicals simultaneously with the acid when irradiated with light. This radical assists the (C) radical photopolymerization initiator to give a cured product excellent in various physical properties such as solvent resistance and transparency after curing of the photosensitive resin composition. It will be possible.

  The (D) photoacid generator contained in the photosensitive resin composition of the present invention is a compound that generates an acid upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. Known compounds such as onium salt compounds, sulfone compounds, sulfonic acid ester compounds, quinonediazide compounds, sulfonimide compounds, and diazomethane compounds can be exemplified. In addition, the triazine compound exemplified as the (C) photoradical polymerization initiator is a compound that also functions as a photoacid generator. In the present specification, (C) photoradical polymerization is used for content calculation and the like. Treat as an initiator.

  In the present invention, the (D) photoacid generator can be used alone or in admixture of two or more. The (D) photoacid generator in the present invention includes an onium salt compound and a sulfonimide compound. It is preferable to contain at least one selected from the group of diazomethane compounds, and it is particularly preferable to contain an onium salt compound.

  Examples of the onium salt compounds include diaryl iodonium salts, triaryl sulfonium salts, and triaryl phosphonium salts.

  Specific examples of the diaryliodonium salt include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroantimonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate Diphenyliodonium salts such as diphenyliodonium-p-toluenesulfonate; 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroantimonate, 4-methoxyphenyl Phenyl iodonium 4-methoxyphenylphenyliodonium salts such as hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoroacetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonate; bis ( 4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluorophosphonate, bis (4-tert-butylphenyl) iodonium hexafluoroantimonate, bis (4-tert-butylphenyl) Iodonium hexafluoroarsenate, bis (4-tert-butylphenyl) iodonium trifluoromethanesulfonate, bis 4-tert-butylphenyl) iodonium trifluoroacetate, bis (4-tert- butylphenyl) iodonium salts such as bis (4-tert- butylphenyl) iodonium -p- toluenesulfonate and the like.

  Specific examples of the triarylsulfonium salt include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium hexafluoroarsenate, and triphenylsulfonium trifluoromethanesulfonate. , Triphenylsulfonium trifluoroacetate, triphenylsulfonium salt such as triphenylsulfonium-p-toluenesulfonate; 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium Hexafluoroantimonate, 4-methoxyph 4-methoxyphenyldiphenylsulfonium salts such as nildiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylsulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate 4-phenylthiophenyldiphenylsulfonium tetrafluoroborate, 4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate, 4-phenylthiophenyldiphenylsulfonium hexafluoroarsenate, 4-phenyl Thiophenyldiphenylsulfonium trifluoro Tan sulfonate, 4-phenylthiophenyl diphenyl sulfonium trifluoroacetate, 4-phenyl-thiophenyl sulfonium -p- toluenesulfonate 4-phenylthiophenyldiphenylsulfonium sulfonium salts and the like.

  Specific examples of the triarylphosphonium salt include triphenylphosphonium tetrafluoroborate, triphenylphosphonium hexafluorophosphonate, triphenylphosphonium hexafluoroantimonate, triphenylphosphonium hexafluoroarsenate, and triphenylphosphonium trifluoromethanesulfonate. , Triphenylphosphonium salts such as triphenylphosphonium trifluoroacetate, triphenylphosphonium-p-toluenesulfonate; 4-methoxyphenyldiphenylphosphonium tetrafluoroborate, 4-methoxyphenyldiphenylphosphonium hexafluorophosphonate, 4-methoxyphenyldiphenylphosphonium Hexafluoroantimonate, 4-methoxyph 4-methoxyphenyldiphenylphosphonium salts such as nildiphenylphosphonium hexafluoroarsenate, 4-methoxyphenyldiphenylphosphonium trifluoromethanesulfonate, 4-methoxyphenyldiphenylphosphonium trifluoroacetate, 4-methoxyphenyldiphenylphosphonium-p-toluenesulfonate Tris (4-methoxyphenyl) phosphonium tetrafluoroborate, tris (4-methoxyphenyl) phosphonium hexafluorophosphonate, tris (4-methoxyphenyl) phosphonium hexafluoroantimonate, tris (4-methoxyphenyl) phosphonium hexafluoroarsenate , Tris (4-methoxyphenyl) phosphonium trifluoromethanesulfonate, Squirrel (4-methoxyphenyl) phosphonium trifluoroacetate, tris (4-methoxyphenyl) tris (4-methoxyphenyl) phosphonium salts such as phosphonium -p- toluenesulfonate, and the like.

  Specific examples of the sulfonimide compound include N- (trifluoromethylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) diphenylmaleimide, N- (Trifluoromethylsulfonyloxy) bicyclo- [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) -7-oxabicyclo- [2,2 , 1] -Hept-5-ene-2,3-dicarboximide, N- (trifluoromethylsulfonyloxy) bicyclo- [2,2,1] -heptane-5,6-oxy-2,3-di N- (trifluoromethyl such as carboximide and N- (trifluoromethylsulfonyloxy) naphthylimide Sulfonimide compounds having a rusulfonyloxy) group; N- (campanylsulfonyloxy) succinimide, N- (campanylsulfonyloxy) phthalimide, N- (campanylsulfonyloxy) diphenylmaleimide, N- (campanylsulfonyloxy) Bicyclo- [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (camphanylsulfonyloxy) -7-oxabicyclo- [2,2,1] -hept-5 Ene-2,3-dicarboximide, N- (campanylsulfonyloxy) bicyclo- [2,2,1] -heptane-5,6-oxy-2,3-dicarboximide, N- (camphanylsulfonyl) Sulfonimides having N- (camphanylsulfonyloxy) groups such as oxy) naphthylimide Compound: N- (4-methylphenylsulfonyloxy) succinimide, N- (4-methylphenylsulfonyloxy) phthalimide, N- (4-methylphenylsulfonyloxy) diphenylmaleimide, N- (4-methylphenylsulfonyloxy) Bicyclo- [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) -7-oxabicyclo- [2,2,1] -hept- 5-ene-2,3-dicarboximide, N- (4-methylphenylsulfonyloxy) bicyclo- [2,2,1] -heptane-5,6-oxy-2,3-dicarboximide, N- Sulfonimides having N- (4-methylphenylsulfonyloxy) groups such as (4-methylphenylsulfonyloxy) naphthylimide Compound: N- (2-trifluoromethylphenylsulfonyloxy) succinimide, N- (2-trifluoromethylphenylsulfonyloxy) phthalimide, N- (2-trifluoromethylphenylsulfonyloxy) diphenylmaleimide, N- (2- Trifluoromethylphenylsulfonyloxy) bicyclo- [2,2,1] -hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) -7-oxabicyclo- [ 2,2,1] -hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy) bicyclo- [2,2,1] -heptane-5,6-oxy -2,3-dicarboximide, N- (2-trifluoromethylphenylsulfonyloxy And the like sulfonimide compound having a N-(2-trifluoromethylphenylsulfonyloxy) groups such naphthylimide.

  Specific examples of the diazomethane compound include bis (trifluoromethylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, and methylsulfonyl-p-. Examples include toluenesulfonyldiazomethane, 1-cyclohexylsulfonyl-1- (1,1-dimethylethylsulfonyl) diazomethane, and bis (1,1-dimethylethylsulfonyl) diazomethane.

  (D) The photoacid generator is preferably an onium salt compound, more preferably a triarylsulfonium salt.

  In the photosensitive resin composition of the present invention, the content of (D) the photoacid generator is preferably 0.01 to 100 parts by mass with respect to 100 parts by mass of (A) the photoradical polymerizable compound. .1 to 50 parts by mass is particularly preferable. If the amount is less than 0.01 parts by mass, the desired effect may not be obtained. If the amount exceeds 100 parts by mass, the electrical characteristics may be deteriorated or the substrate may be corroded.

(E) Colorant As the (E) colorant contained in the photosensitive resin composition of the present invention, pigments and dyes are preferably used. As the above pigment, those usually used as organic pigments can be used, and are not particularly limited. For example, azo pigments, phthalocyanine pigments, polycyclic pigments (quinacridone, perylene, perinone, Preferable examples include isoindolinone, isoindoline, dioxazine, thioindigo, anthraquinone, quinophthalone, metal complex, diketopyrrolopyrrole, and dye lake pigments. Examples of pigment colors that can be used include yellow, red, purple, blue, green, brown, black, white, and azo dyes.

The pigment may be subjected to surface treatment such as rosin treatment, surfactant treatment, resin dispersant treatment, pigment derivative treatment, oxide film treatment, silica coating, wax coating and the like according to the purpose and application. Specific examples of pigments include, for example, compounds classified as Pigments in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the Color Index (CI) numbers as shown below. What is attached can be mentioned.
CI Pigment Yellow 1, CI Pigment Yellow 3, CI Pigment Yellow 12, CI Pigment Yellow 13, CI Pigment Yellow 14, CI Pigment Yellow 15, CI Pigment Yellow 16, CI Pigment Yellow 17, CI Pigment Yellow 20, CI Pigment Yellow 24, CI Pigment Yellow 31, CI Pigment Yellow 55, CI Pigment Yellow 60, CI Pigment Yellow 61, CI Pigment Yellow 65, CI Pigment Yellow 71, CI Pigment Yellow 73, CI Pigment Yellow 74, CI Pigment Yellow 81, CI Pigment Yellow 83, CI Pigment Yellow 93, CI Pigment Yellow 95, CI Pigment Yellow 97, CI Pigment Yellow 98, CI Pigment Yellow 100, CI Pigment Yellow 101, CI Pigment CI Yellow 104, CI Pigment Yellow 106, CI Pigment Yellow 108, CI Pigment Yellow 109, CI Pigment Yellow 110, CI Pigment Yellow 113, CI Pigment Yellow 114, CI Pigment Yellow 116, CI Pigment Yellow 117, CI Pigment Yellow 119, CI CI Pigment Yellow 120, CI Pigment Yellow 126, CI Pigment Yellow 127, CI Pigment Yellow 128, CI Pigment Yellow 129, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 175;
CI Pigment Violet 1, CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38;
CI Pigment Red 1, CI Pigment Red 2, CI Pigment Red 3, CI Pigment Red 4, CI Pigment Red 5, CI Pigment Red 6, CI Pigment Red 7, CI Pigment Red 8, CI Pigment Red 9, CI Pigment Red 10, CI Pigment Red 11, CI Pigment Red 12, CI Pigment Red 14, CI Pigment Red 15, CI Pigment Red 16, CI Pigment Red 17, CI Pigment Red 18, CI Pigment Red 19, CI Pigment Red 21, CI Pigment Red 22, CI Pigment Red 23, CI Pigment Red 30, CI Pigment Red 31, CI Pigment Red 32, CI Pigment Red 37, CI Pigment Red 38, CI Pigment Red 40, CI Pigment Red 41, CI Pigment Red 42, CI Pigment Tread 48: 1, CI Pigment Red 48: 2, CI Pigment Red 48: 3, CI Pigment Red 48: 4, CI Pigment Red 49: 1, CI Pigment Red 49: 2, CI Pigment Red 50: 1, CI Pigment Red 52: 1, CI Pigment Red 53: 1, CI Pigment Red 57, CI Pigment Red 57: 1, CI Pigment Red 57: 2, CI Pigment Red 58: 2, CI Pigment Red 58: 4, CI Pigment Red 60: 1 CI Pigment Red 63: 1, CI Pigment Red 63: 2, CI Pigment Red 64: 1, CI Pigment Red 81: 1, CI Pigment Red 83, CI Pigment Red 88, CI Pigment Red 90: 1, CI Pigment Red 97 CI Pigment Red 101, CI Pigment Red 102, CI Pigment Red 104, CI Pigment Red 105, CI Pigment Red 106, CI Pigment Red 108, CI Pigment Red 112, CI Pigment Red 113, CI Pigment Red 114, CI Pigment Red 122, CI Pigment Red 123, CI Pigment Red 144, CI Pigment Red 146, CI Pigment Red 149, CI Pigment Red 150, CI Pigment Red 151, CI Pigment Red 166, CI Pigment Red 168, CI Pigment Red 170, CI Pigment Red 171, CI Pigment Red 172, CI Pigment Red 174, CI Pigment Red 175, CI Pigment Red 176, CI Pigment Red 177, CI Pigment Red 178, CI Pigment Red 179, CI Pigment Red 180, CI Pigment Red 1 85, CI Pigment Red 187, CI Pigment Red 188, CI Pigment Red 190, CI Pigment Red 193, CI Pigment Red 194, CI Pigment Red 202, CI Pigment Red 206, CI Pigment Red 207, CI Pigment Red 208, CI Pigment Red 209, CI Pigment Red 215, CI Pigment Red 216, CI Pigment Red 220, CI Pigment Red 224, CI Pigment Red 226, CI Pigment Red 242, CI Pigment Red 243, CI Pigment Red 245, CI Pigment Red 254, CI Pigment Red 255, CI Pigment Red 264, CI Pigment Red 265;
CI Pigment Blue 1, CI Pigment Blue 15, CI Pigment Blue 15: 1, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60; CI Pigment Green 7, CI Pigment Green 36; CI Pigment Green 58 etc. are raised. These may be used alone or in combination of two or more.

  Further, as the dye, for example, organic dyes described in JP 2010-9033 A, JP 2010-211198 A, JP 2009-51896 A, and JP 2008-50599 A are used. Can do. These dyes and pigments may be used alone or in combination of two or more. Furthermore, a combination of a pigment and a dye can also be used. In particular, when forming red, blue, and green pixels of a color filter, a technique that exhibits desired color characteristics by combining color materials such as blue and purple and green and yellow is preferably used.

The content of the colorant (E) is preferably 10 to 70% by mass, particularly preferably 10 to 60% by mass, based on the entire solid component of the photosensitive resin composition. If the content exceeds 70%, the developability may be reduced.
Moreover, it is preferable that (B) alkali-soluble resin is 10-500 mass parts with respect to (E) 100 mass parts of coloring agents, and it is especially preferable that it is 20-300 mass parts. If it is less than 10 parts by mass, the developability may be reduced, and if it exceeds 500 parts by mass, the color material concentration may be lowered or the adhesion to the substrate may be reduced.
Moreover, it is preferable that (A) radical photopolymerizable compound is 10-500 mass parts with respect to 100 mass parts of (E) coloring agents, and it is especially preferable that it is 20-300 mass parts. If it is less than 10 parts by mass, the curability may be insufficient, and if it exceeds 500 parts by mass, the color material concentration may not be sufficient.

The content ratios of the components (A) to (E) can be combined as appropriate, but a more preferable content ratio is as follows with respect to 100% by mass of the total solid content of the photosensitive resin composition. it can.
(A) 5-50% by mass of a photo-radically polymerizable compound,
(B) 10-50% by mass of an alkali-soluble resin,
(C) 0.5-20 parts by mass of a radical photopolymerization initiator,
(D) 0.01-20% by mass of a photoacid generator,
(E) Colorant 10-70 mass%.

  Moreover, (A) 10 to 300 parts by mass of the photo-radical polymerizable compound, (C) 1 to 80 parts by mass of the photo-radical polymerization initiator, and (D) photoacid generation with respect to 100 parts by mass of the (B) alkali-soluble resin. 0.05 to 50 parts by weight of the agent, (E) 30 to 600 parts by weight of the colorant, and more preferably (A) 30 to 200 parts by weight of the radical photopolymerizable compound, (C) 5 to radical photopolymerization initiator 5 40 parts by mass, (D) 0.1 to 25 parts by mass of a photoacid generator, and (E) 50 to 400 parts by mass of a colorant. By adjusting to the said range, sclerosis | hardenability and solvent resistance will become higher.

It is preferable that the photosensitive resin composition of the present invention also contains a solvent. The solvent can dissolve or disperse each component in the photosensitive resin composition used for reducing the viscosity and improving the handleability, forming a coating film by drying, or as a dispersion medium for the coloring material, etc. It is a low viscosity organic solvent.
As the solvent, those usually used can be used, and may be appropriately selected according to the purpose and application, and are not particularly limited. For example, methanol, ethanol, isopropanol, n-butanol, s-butanol and the like are used. Monoalcohols; glycols such as ethylene glycol and propylene glycol; cyclic ethers such as tetrahydrofuran and dioxane; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono Butyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobuty Glycol monoethers such as ether and 3-methoxybutanol; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol ethyl methyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, etc. Glycol ethers; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobuty Ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, 3-methoxybutyl acetate, etc. Esters of glycol monoethers; methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, methyl propionate, ethyl propionate, butyl propionate, methyl lactate, ethyl lactate, butyl lactate, methyl 3-methoxypropionate , Ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxy Alkyl esters such as ethyl propionate, methyl acetoacetate and ethyl acetoacetate; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene; hexane, cyclohexane, Aliphatic hydrocarbons such as octane; Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, water and the like. These may be used alone or in combination of two or more.
The amount of the solvent used may be appropriately set depending on the purpose and application, and is not particularly limited, but is 100 to 1000% by mass with respect to 100% by mass of the photosensitive resin composition (solid component) of the present invention. Preferably there is.

  The photosensitive resin composition of the present invention is a curing aid for fillers, epoxy resins, phenolic resins, polyvinylphenol and other thermosetting resins, polyfunctional thiol compounds, etc., in addition to the components described above, depending on the required properties of each application. Agent, heat resistance improver, development aid, plasticizer, polymerization inhibitor, UV absorber, antioxidant, matting agent, antifoaming agent, leveling agent, antistatic agent, slip agent, surface modifier, shaking change Components such as an agent, a thixotropic agent, a coupling agent such as silane, aluminum, and titanium, a quinonediazide compound, a polyhydric phenol compound, a cationic polymerizable compound, and an acid generator may be blended. Below, other components suitable when using the photosensitive resin composition of this invention as a resist for color filters (preferably negative resist) are demonstrated. In the photosensitive resin composition of the present invention, the thermosetting resin such as epoxy resin, phenol resin, and polyvinylphenol is preferably 5% by mass or less, more preferably 100% by mass with respect to 100% by mass of the composition (solid component). Is preferably 3% by mass or less, most preferably 1% by mass or less.

<Antioxidant>
As the antioxidant used in the present invention, a hindered phenol-based antioxidant or a phosphite-based antioxidant is preferable.

As the hindered phenol-based antioxidant, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-tert-butylphenyl) propionate, 3,9-bis [1,1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl ] 2,4,8,10-tetraoxaspiro [5,5] -undecane, 2- [1- (2-hydroxy-3,5-di-t-pentylphenyl) ethyl] -4,6-di- t-pentylphenyl acrylate, 2-t-butyl-6- (3-t-butyl-2-hydroxy-5-methylbenzyl) -4-methylphenyl acrylate, 2,6-di-t-butyl 4-methylphenol, 2,4,6-tri-t-butylphenol, 2,6-di-t-butylphenol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t- Butyl-4-ethylphenol, 2,6-di-t-butyl-4-n-butylphenol, 2,6-di-t-butyl-4-isobutylphenol, 2,6-dicyclopentyl-4-methylphenol, 2- (α-methylcyclohexyl) -4,6-dimethylphenol, 2,6-diocudadecyl-4-methylphenol, 2,4,6-tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxy Methylphenol, 2,6-di-nonyl-4-methylphenol, 2,4-dimethyl-6- (1'-methylundecyl-1'-yl) phenol, 2,4-dimethyl Alkylated mono, such as ru-6- (1'-methylheptadecyl-1'-yl) phenol, 2,4-dimethyl-6- (1'-methyltridecyl-1'-yl) phenol and mixtures thereof Phenol;
2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4-dioctylthiomethyl-6-methylphenol, 2,4-dioctylthiomethyl-6-ethylphenol, 2,6-didodecylthiomethyl-4 -Alkylthiomethylphenols such as nonylphenol and mixtures thereof;
2,2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 2,2′-methylenebis [4-methyl-6- ( α-methylcyclohexyl) phenol]], 2,2′-methylenebis (4-methyl-6-cyclohexylphenol), 2,2′-methylenebis (4-methyl-6-nonylphenol), 2,2′-methylenebis (4 , 6-di-t-butylphenol), 2,2′-ethylidenebis (4,6-di-t-butylphenol), 2,2′-ethylidenebis (4-isobutyl-6-t-butylphenol), 2, 2′-methylenebis [6- (α-methylbenzyl) -4-nonylphenol], 2,2′-methylenebis [6- (α, α-dimethylbenzyl) -4-nonylphenol 4,4′-methylenebis (6-tert-butyl-2-methylphenol), 4,4′-methylenebis (2,6-di-tert-butylphenol), 4,4′-butylidenebis (3-methyl) -6-tert-butylphenol), 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, 2,6-bis ( 3-t-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol, 1,1,3-tris (5-t-butyl-4-hydroxy-2-methylphenyl) butane, 1,1- Bis (5-t-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercaptobutane, ethylene glycol bis [3,3-bis-3′-t-butyl-4′-hydroxyphene Nyl] butyrate], bis (3-t-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene, bis [2- (3′-t-butyl-2′-hydroxy-5′-methylbenzyl)- 6-tert-butyl-4-methylphenyl] terephthalate, 1,1-bis (3,5-dimethyl-2-hydroxyphenyl) butane, 2,2-bis (3,5-di-tert-butyl-4- Hydroxyphenyl) propane, 2,2-bis (5-t-butyl-4-hydroxy-2-methylphenyl) -4-n-dodecylmercaptobutane, 1,1,5,5-tetra (5-t-butyl) Alkylidene bisphenol and derivatives thereof such as -4-hydroxy-2-methylphenyl) pentane and mixtures thereof;
Etc. Among them, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], which has a high antioxidant ability and is easily industrially available, is preferable.

  Phosphite antioxidants include triphenyl phosphite, tris (nonylphenyl) phosphite, triethyl phosphite, tridecyl phosphite, tris (tridecyl) phosphite, diphenyl mono (2-ethylhexyl) phosphite, Diphenyl monodecyl phosphite, diphenyl mono (tridecyl) phosphite, tristearyl phosphite, tris (2,4-di-tert-butylphenyl) phosphite and the like are preferable.

  As a preferable compounding quantity of antioxidant, 0.01 mass%-2 mass% are preferable with respect to (B) alkali-soluble resin, and 0.05 mass%-1 mass% are still more preferable. When the blending amount of the antioxidant is less than the above range, the coloring prevention effect may be decreased, and when it exceeds the above range, curing as the photosensitive resin composition may be inhibited.

<Dispersant>
A dispersant has an interaction site with a pigment and an interaction site with a dispersion medium (solvent or binder resin), and has a function of stabilizing the dispersion of the pigment in the dispersion medium. Are classified into resin type dispersants (polymer dispersants), surfactants (low molecular dispersants), and pigment derivatives. As such a dispersant, a commonly used dispersant can be used.

Examples of the resin-type dispersant include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, and polysiloxanes. , Long-chain polyaminoamide phosphate, hydrogen group-containing polycarboxylic acid ester, amide formed by reaction of poly (lower alkyleneimine) with polyester having a free carboxyl group, or a salt thereof, (meth) acrylic acid-styrene Copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, polyester, modified polyacrylate, ethylene oxide / polypropylene oxide adduct, etc. All It is.
The resin-type dispersant has a graft structure resin in which the main chain is an anchor chain having an interaction site with a pigment, and the graft chain is a compatible chain having an interaction property with a dispersion medium. In addition, a resin in which an anchor chain and a compatible chain have a block structure is particularly preferably used.

  Examples of the surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, Anionic surfactants such as sodium stearate and sodium lauryl sulfate; nonions such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate Surfactant; Cationic field of alkyl quaternary ammonium salts and their ethylene oxide adducts Alkyl betaines such as alkyl dimethylamino acetic acid betaine, and amphoteric surfactants such as alkyl imidazolines; active agents.

The dye derivative is a compound having a structure in which a functional group is introduced into the dye. Examples of the functional group include a sulfonic acid group, a sulfonamide group and a quaternary salt thereof, a dialkylamino group, a hydroxy group, a carboxyl group, and an amide. Group, phthalimide group, etc., and examples of the structure of the dye as a base include, for example, azo, anthraquinone, quinophthalone, phthalocyanine, quinacridone, benzimidazolone, isoindoline, dioxazine, indanthrene System, perylene system, diketopyrrolopyrrole system and the like.
Examples of the trade name of the dispersant include the following. However, the dispersant is not limited to these.
For example, EFKA-46, 47, 48, 745, 1101, 1120, 1125, 4008, 4009, 4046, 4047, 4520, 4540, 4550, 6750, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 1210, 2150, KS860, KS873N, 7004, 1813, 1860, 1401, 1200, 550, EDAPLAN 470, 472, 480, 482, K-SPERSE 131, 1525070, 5207 (above, manufactured by EFKA ADDITIVES), Anti -Terra-U, Anti-Terra-U100, Anti-Terra-204, Anti-Terra-205, Anti-Terra-P, Disperbyk-101, 102, 103, 106, 108, 109, 110, 111, 112, 151 , 160, 161, 162, 163, 164, 166, 182, P-104, P-104S, P105, 220S, 203, 204, 205, 2000, 2001, 9075, 9076, 9077 (above, manufactured by Big Chemie), SOLPERSE 3000, 5000, 9000, 12000, 13240, 13940, 17000, 20000, 22000, 24000, 24000GR, 26000, 28000 (above, manufactured by Nihon Lubrizol), Disperlon 730 325, 374, 234, 1220, 2100, 2200, KS260, KS273N, 152MS (above, manufactured by Enomoto Kasei Co., Ltd.), Ajisper PB-711, 821, 822, 880, PN-411, PA-111 (above, Ajinomoto Fine Techno), KP series (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow series (manufactured by Kyoeisha Chemical Co., Ltd.), mega-fuck series (manufactured by DIC (DIC)), dispar aid series (manufactured by Sannopco), etc. .
These dispersants can be used alone or in combination of two or more.

  The amount of the dispersant used may be appropriately set according to the purpose and application, but in order to balance dispersion stability, durability (heat resistance, light resistance, weather resistance, etc.) and transparency, It is preferable that it is 0.01-60 mass% with respect to 100 mass% of total solid of the photosensitive resin composition of this invention, More preferably, it is 0.1-50 mass%, More preferably, it is 0.00. It is 5-40 mass%.

<Leveling agent>
A leveling agent can be added to the photosensitive resin composition of the present invention to improve leveling properties. As the leveling agent, a fluorine-based or silicon-based surfactant is preferable.

<Coupling agent>
A coupling agent can be added to the photosensitive resin composition of the present invention to improve adhesion. As the coupling agent, a silane coupling agent is preferable, and examples thereof include an epoxy-based, methacrylic-based, and amino-based silane coupling agent, and among them, an epoxy-based silane coupling agent is preferable.

<Development aid>
In order to improve developability, the photosensitive resin composition of the present invention includes, for example, monocarboxylic acids such as (meth) acrylic acid, acetic acid, propionic acid; maleic acid, fumaric acid, succinic acid, tetrahydrophthalic acid, trimellit Polycarboxylic acids such as acids; carboxylic acid anhydrides such as maleic anhydride, succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride; etc. can be added as a development aid.

  The photosensitive resin composition of the present invention can be prepared by mixing and dispersing the constituent components using various mixers and dispersers. Particularly, when the photosensitive resin composition of the present invention contains a pigment, It is manufactured through a pigment dispersion treatment process. As the pigment dispersion treatment step, for example, first, a predetermined amount of each of an organic pigment, a dispersant, a binder resin, and a solvent is weighed, and paint conditioner, bead mill, roll mill, ball mill, jet mill, homogenizer, kneader, blender, etc. Using a disperser, the pigment is finely dispersed to form a liquid color material dispersion (mill base). Preferably, after kneading and dispersing with a roll mill, kneader, blender or the like, fine dispersion is performed with a media mill such as a bead mill filled with 0.01 to 1 mm beads. To the obtained mill base, a transparent resist solution containing a radical polymerizable compound, a photopolymerization initiator, a binder resin, a solvent, a leveling agent, etc., which has been separately stirred and mixed, is added and mixed to obtain a uniform dispersion solution. A resin composition is obtained. The obtained photosensitive resin composition is desirably filtered through a filter or the like to remove fine dust.

[Hardened product (cured film)]
The cured product (cured film) of the present invention can be formed by irradiating (exposing) an active energy ray to the photosensitive resin composition. Specifically, for example, the photosensitive resin composition is applied onto a substrate (also referred to as a base material) and dried, and a cured film is formed by irradiating (exposing) an active energy beam to the coated surface. It is preferable. Thus, the cured film formed with the said photosensitive resin composition is also one of this invention. In addition, since the photosensitive resin composition is suitably used as a resist material, the form in which the cured film formed from the photosensitive resin composition is a resist cured film is also a preferred form of the present invention. One.

  The substrate on which the photosensitive resin composition is applied is not particularly limited. For example, a transparent glass substrate such as white plate glass, blue plate glass, silica-coated blue plate glass; polyethylene terephthalate (PET), polyester, polycarbonate, polyolefin, polysulfone Sheets or films made of thermoplastic resins such as ring-opened polymers of cyclic olefins and hydrogenated products thereof; Sheets or films made of thermosetting resins such as epoxy resins and unsaturated polyester resins; Aluminum plates, copper plates, nickel plates And a metal substrate such as a stainless steel plate; a ceramic substrate; a semiconductor substrate having a photoelectric conversion element; a member made of various materials such as a glass substrate (color filter for LCD) having a color material layer on the surface; Especially, the sheet | seat or film which consists of heat resistant resin among a glass substrate and a plastic substrate from a heat resistant point is preferable. The substrate is preferably a transparent substrate.

  Further, the substrate may be subjected to corona discharge treatment, ozone treatment, chemical treatment with a silane coupling agent, etc., if necessary, and an inorganic material such as a gas barrier layer or a protective film on both sides or one side of the substrate. You may form the coating film of a component or an organic component. Moreover, when using a cured film for the member for display apparatuses, it is suitable to form electrodes, such as ITO, on the said board | substrate. In addition, the cured film of this invention is excellent also in adhesiveness with not only a board | substrate but electrodes, such as an ITO film | membrane.

The method for applying the photosensitive resin composition to the substrate is not particularly limited, and examples thereof include spin coating, slit coating, roll coating, and cast coating, and any method can be preferably used.
The coating film after being applied to the substrate can be dried using, for example, a hot plate, an IR oven, a convection oven, or the like. The drying conditions are appropriately selected according to the boiling point of the solvent component contained, the type of the curing component, the film thickness, the performance of the dryer, etc., but are usually performed at a temperature of 50 to 150 ° C. for 10 seconds to 300 seconds. Is preferred.

Examples of the light source of the active energy beam include a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a lamp light source such as a carbon arc, a fluorescent lamp, and an argon ion laser. Laser light sources such as YAG laser, excimer laser, nitrogen laser, helium cadmium laser, and semiconductor laser are used. Further, examples of the exposure system include a proximity system, a mirror projection system, and a stepper system, but the proximity system is preferably used.
In the irradiation process of the active energy beam, the active energy beam may be irradiated through a predetermined mask pattern depending on the application. In this case, the exposed portion is cured, and the cured portion is insolubilized or hardly soluble in the developer.

  Further, if necessary, after the step of irradiating with the active energy beam, a step of developing with a developer to remove an unexposed portion and forming a pattern (also referred to as a developing step) may be performed. Thereby, a patterned cured film can be obtained.

The development process in the development step can be usually performed at a development temperature of 10 to 50 ° C. by a method such as immersion development, spray development, brush development, or ultrasonic development. In addition, when using alkaline aqueous solution as a developing solution, it is preferable to wash | clean with water after image development.
The developer is not particularly limited as long as it dissolves the photosensitive resin composition of the present invention. Usually, an organic solvent or an alkaline aqueous solution is used, and a mixture thereof may be used.
Examples of the organic solvent suitable as the developer include an ether solvent and an alcohol solvent. Specifically, for example, dialkyl ethers, ethylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dialkyl ethers, triethylene glycol dialkyl ethers, alkyl phenyl ethers, aralkyl phenyl ethers, diaromatic ethers , Isopropanol, benzyl alcohol and the like.

In addition to the alkaline agent, the alkaline aqueous solution may contain a surfactant, an organic solvent, a buffering agent, a dye, a pigment, and the like as necessary. Examples of the organic solvent in this case include organic solvents suitable as the developer described above.
Examples of the alkali agent include inorganic substances such as sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, lithium hydroxide, tribasic sodium phosphate, dibasic sodium phosphate, sodium carbonate, potassium carbonate, and sodium bicarbonate. Alkali agents: Examples include amines such as trimethylamine, diethylamine, isopropylamine, n-butylamine, monoethanolamine, diethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, and these may be used alone or in combination of two or more. May be combined.

  Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, sorbitan acid alkyl esters, monoglyceride alkyl esters; alkylbenzene sulfonates, alkylnaphthalene sulfonic acids, and the like. Anionic surfactants such as salts, alkyl sulfates, alkyl sulfonates, sulfosuccinic acid ester salts; amphoteric surfactants such as alkylbetaines and amino acids, and the like. These may be used alone or in combination of two or more. Also good.

Further, if necessary, a post-curing step (also referred to as post-baking or post-treatment step) may be performed. The post-curing step includes, for example, a post-heating step (also referred to as a heat treatment step) in addition to a step of exposing with a light amount of, for example, 0.5 to 5 J / cm ² using a light source such as a high-pressure mercury lamp. . By performing such post-treatment, it becomes possible to further strengthen the hardness and adhesion of the patterned cured film.

  Among the post-treatment steps described above, the latter heat treatment step is preferred, and the temperature at that time is preferably 60 ° C. or higher. By performing the heat treatment step in this temperature range, the reactive compound is decomposed, and the effects of the present invention can be more fully exhibited. A form in which the cured film is heat-treated at a temperature of 60 ° C. or higher is also a preferred form of the present invention. The heat treatment temperature is more preferably 80 ° C. or higher, and preferably 300 ° C. or lower. Moreover, although heat processing time is not specifically limited, For example, it is preferable that it is 10 seconds-300 minutes.

[Color filters, liquid crystal display devices, organic EL displays, etc.]
The color filter and the liquid crystal panel of the present invention can be formed by applying the photosensitive resin composition on a substrate. As a substrate to which the composition is applied, in addition to glass plates, polyester, polycarbonate, polyolefin, polysulfone, cyclic olefin ring-opened polymers and thermoplastics such as hydrogenated products, epoxy resins, unsaturated polyester resins, etc. These are thermosetting plastic sheets. Among these, a glass plate or a heat resistant plastic sheet is preferable from the viewpoint of heat resistance. Further, the substrate may be subjected to chemical treatment with a corona discharge treatment, an ozone treatment, a silane coupling agent, or the like, if necessary.

  As described above, the photosensitive resin composition of the present invention provides a cured product (cured film) that is particularly excellent in solvent resistance and surface hardness, and also excellent in developability and adhesion to a substrate. Therefore, the cured product (cured film) formed from such a photosensitive resin composition is, for example, a component member of various display devices such as a liquid crystal display device, a solid-state imaging device, a touch panel display device, ink, printing, and the like. It is preferably used for various applications such as various optical members such as plates, printed wiring boards, semiconductor elements, and photoresists, electric machines and electronic devices. Preferably, a color filter in which a cured product of the photosensitive resin composition is formed on a substrate, a liquid crystal display device on which the color filter is mounted, and an organic EL display on which the color filter is mounted. Use in a color filter used in a liquid crystal display device, a solid-state image sensor, or the like is a preferred mode. As a result, the reliability of display quality and imaging quality of various display devices can be sufficiently increased to the extent that it can sufficiently meet the recent demand for higher performance. Thus, the cured film formed with the said photosensitive resin composition, the member for display apparatuses which has this cured film, and the display apparatus which has this cured film are contained in this invention.

  The display device member and the display device of the present invention may have one or more other constituent members as long as the cured film is included. The cured film is excellent in solvent resistance and surface hardness, stably excellent in adhesion to a substrate and the like, and has high smoothness and high transmittance. The display device member may be a film-like single layer or multilayer member composed of the cured film, or a member in which another layer is combined with the single layer or multilayer member. However, a cured product having a color material is preferably a color filter because it is excellent in solvent resistance.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples. Unless otherwise specified, “part” means “part by mass” and “%” means “% by mass”.
In the following Examples and Comparative Examples, various physical properties and the like were measured as follows.

<Weight average molecular weight>
Weight average molecular weight was measured by GPC (gel permeation chromatography) method using HLC-8220GPC (manufactured by Tosoh Corporation) and column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation) using polystyrene as a standard substance and tetrahydrofuran as an eluent.

<Solid content>
About 1 g of the polymer solution was weighed into an aluminum cup, dissolved by adding about 2 g of acetone, and then naturally dried at room temperature. Then, using a hot air dryer (trade name: PHH-101, manufactured by ESPEC CORP.), It was dried in a vacuum at 160 ° C. for 3 hours, then allowed to cool in a desiccator, and the weight was measured. From the weight loss, the solid content of the polymer solution was calculated.

<Acid value>
2 g of the resin solution is precisely weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water, and an automatic titration apparatus (manufactured by Hiranuma Sangyo Co., Ltd., trade name: COM-555) using a 0.1 N aqueous KOH solution as a titrant ), The acid value of the polymer solution was measured, and the acid value per gram of the solid content was determined from the acid value of the solution and the solid content of the solution.

<Solvent resistance of curable resin composition>
A curable resin composition was spin-coated on a 5 cm square glass substrate, dried at 90 ° C. for 3 minutes, exposed to 50 mJ with a high-pressure mercury lamp, and heat-treated at 230 ° C. for 30 minutes to form a thin film having a thickness of 2 μm. Obtained. Then, it was immersed in 20 g of 1-methyl-2-pyrrolidone (NMP) at 50 ° C. for 10 minutes, and the hue of 1-methyl-2-pyrrolidone eluted from the coating film was measured with a spectrophotometer UV3100 (manufactured by Shimadzu Corporation). The absorbance at 600 nm was determined (evaluation of the amount of the pigment component exuded from the glass substrate by measuring the absorbance of the NMP immersion liquid after the test).

Production Example 1
<Synthesis of Polymer A>
A separable flask equipped with a cooling tube was prepared as a reaction tank, and dimethyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate (hereinafter referred to as “MD”) 10 mass as a monomer dropping tank. Parts, cyclohexyl methacrylate (hereinafter referred to as “CHMA”) 60 parts by mass, methyl methacrylate (hereinafter referred to as “MMA”) 10 parts by mass, methacrylic acid (hereinafter referred to as “MAA”) 20 parts by mass, t-butyl par 2 parts by mass of oxy-2-ethylhexanoate (trade name “Perbutyl O”, manufactured by NOF Corporation; hereinafter referred to as “PBO”) and 40 parts by mass of propylene glycol monomethyl ether acetate (hereinafter referred to as “PGMEA”) are well stirred. A mixture was prepared and used as a chain transfer agent dropping tank, n-dodecanethiol (hereinafter referred to as “n-DM”). ) 3 parts by mass and 32 parts by mass of PGMEA were prepared by thoroughly stirring and mixing them.
The reaction vessel was charged with 128 parts by mass of PGMEA and purged with nitrogen, and then heated in an oil bath while stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction vessel was stabilized at 90 ° C., dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The dropwise addition was performed for 135 minutes each while maintaining the temperature at 90 ° C. After 60 minutes from the end of dropping, the temperature was raised to 110 ° C. and maintained at 110 ° C. for 3 hours. Once the internal temperature was cooled to room temperature, a gas introduction tube was attached to the separable flask, and bubbling of oxygen / nitrogen = 5/95 (v / v) mixed gas was started. Next, 5 parts of glycidyl methacrylate (hereinafter referred to as “GMA”), 0.10 parts of 6-t-butyl-2,4-xylenol, and 0.4 parts of triethylamine (hereinafter referred to as “TEA”) are added to the reaction vessel. The reaction was carried out at 110 ° C. for 8 hours. Thereafter, 36 parts of PGMEA was added and cooled to room temperature to obtain a polymer solution A having a concentration of 35%. The weight average molecular weight of the polymer A was 10,000, the acid value was 100 mgKOH / g, and the double bond equivalent of the polymer was 1900 g / mol.

Production Example 2
<Synthesis of Polymer B>
Polymer B was synthesized in the same manner as Polymer A with the composition changed to MD 10 parts, CHMA 60 parts, MMA 5 parts, MAA 25 parts and GMA 10 parts. The weight average molecular weight of the polymer B was 10,000, the acid value was 100 mgKOH / g, and the double bond equivalent of the polymer was 1000 g / mol.

Production Example 3
<Synthesis of Polymer C>
Polymer C was synthesized in the same manner as Polymer A with the composition changed to MD 10 parts, CHMA 40 parts, MMA 5 parts, MAA 45 parts and GMA 25 parts. The weight average molecular weight of the polymer C was 15000, the acid value was 110 mgKOH / g, and the double bond equivalent of the polymer was 500 g / mol.

Production Example 4
<Synthesis of Polymer D>
Polymer D has the same composition as Polymer A except that the composition is changed to 10 parts MD, 30 parts CHMA, 30 parts MMA, 15 parts 2-hydroxyethyl methacrylate (hereinafter referred to as “HEMA”), and 15 parts MAA. Were synthesized. The weight average molecular weight of the polymer D was 10,000, and the acid value was 100 mgKOH / g.

Production Example 5
<Synthesis of Polymer E>
Polymer E was synthesized in the same manner as Polymer A except that the composition was changed to 30 parts CHMA, 40 parts MMA, 15 parts HEMA, and 15 parts MAA, and no GMA addition was performed. The weight average molecular weight of the polymer E was 15000, and the acid value was 100 mgKOH / g.

Comparative Production Example <Synthesis of Polymer F>
Polymer F was synthesized in the same manner as Polymer A except that the composition was changed to 10 parts MD, 30 parts CHMA, 45 parts MMA, and 15 parts MAA, and no GMA addition was performed. The weight average molecular weight of the polymer F was 10,000, and the acid value was 100 mgKOH / g.

<Example 1>
The blue color material dispersion is 30 parts in terms of solid content, the resin (polymer A) is 30 parts in terms of solid content, 30 parts of dipentaerythritol hexaacrylate (hereinafter referred to as “DPHA”), and the photo radical initiator “IRGACURE” 369 ”(manufactured by BASF; hereinafter referred to as Irg369), photoacid generator“ CPI-100P ”[triarylmonosulfonium salt (4-phenylthiophenyldiphenylsulfonium hexafluorophosphonate); manufactured by San Apro Co., Ltd.] (Solid content conversion value) was diluted with PGMEA and mixed well to prepare curable resin composition 1 (solid content 20% by mass).
As the blue color material dispersion, “CI Pigment Violet 23 (manufactured by Clariant)”: “CI Pigment Blue 15: 6 (manufactured by BASF)” = 2: 8 (weight ratio) (solid) A quantity of 20% by weight) was used.
The obtained resin composition was applied onto a glass plate with a spin coater so that the film thickness after drying was 2 μm, and dried at 90 ° C. for 3 minutes with a hot air dryer. Thereafter, ultraviolet rays were irradiated with an ultrahigh pressure mercury lamp so that the irradiation amount was 50 mJ. After the irradiation, the test piece 1 was obtained by heating at 230 ° C. for 30 minutes with a hot air dryer. The obtained test piece was immersed in an NMP solution, heated at 50 ° C. for 10 minutes with a hot air dryer, then the test piece was taken out, and the absorbance of the remaining NMP solution was measured with a spectrophotometer. The results are shown in Table 1 as solvent resistance.

<Examples 2 to 5>
The resin was changed from polymer A to BE, and the same evaluation was performed.

<Example 6>
Evaluation was performed in the same manner as in Example 1 except that the polymer D was used and the photoacid generator was reduced to 1 part.

<Comparative Examples 1-5>
Evaluation was performed in the same manner except that the photoacid generator was removed from the compositions of Examples 1 to 5.

<Comparative Examples 6 and 7>
Using the polymer F, the same evaluation was performed by adding 5 parts of a photoacid generator in Comparative Example 6 and no photoacid generator in Comparative Example 6.

<Comparative Example 8>
In the system using the polymer B of Comparative Example 2, the same evaluation was performed except that the photo radical initiator was replaced with a photo acid generator. The results are shown in Table 2 as solvent resistance.

In Tables 1 and 2 above, the solvent resistance indicates the amount of pigment (coloring material) that has oozed into the NMP solution, and the lower the value, the better.
Further, in Table 1 above, the solvent resistance improvement rate represents how much the solvent resistance has been improved as compared with the case where there is no acid generator, and was calculated by the following formula.
Solvent resistance improvement rate (%) = [1-{(solvent resistance value in the presence of acid generator) / (solvent resistance value in the absence of acid generator)}] × 100
The higher the value of the solvent resistance improvement rate, the better the solvent resistance.

As shown in the solvent resistance improvement rate, in the resin having a double bond (Examples 1 to 3) and the resin having a hydroxy group (Examples 4 and 5), the solvent resistance can be improved by adding an acid generator. A significant improvement was confirmed. On the other hand, although the resin having no double bond and having no hydroxy group was improved, the effect was low (Comparative Examples 6 and 7). In the resins of Comparative Examples 6 and 7, the solvent resistance improvement rate by addition of the acid generator was 21%.
In addition, the photoradical initiator or the acid generator alone did not have a sufficient solvent resistance effect (Comparative Examples 2 and 8).

The photosensitive resin composition of the present invention is excellent in curability, alkali developability and adhesion, and is a resist for forming a member in the field of electronic information, for example, a solder resist, an etching resist, an interlayer insulating material, a plating resist, a color filter It is particularly suitable for forming a pixel (colored layer) of a color filter since it is suitable for a resist and excellent in solvent resistance.

Claims (6)

(A) a photoradically polymerizable compound, (B) an alkali-soluble resin, (C) a photoradical polymerization initiator, (D) a photoacid generator, and (E) a colorant,
The (B) alkali-soluble resin has structural units represented by the following formulas (a), (b) and (c), or is represented by the following formulas (a), (b) and (d). A photosensitive resin composition having a structural unit.

[In the above formulas (a), (b), (c) and (d), R ¹ and R ³ each independently represents a hydrogen atom or a methyl group. In the above formula (a), R ² is an alkyl group optionally substituted with a functional group other than the primary hydroxy group, an alicyclic group, a group containing an aromatic ring optionally substituted with a functional group, or ether A functional group having a bond is represented. Each Y in the above formulas (a), (b), (c) and (d) independently represents a carboxylate group (—COO—) or (—OCO—), a phosphate group (— PO ₃ —) or (—OPO ₂ —), a sulfonic acid ester group (—SO ₃ —) or (—OSO ₂ —), or a phenylene group. Z in the formula (c) and X in the formula (d) each independently represent a divalent hydrocarbon group which may have a substituent. ] The (B) alkali-soluble resin further comprises a dialkyl-2,2 ′-(oxydimethylene) diacrylate monomer, an N-substituted maleimide monomer, and an α- (unsaturated alkoxyalkyl) acrylate monomer. The photosensitive resin composition according to claim 1, comprising a structural unit derived from at least one monomer selected from the group consisting of bodies. Hardened | cured material formed by hardening | curing the photosensitive resin composition of Claim 1 or 2. A color filter having the cured product according to claim 3 on a substrate. A liquid crystal display device equipped with the color filter according to claim 4. An organic EL display equipped with the color filter according to claim 4.