JP2019045736A - Photosensitive resin composition and cured film - Google Patents

Abstract

The present invention provides an alkali-developable photosensitive resin composition capable of forming a cured film having excellent low-temperature curability, high hardness, excellent substrate adhesion, and chemical resistance, and the photosensitive resin composition An object of the present invention is to provide a high-quality cured film suitable for an overcoat used for a touch panel. The object is to provide a photosensitive resin composition containing a photocationic polymerization initiator (A), a cationically polymerizable compound (B) and an alkali-soluble resin, wherein the cationically polymerizable compound (B) is at least This is solved by a photosensitive resin composition comprising an episulfide compound (B1) and a cationically polymerizable compound (B2) other than the episulfide compound. [Selection figure] None

Description

  The present invention relates to a photosensitive resin composition, an organic electroluminescent display device formed using the same, and a cured film suitable for a touch panel.

  BACKGROUND OF THE INVENTION Displays such as liquid crystal display devices and organic electroluminescent devices are being widely used at present, with the development of applications for TVs, personal computer monitors, smartphones, and tablet terminals rapidly advancing. Recently, with the progress of making displays flexible and wearable, there is a growing need to manufacture devices using flexible substrates without using conventional rigid glass substrates, but many of the flexible substrates It is necessary to lower the temperature of the manufacturing process because it is made of an organic material and the heat resistance is lower than that of the glass substrate. In such a display manufacturing process, it is necessary to lower the heating temperature at the time of forming various cured films such as an insulating film and a protective film from the viewpoint of heat resistance problems of substrates, circuit elements, etc. and further energy saving. There is a need for a cured film composition that can be cured even under manufacturing conditions where the heating temperature is low.

  As a composition corresponding to the above-mentioned low temperature curing process, for example, an alkali soluble copolymer described in Patent Document 1, a polymerizable compound having an ethylenically unsaturated bond, a photo radical generator, two or more oxetanyl groups in one molecule. Radiation-sensitive resin composition containing a compound having an acid generator and a carboxyl group-containing polysiloxane described in Patent Document 2, a solvent, a compound having a double bond and / or a triple bond, and a resin containing a photopolymerization initiator Compositions have been proposed. However, although these compositions improve the adhesion to glass having Si atoms and a silicon nitride substrate, the adhesion after heat treatment and chemical treatment is insufficient on substrates having no Si atoms such as ITO and molybdenum. Met.

JP, 2009-3366, A JP, 2008-208342, A

  The present invention uses an alkali-developable photosensitive resin composition capable of forming a cured film excellent in low-temperature curability and high in hardness and excellent in substrate adhesion and chemical resistance, and the photosensitive resin composition It is an object of the present invention to provide a high quality cured film suitable for an overcoat used in a touch panel and a method for producing the same.

  A photosensitive resin composition comprising a cationic photopolymerization initiator (A), a cationically polymerizable compound (B) and an alkali-soluble resin, wherein the cationically polymerizable compound (B) is at least an episulfide compound (B1) and an episulfide By including a cationically polymerizable compound (B2) other than the compound, a cured film having high hardness and high transparency, excellent in pattern linearity and chemical resistance can be formed, and excellent in low temperature curability I found something.

  That is, the present invention is a photosensitive resin composition containing a cationic photopolymerization initiator (A), a cationically polymerizable compound (B) and an alkali-soluble resin, wherein the cationically polymerizable compound (B) is at least an episulfide. The present invention relates to a photosensitive resin composition containing a compound (B1) and a cationically polymerizable compound (B2) other than an episulfide compound.

  The present invention also relates to the above photosensitive resin composition, wherein the cationically polymerizable compound (B2) other than the episulfide compound contains at least one selected from the group consisting of an oxetane compound, a vinyl ether compound and an epoxy compound.

  The present invention also relates to the photosensitive resin composition as described above, wherein the cationically polymerizable compound (B2) other than the episulfide compound contains at least an oxetane compound.

  The present invention also relates to the above photosensitive resin composition, wherein the cationically polymerizable compound (B2) other than the episulfide compound contains at least an oxetane compound and a vinyl ether compound.

  In the photosensitive resin composition according to the present invention, the content ratio of the episulfide compound (B1) and the cationically polymerizable compound (B2) other than the episulfide compound is (B1) :( B2) = 20: 80 to 80:20. Related to things.

Further, the present invention provides the above photosensitive resin composition, wherein the oxetane compound comprises a polymer represented by the following chemical formula (3-5) or a polymer obtained by polymerizing (3-ethyl oxetan-3-yl) methyl (meth) acrylate Related to things.

  The present invention also relates to the photosensitive resin composition as described above, wherein the cationic photopolymerization initiator (A) contains an aromatic sulfonium salt (a1) or an aromatic iodonium salt (a2).

  The present invention also relates to the above photosensitive resin composition further comprising a photo radical polymerization initiator (C).

  The present invention is also directed to the above photosensitivity wherein the photo radical polymerization initiator (C) contains at least one selected from the group consisting of oxime ester photopolymerization initiators, thioxanthone photopolymerization initiators and acetophenone photopolymerization initiators. It relates to a resin composition.

  Moreover, this invention is the said photosensitive resin whose content ratio of a photocationic polymerization initiator (A) and a photoradical polymerization initiator (C) is (A) :( C) = 30: 70-: 80: 20. It relates to a composition.

  Moreover, this invention relates to the cured film formed using the said photosensitive resin composition.

  The present invention also relates to a method for producing a cured film, comprising the steps of applying the photosensitive resin composition onto a substrate, exposing it through a mask, developing it to form a pattern, and heating and baking it.

  Moreover, this invention relates to the manufacturing method of the said cured film whose temperature of heat-firing is 100 degrees C or less.

  The present invention also relates to the above-mentioned cured film which is an interlayer insulating film or an overcoat film.

  Furthermore, the present invention relates to the above-mentioned cured film for a touch panel.

  The photosensitive resin composition of the present invention not only has high hardness and high transmittance, but also is excellent in low-temperature curability, so a cured film excellent in pattern linearity, adhesion and chemical resistance at low temperature curing is obtained. Can. In addition, the composition can provide a cured film having high hardness and high transmittance, and excellent in pattern linearity, adhesion, and chemical resistance. That is, the photosensitive resin composition and the cured film of the present invention are suitable for insulating films and overcoats used in organic electroluminescent display devices and touch panels.

First, various components of the photosensitive resin composition of the present invention will be described.
In the present application, “(meth) acryloyl”, “(meth) acrylic”, “(meth) acrylic acid”, “(meth) acrylate” or “(meth) acrylamide” are particularly described. Unless there is any, respectively, "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide" It shall represent.

  The photosensitive resin composition of the present invention is a photosensitive resin composition containing a cationic photopolymerization initiator (A), a cationically polymerizable compound (B) and an alkali-soluble resin, and the cationically polymerizable compound (B) Are characterized by including at least an episulfide compound (B1) and a cationically polymerizable compound (B2) other than the episulfide compound.

<Photo cationic polymerization initiator (A)>
The photocationic polymerization initiator (A) generates strong acids such as tetrafluoroboric acid and hexafluorophosphoric acid by UV irradiation or heating, and the strong acids protonate the oxygen atom of the cationically polymerizable compound described later to form cationically active species. Is formed to initiate the polymerization reaction, and known compounds can be used without particular limitation.

As the photocationic polymerization initiator (A), for example, the cation moiety is aromatic sulfonium, aromatic iodonium, aromatic diazonium, aromatic ammonium, thioxanthonium, (2,4-cyclopentadien-1-yl) [(1 -Methylethyl) benzene] -iron cation or thiansurenium, wherein the anion moiety is BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , or [BX ₄ ] ⁻ (where X is a phenyl group) Aromatic sulfonium salt (a1), aromatic iodonium salt (a2), aromatic diazonium salt, each of which represents a functional group substituted by two or more hydrogen atoms by a fluorine atom or a trifluoromethyl group. , Aromatic ammonium salts, thioxanthonium salts, or (2,4-cyclopentadien-1-yl) [(1-methyl ether) And the like), and the like.
These photocationic polymerization initiators can be used alone or in combination of two or more at an arbitrary ratio as required.

(Aromatic sulfonium salt (a1))
Examples of the aromatic sulfonium salt (a1) include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, and bis [4- (Diphenylsulfonio) phenyl] sulfide Bis tetrafluoroborate, bis [4- (diphenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate, diphenyl-4- (phenylthio) phenylsulfonium hexafluorophosphate, diphenyl-4- (Phenylthio) phenylsulfonium hexafluoroantimonate, diphenyl-4- (phenylthio) phenylsulfonium tetrafluoroborate, diphenyl-4- (pheny) (Luthio) phenylsulfonium tetrakis (pentafluorophenyl) borate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrafluoroborate, triphenylsulfonium tetrakis (pentafluorophenyl) borate, bis [4- ( Di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bishexafluoroantimo , Bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bis tetrafluoroborate, bis [4 -(Di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide Tetrakis (pentafluorophenyl) borate and the like can be used.

(Aromatic iodonium salt (a2))
Also, as the aromatic iodonium salt (a2), for example, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, bis (dodecylphenyl) iodonium hexafluoro Phosphate, bis (dodecylphenyl) iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrafluoroborate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, 4-methylphenyl-4- (1-methylethyl) Phenyliodonium hexafluorophosphate, 4-methylphenyl-4- (1-) Ethylethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate Etc. can be used.

(Aromatic diazonium salt)
Further, as the aromatic diazonium salt, for example, phenyldiazonium hexafluorophosphate, phenyldiazonium hexafluoroantimonate, phenyldiazonium tetrafluoroborate, phenyldiazonium tetrakis (pentafluorophenyl) borate and the like can be used.

(Aromatic ammonium salt)
Also, as the aromatic ammonium salt, 1-benzyl-2-cyanopyridinium hexafluorophosphate, 1-benzyl-2-cyanopyridinium hexafluoroantimonate, 1-benzyl-2-cyanopyridinium tetrafluoroborate, 1-benzyl- 2-cyanopyridinium tetrakis (pentafluorophenyl) borate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluorophosphate, 1- (naphthylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl)- 2-Cyanopyridinium tetrafluoroborate, 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate and the like can be used.

(Thioxanthonium salt)
Moreover, as thioxanthonium salt, S-biphenyl 2-isopropyl thioxanthonium hexafluorophosphate etc. can be used.

((2,4-Cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron salt)
Moreover, as (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron salt, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -Iron (II) hexafluorophosphate, (2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron (II) hexafluoroantimonate, 2,4-cyclopentadien-1-yl ) [(1-Methylethyl) benzene] -iron (II) tetrafluoroborate, 2,4-cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron (II) tetrakis (pentafluorophenyl) Borate etc. can be used.

  Among these, aromatic sulfonium salt (a1) or aromatic iodonium salt (a2) is preferable for improving the residual film rate and adhesion, and from the viewpoint of improving the residual film rate, more preferably aromatic iodonium salt (a2) It is.

  As a photocationic polymerization initiator (A), CPI-100P, CPI-200K, CPI-101A (above, San-Apro Co., Ltd. product), thyra cure photocuring initiator UVI-6990, thyra cure photocuring initiator UVI- 6992, CYRA CURE Photo-curing initiator UVI-6976 (all, Dow Chemical Japan Ltd.), Adeka Optomer SP-150, Adeka Optomer SP-152, Adeka Optomer SP-170, Adeka Optomer SP-172 (Above, Asahi Denka Kogyo Co., Ltd. product), CI-5102, CI-2855 (above, Nippon Soda Co., Ltd. product), San Aid SI-60L, San Aid SI-80 L, San Aid SI-100 L, San Aid SI-110 L, San Aid SI-180L, San Aid SI-110, San Aid SI-145 San-Aid SI-150, San-Aid SI-160, San-Aid SI-180 (manufactured by Sanshin Chemical Industry Co., Ltd.), Esacure 1064, Esacure 1187 (manufactured by Lamberti, Inc.), Omni Cat 432, Omni Cat 440, Omni Cat 445, Omni Cat 550, Omni Cat 650, Omni Cat BL-550 (manufactured by ID Resin Co., Ltd.), Irgacure 250 (manufactured by BASF Corp.), Rhodesil Photoinitiator 2074 (RHODORSIL PHOTOINITIATOR 2074 (Rodia Japan Co., Ltd.) And WPI-113, WPI-116, WPI-169, WPI-170 (manufactured by Wako Pure Chemical Industries, Ltd.) and the like are commercially available.

  Among these, aromatic sulfonium salt (a1) CPI-100P, CPI-101A, CPI-200K, CPI-210S manufactured by San-Apro, or BASF Irgacure 250 manufactured by aromatic iodonium salt, Wako Pure Chemical Industries, Ltd. Company WPI-113, WPI-116, WPI-169, WPI-170 are preferable.

  The photocationic polymerization initiator (A) is preferably used in an amount of 0.1 to 30% by mass in the total 100% by mass of the solid content of the photosensitive resin composition, and the residual film ratio, chemical resistance, and transmittance It is more preferable to use in the amount of 1 to 20% by mass from the viewpoint of

<Photo radical polymerization initiator (C)>
In the photosensitive resin composition of the present invention, in order to cure the composition by ultraviolet irradiation and form a coating film by a photolithography method, a photo-radical polymerization initiator is further added to form a solvent developing type or an alkali developing type. It can be prepared in the form of a photosensitive resin composition of Any of conventionally known photoradical polymerization initiators can be used.

  Examples of photo radical polymerization initiators include oxime ester photopolymerization initiators, thioxanthone photopolymerization initiators, acetophenone photopolymerization initiators, benzoin photopolymerization initiators, benzophenone photopolymerization initiators, and triazine photopolymerization initiators. And borate type photopolymerization initiators, carbazole type photopolymerization initiators, imidazole type photopolymerization initiators, and acyl phosphine oxide type photopolymerization initiators, but not limited thereto.

Specifically, for example, 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) Oxime ester type photoinitiators, such as -9H-carbazol-3-yl]-, 1- (o-acetyl oxime);
Thioxanthone photopolymerization initiators such as thioxanthone, 2-chlorothioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diisopropyl thioxanthone,
4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Acetophenones such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one and 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one Photo initiator,
Acylphosphine oxide photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide;
Benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl dimethyl ketal,
Benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, etc.
2,4,6-Trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloro) Methyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-tri Triazine photoinitiators such as azine,
Borate photopolymerization initiators, carbazole photopolymerization initiators,
An imidazole type photoinitiator etc. are mentioned.
These photopolymerization initiators can be used alone or in combination of two or more at an arbitrary ratio as required.

  Among these, low-temperature curing is provided that the photo radical polymerization initiator contains at least one selected from the group consisting of an oxime ester photopolymerization initiator, a thioxanthone photopolymerization initiator, and an acetophenone photopolymerization initiator. In the case where it contains at least two types, it is possible to have excellent chemical resistance.

  The radical photopolymerization initiator is preferably used in an amount of 1 to 15% by mass, and more preferably 1 to 10% by mass, in the total 100% by mass of the solid content of the resin composition from the viewpoint of transmittance. preferable. In the present invention, the content ratio of the cationic photopolymerization initiator (A) and the radical photopolymerization initiator (C) is in the range of (A) :( C) = 30: 70 to: 80: 20. ,preferable.

<Sensitizer>
The photosensitive resin composition of the present invention may further contain, as a sensitizer, α-acyloxy ester, acyl phosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone Compounds such as 4,4'-diethylisophthalophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-diethylaminobenzophenone can also be used in combination. These sensitizers can be used alone or in combination of two or more at an arbitrary ratio as needed. The content of the sensitizer can be used in an amount of 0.1 to 150 parts by mass with respect to 100 parts by mass of the photo cationic polymerization initiator (A).

<Cationically Polymerizable Compound (B)>
The cationically polymerizable compound in the present invention is a compound which reacts with a strong acid such as tetrafluoroboric acid or hexafluorophosphoric acid generated by UV irradiation or heating to the above-mentioned photocationic polymerization initiator (A) to generate cationically active species. It is The cationically polymerizable compound (B) of the present invention contains at least an episulfide compound (B1) and a cationically polymerizable compound (B2) other than the episulfide compound.

(Episulfide compound (B1))
As the episulfide compound (B1) used in the photosensitive resin composition of the present invention, any known compound can be used without particular limitation, and a polyfunctional compound having two or more episulfide groups in one molecule is preferable. Examples of polyfunctional episulfide compounds include 2,2-bis (4- (2,3-epithiopropoxy) phenyl) propane, bis (4- (2,3-epithiopropoxy) phenyl) methane, bis (3, 5-dimethyl-4- (2,3-epithiopropoxy) phenyl) methane, 1,6-di (2,3-epithiopropoxy) naphthalene, 1,1,1-tris- (4- (2,3) -Epithiopropoxy) phenyl) ethane, 2,2-bis (4- (2,3-epithiopropoxy) cyclohexyl) propane, bis (4- (2,3-epithiopropoxy) cyclohexyl) methane, 1,1 1,1-tris- (4- (2,3-epithiopropoxy) cyclohexyl) ethane, 2,3-epithiocyclohexyl) ether of 1,5-pentanediol, 1,6-hexane Di (3,4-epithiooctyl) ether of sandiol, 1,3-bis (β-epithiopropylthio) cyclohexane, 1,3-bis (β-epithiopropylthiomethyl) cyclohexane, bis [4- (Β-epithiopropylthio) cyclohexyl] methane, 2,2-bis [4- (β-epithiopropylthio) cyclohexyl] propane, bis [4- (β-epithiopropylthio) cyclohexyl] sulfide, 2 ,, 5-bis (.beta.-epithiopropylthio) -1,4-dithiane, 2,5-bis (.beta.-epithiopropylthioethylthiomethyl) -1,4-dithiane, 1,3-bis (beta-epi) Thiopropylthio) benzene, 1,3-bis (β-epithiopropylthiomethyl) benzene, bis [4- (β-epithiopropylthio) phenyl] methane, 2 , 2-Bis [4- (β-epithiopropylthio) phenyl] propane, bis [4- (β-epithiopropylthio) phenyl] sulfide, bis [4- (β-epithiopropylthio) phenyl] sulfin 4,4-bis (β-epithiopropylthio) biphenyl, 2- (2-β-epithiopropylthioethylthio) -1,3-bis (β-epithiopropylthio) propane, 1,2- Bis [(2-β-epithiopropylthioethyl) thio] -3- (β-epithiopropylthio) propane, tetrakis (β-epithiopropylthiomethyl) methane, 1,1,1-tris (β- Epithiopropylthiomethyl) propane, 9,9-bis {4- [2- (2,3-epithiopropoxy) ethoxy] phenyl} fluorene, 9,9-bis {4- [2- (2,3-) The Thiopropoxy) ethoxy] -3-methylphenyl} fluorene, 9,9-bis {4- [2- (2,3-epithiopropoxy) ethoxy] -3,5-dimethylphenyl} fluorene, 9,9-bis {4- [2- (2,3-epithiopropoxy) ethoxy] -3-phenylphenyl} fluorene, 9,9-bis {6- [2- (2,3-epithiopropoxy) ethoxy] -2- Naphthyl} fluorene, 9,9-bis {5- [2- (2,3-epithiopropoxy) ethoxy] -1-naphthyl} fluorene and the like can be mentioned.

  Among these episulfide compounds, 2,2-bis (4- (2,3-epithiopropoxy) phenyl) propane and bis (3,5-dimethyl-4- (2) from the viewpoint of high sensitivity and availability. , 3-epithiopropoxy) phenyl) methane and 2,2-bis (4- (2,3-epithiopropoxy) cyclohexyl) propane are preferable, and from the viewpoint of transmittance, 2,2-bis (4- (2 (bis) Preferred is 3, 3-epithiopropoxy) cyclohexyl) propane.

  Episulfide compounds can be produced by various methods. For example, thermal dehydration decomposition of 2-hydroxymercaptan, treatment with a weak alkaline solution of 1,2-chlorothiol, treatment with a compound such as sulfur of an ethylenically unsaturated ether or polysulfide dialkyl can be mentioned. There is also known a method of obtaining a thiirane group-containing compound by substituting a known epoxy compound as a raw material for substituting all or part of oxygen atoms of the epoxy group with sulfur atoms. For example, the method using the epoxy compound and the thiocyanate described in J. Polym. Sci. Polym. Phys., 17, 329 (1979), or the method described in J. Org. Chem., 26, 3467 (1961) Although the method of using an epoxy compound and thiourea, the method etc. which are shown by Unexamined-Japanese-Patent No. 2000-351829, 2001-342253, etc. are mentioned, It is not limited to these.

(Cationically Polymerizable Compound (B2) Other than Episulfide Compound)
Examples of the cationically polymerizable compound (B2) other than the episulfide compound include oxetane compounds, vinyl ether compounds, epoxy compounds, styrene derivatives, diene compounds and the like.

  The cationically polymerizable compound (B2) other than the episulfide compound preferably contains at least one selected from the group consisting of an oxetane compound, a vinyl ether compound and an epoxy compound, more preferably at least an oxetane compound, still more preferably At least an oxetane compound and a vinyl ether compound.

(Oxetane compound)
As the oxetane compound, known compounds having an oxetane group can be used without particular limitation. Examples of the oxetane compound include one having a monofunctional oxetane group, one having a bifunctional oxetane group, and one having a trifunctional or more oxetane group.

As an oxetane group is monofunctional,
(3-ethyloxetan-3-yl) methyl acrylate (for example, OXE-10 manufactured by Osaka Organic Chemical Industry Ltd.), (3-ethyloxetan-3-yl) methyl methacrylate (for example, OXE-30 manufactured by Osaka Organic Chemical Industry Ltd.) ), 3-ethyl-3-hydroxymethyl oxetane (for example, OXT-212 manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane And 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxysilyl) propoxy] methyl} oxetane and the like.

  Among those in which the oxetane group is monofunctional, preferably 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane represented by the following formula (3-1) or formula (3-2): Or 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane is preferred.

As an oxetane group is a bifunctional thing,
4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl (e.g., Ube Industries, Ltd., OXBP), 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl Benzene (for example, OXTP manufactured by Ube Industries, Ltd.), 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene (for example, OXT-121 manufactured by Toagosei Co., Ltd.), [1-ethyl (3-oxetanyl)] methyl ether (for example, OXT-221, manufactured by Toagosei Co., Ltd.), di [1-ethyl (3-oxetanyl)] methyl ether 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3-oxeta) Nil) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene Glycose bis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, polyethylene glycol bis ( 3-Ethyl-3-oxetanylmethyl) ether, ethyleneo SID (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis (3 -Ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether, Toagosei Co., Ltd. Manufactured by OXT-191.

  Among those in which the oxetane group is bifunctional, preferably, compounds represented by the following general formula (3-3), general formula (3-4), or chemical formula (3-5) can be mentioned. In particular, the use of the compound represented by the chemical formula (3-5) is preferable because hardness, a residual film rate, and adhesion are improved.

[In general formula (3-3), R ² may be the same or different and is a hydrocarbon group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or 1 to 10 carbon atoms] Represents a hydroxyalkylene group of R ³ represents a divalent organic group having 1 to 30 carbon atoms. n ¹ is an integer of ¹ to 20; ]

The number of carbon atoms of R ² is more preferably 1-4, still more preferably 1 or 2, and particularly preferably 1.

n ² is preferably one represented by an integer from 1 to 10.

As an oxetane group is what is trifunctional or more,
Pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta Kiss (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, caprolactone modified di Pentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, oxe Polymerizing (meth) acrylic monomers such as resins containing tan groups (e.g., oxetane-modified phenolic novolac resins described in Japanese Patent No. 378 3462) and the aforementioned (3-ethyl oxetan-3-yl) methyl (meth) acrylate And polymers obtained by Such polymers can be obtained using known polymerization methods.

  Among those having trifunctional or more oxetane groups, it is preferable from the viewpoint of hardness and chemical resistance that the oxetane compound is a polymer obtained by polymerizing (3-ethyl oxetan-3-yl) methyl (meth) acrylate. .

  The oxetane compound is preferably a compound which is preferably bifunctional or more, more preferably bifunctional, and particularly preferably a compound represented by the chemical formula (3-5).

  The content of the oxetane compound used in the photosensitive resin composition of the present invention is usually 0.5 to 50% by mass, preferably 5 to 40%, based on the solid content of the photosensitive resin composition (100% by mass). %. When the content of the oxetane compound is in the above range, the chemical resistance is high and an excellent coating film is obtained, which is preferable.

(Vinyl ether compound)
As the vinyl ether compound, any known compound can be used without particular limitation, but those having 3 to 35 carbon atoms are preferable, and examples thereof include the following monofunctional or polyfunctional vinyl ethers. The "monofunctional vinyl ether" means a vinyl ether compound having one vinyl group, and the "polyfunctional vinyl ether" means a vinyl ether compound having two or more vinyl groups.
Examples of monofunctional vinyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methyl Cyclohexylmethylvinylether, benzylvinylether, dicyclopentenylvinylether, 2-dicyclopentenoxyethylvinylether, methoxyethylvinylether, ethoxyethylvinylether, butoxyethylvinylether, methoxyethoxyethylvinylether, ethoxyethoxyethylvinylether, methoxypolyethylene glycol vinyl ether Tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethyl cyclohexyl methyl vinyl ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxy Ethyl vinyl ether, phenyl ethyl vinyl ether and phenoxy polyethylene glycol vinyl ether, ethyl oxetane methyl vinyl ether, dicyclopentadiene vinyl ether, cyclohexane dimethanol vinyl glycidyl ether, tricyclodecane vinyl ether acrylic acid 2- (vinyloxyethoxy) ethyl, metha cylco Acid 2- (vinyloxy) ethyl, and the like.

Examples of polyfunctional vinyl ethers include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, propylene glycol divinyl ether, butylene glycol divinyl ether, hexanediol divinyl ether, bisphenol A alkylene oxide divinyl ether, Divinyl ethers such as bisphenol F alkylene oxide divinyl ether; trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, pentaerythritol tetravinyl ether, dipentaerythritol pentavinyl ether Ter, dipentaerythritol hexavinyl ether, EO addition trimethylolpropane trivinyl ether, PO addition trimethylolpropane trivinyl ether, EO addition ditrimethylolpropane tetravinyl ether, PO addition ditrimethylolpropane tetravinyl ether, EO addition pentaerythritol tetravinyl ether, PO addition penta Examples thereof include erythritol tetravinyl ether, EO-added dipentaerythritol hexavinyl ether, and PO-added dipentaerythritol hexavinyl ether.
These vinyl ethers can be used alone or in combination of two or more at an arbitrary ratio as needed.

  Among these vinyl ethers, diethylene glycol divinyl ether or triethylene glycol divinyl ether is preferable from the viewpoint of high sensitivity and availability, and ethyl oxetane methyl vinyl ether or dicyclopentadiene vinyl ether is preferable from the viewpoint of chemical resistance.

  The content of the vinyl ether compound used in the photosensitive resin composition of the present invention is usually 0.5 to 30% by mass, preferably 1 to 10% by mass, based on the solid content of the photosensitive resin composition (100% by mass). %. When the content of the vinyl ether compound is in the above range, the residual film rate and the chemical resistance are high and an excellent coating film is obtained, which is preferable.

(Epoxy compound)
As an epoxy compound used for the photosensitive resin composition of this invention, the well-known compound which has an epoxy group can be used without being specifically limited. Specific examples of the epoxy compound include phenol novolac epoxy resin, cresol novolac epoxy resin, trishydroxyphenylmethane epoxy resin, dicyclopentadiene phenol epoxy resin, bisphenol-A epoxy resin, bisphenol-F epoxy resin, Examples thereof include biphenol type epoxy resin, bisphenol-A novolac type epoxy resin, naphthalene skeleton-containing epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin and the like. Among these, the epoxy compound is preferably a phenol novolac epoxy resin or a cresol novolac epoxy resin from the viewpoint of the residual film rate and the chemical resistance. Further, among these epoxy compounds, those having an epoxy equivalent (g / eq.) Of 150 to 250 are preferable, and those of 170 to 220 are particularly preferable, from the viewpoint of rapid curing and chemical resistance.

(Phenol novolac epoxy resin)
Examples of phenol novolac type epoxy resins include Epiclon N-740, Epiclon N-770, Epiclon N-775 (manufactured by DIC Corporation), D.I. E. N438 (Dow Chemical Co., Ltd.), RE-306 (Nippon Kayaku Co., Ltd.), jER152, jER154 (all are Mitsubishi Chemical Co., Ltd.), etc. are mentioned.

(Cresol novolac epoxy resin)
Examples of cresol novolac type epoxy resins include Epiclon N-660, Epiclon N-665, Epiclon N-670, Epiclon N-673, Epiclon N-680, Epiclon N-695, Epiclon N-665-EXP, Epiclon N- 672-EXP (all are manufactured by DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S (all are manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 (manufactured by Union Carbide Corporation), ESCN- 195 (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

  Examples of trishydroxyphenylmethane type epoxy resins include EPPN-503, EPPN-502H, and EPPN-501H (all manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Co., Ltd.), jER E1032H60. (Mitsubishi Chemical Co., Ltd. product) etc. are mentioned.

  Examples of the dicyclopentadiene phenol type epoxy resin include Epiclon EXA-7200 (manufactured by DIC Corporation), TACTIX-556 (manufactured by Dow Chemical Corporation), and the like.

  As bisphenol type epoxy resins, for example, jER 828, jER 1001 (all are manufactured by Mitsubishi Chemical Corporation), UVR-6410 (manufactured by Union Carbide Corporation), D.I. E. Bisphenol-A type epoxy resin such as R-331 (manufactured by Dow Chemical Co., Ltd.), YD-8125 (manufactured by Toto Kasei Co., Ltd.), UVR-6490 (manufactured by Union Carbide), YDF-8170 (Toto Kasei And other bisphenol-F epoxy resins, etc.

  Examples of the biphenol type epoxy resin include biphenol type epoxy resins such as NC-3000 and NC-3000H (all manufactured by Nippon Kayaku Co., Ltd.), and bixylenol such as jER YX-4000 (manufactured by Mitsubishi Chemical Co., Ltd.) Type epoxy resin, jER YL-6121 (manufactured by Mitsubishi Chemical Corporation), and the like.

  Examples of the bisphenol A novolac epoxy resin include Epiclon N-880 (manufactured by DIC Corporation), jER E157S75 (manufactured by Mitsubishi Chemical Corporation), and the like.

  As a naphthalene frame | skeleton containing epoxy resin, NC-7000, NC-7300 (all are Nippon Kayaku Co., Ltd. product), EXA-4750 (DIC Corporation product) etc. are mentioned, for example.

  Examples of the alicyclic epoxy resin include Celoxide 2021 P, EHPE-3150, and Epolide GT 401 (manufactured by Daicel Co., Ltd.).

  As a heterocyclic epoxy resin, TEPIC-L, TEPIC-H, TEPIC-S (all are Nissan Chemical Industries Co., Ltd. product) etc. are mentioned, for example.

  These epoxy compounds may be used alone or in combination of two or more at an arbitrary ratio as needed.

  The content of the epoxy compound used in the photosensitive resin composition of the present invention is usually 0.5 to 50% by mass, preferably 1 to 40%, based on the solid content of the photosensitive resin composition (100% by mass). %. When the content of the epoxy compound is in the above range, it is preferable because the chemical resistance is high and an excellent coating film can be obtained.

  Cationic Polymerization of the Present Invention The cationically polymerizable compound (B) of the present invention contains at least an episulfide compound (B1) and a cationically polymerizable compound (B2) other than the episulfide compound, and is other than the episulfide compound (B1) and the episulfide compound When the content ratio of the cationically polymerizable compound (B2) is in the range of (B1) :( B2) = 20: 80 to 80:20, the hardness, adhesion, and chemical resistance are high, and the coating film is excellent It is preferable because it can be obtained.

<Alkali-soluble resin>
As alkali-soluble resin contained in the photosensitive resin composition of this invention, a thermoplastic resin etc. are mentioned, for example. The alkali-soluble resin is preferably a transparent resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light range. Moreover, when using in the form of an alkali-developable photosensitive composition, it is preferable to use an alkali-soluble acrylic resin obtained by copolymerizing an acidic substituent-containing ethylenically unsaturated monomer. Furthermore, in order to further improve the photosensitivity, an active energy ray curable resin having an ethylenically unsaturated double bond can also be used.

  As a thermoplastic resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin And polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

  Examples of the acrylic alkali-soluble resin obtained by copolymerizing the acidic substituent-containing ethylenically unsaturated monomer include resins having an acidic substituent such as a carboxyl group or a sulfone group. Specifically as the alkali-soluble resin, an acrylic resin having an acidic substituent, an α-olefin / (maleic anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, Or isobutylene / (anhydride) maleic acid copolymer and the like. Among them, at least one resin selected from an acrylic resin having an acidic substituent and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, is preferably used because it is high in heat resistance and transparency. Be

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins in which an ethylenically unsaturated double bond is introduced by the method (i) or (ii) shown below.

[Method (i)]
As the method (i), for example, to a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers. A carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added, and a polybasic acid anhydride is further reacted with the produced hydroxyl group to form an ethylenically unsaturated double bond and a carboxyl group There is a way to introduce it. The resin thus obtained is preferable because it is excellent in residual film rate and hardness.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, 3,4-epoxybutyl (meth) acrylate And 3,4-epoxycyclohexyl (meth) acrylates, which may be used alone or in combination of two or more. Glycidyl (meth) acrylate is preferred from the viewpoint of the reactivity with the unsaturated monobasic acid in the next step.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano-substituted, etc. Monocarboxylic acids and the like can be mentioned, and these may be used alone or in combination of two or more.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, which may be used alone or in combination of two or more. I do not mind. The remaining anhydride is obtained by using tricarboxylic acid anhydride such as trimellitic acid anhydride or using tetracarboxylic acid dianhydride such as pyromellitic acid dianhydride, if necessary, such as increasing the number of carboxyl groups. It is also possible to hydrolyze the group, etc. In addition, when tetrahydrophthalic anhydride having an ethylenically unsaturated double bond, or maleic anhydride is used as a polybasic acid anhydride, the number of ethylenically unsaturated double bonds can be further increased.

  As an analogous method of the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of the carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and the monomer of another unsaturated monobasic acid having a carboxyl group or the other monomer is copolymerized. There is a method of reacting the isocyanate group of the ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

  As the ethylenically unsaturated monomer having a hydroxyl group, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol There may be mentioned hydroxyalkyl methacrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, which may be used alone or in combination of two or more. In addition, polyether mono (meth) acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and / or butylene oxide etc. to the above hydroxyalkyl (meth) acrylate, poly γ-valerolactone, poly ε-caprolactone, and / or Polyester mono (meth) acrylates to which poly 12-hydroxystearic acid or the like is added can also be used. 2-hydroxyethyl methacrylate or glycerol methacrylate is preferable from the viewpoint of coating foreign matter suppression.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [methacryloyloxy] ethyl isocyanate, but not limited thereto. Two or more types can be used in combination.

  The weight average molecular weight of polystyrene conversion of alkali-soluble resin becomes like this. Preferably, it is 3000-100000, More preferably, it is 5000-50000. When the weight average molecular weight of the alkali-soluble resin is in the above range, the coatability is good, and when it is used as the alkali-soluble resin, film reduction hardly occurs during development, and the developability of the unexposed part during development Tend to be good and are preferred. The molecular weight distribution [weight average molecular weight / number average molecular weight] of the alkali soluble resin is preferably 1.5 to 6.0, and more preferably 1.8 to 4.0. When the molecular weight distribution is in the above range, it is preferable because the developability is excellent.

  The content of the alkali-soluble resin is usually 5 to 90% by mass, preferably 10 to 70% by mass, based on the solid content of the photosensitive resin composition (100% by mass). When the content of the alkali-soluble resin is in the above-mentioned range, it is preferable because the solubility in a developing solution is excellent, the development residue is hardly generated, and the film reduction of the exposed portion is hardly generated at the time of development.

<Radical polymerizable compound having (meth) acrylic group>
The photosensitive resin composition of the present invention may further contain a radically polymerizable compound having a (meth) acrylic group. By including a radically polymerizable compound having a (meth) acrylic group, a coating film having more excellent hardness can be obtained. The radically polymerizable compound having a (meth) acrylic group is preferably at least trifunctional or more from the viewpoint of hardness and a residual film rate.

  Specific examples of the radically polymerizable compound having a (meth) acrylic group include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, and dipentamer. Erythritol hexa (meth) acrylate, caprolactone modified dipentaerythritol hexaacrylate, reaction product of pentaerythritol tri (meth) acrylate and acid anhydride, reaction product of dipentaerythritol penta (meth) acrylate and acid anhydride And a reaction product of a homopolymer of pentaerythritol and acrylic acid.

Further, it may have an acid group, for example, an esterified product of free hydroxyl group-containing poly (meth) acrylate of polyhydric alcohol and (meth) acrylic acid, and dicarboxylic acid; polyvalent carboxylic acid, mono Esterified products with hydroxyalkyl (meth) acrylates can be mentioned. Specific examples thereof include monohydroxy oligo acrylate or mono hydroxy oligo methacrylates such as pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc., malonic acid, succinic acid, glutaric acid, terephthalic acid Carboxylic acid-containing monoesters with dicarboxylic acids such as acids; propane-1,2,3,4-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, benzene-1,2,3 Tetracarboxylic acids such as 2,4-tetracarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc. It can be given free carboxyl group-containing oligo esterified products of monohydroxy monoacrylate or monohydroxymonocarboxylic methacrylates.
These radically polymerizable compounds having a (meth) acrylic group may be used alone or in combination of two or more at an arbitrary ratio as needed.

  As commercially available radically polymerizable compounds having such (meth) acrylic groups, for example, ARONIX M-400, ARONIX M-460, ARONIX M-402, ARONIX M-510, ARONIX M-520 (Toagosei Co., Ltd. ), KAYARAD T-1420, KAYARAD DPHA, KAYARAD DPCA20, KAYARAD DPCA30, KAYARAD DPCA60, KAYARAD DPCA 120 (manufactured by Nippon Kayaku Co., Ltd.), Viscote # 802, Viscote # 2500, Viscote # 1000, Viscote # 1080 (Osaka organic chemistry) Industrial Co., Ltd.) can be mentioned.

  When using the radically polymerizable compound which has a (meth) acryl group, it is preferable to use content in the quantity of 5-80 mass% in a total of 100 mass% of solid content of a resin composition. In this case, if the content of the radically polymerizable compound having an ethylenically unsaturated double bond is less than 5% by mass, the effect of increasing the hardness or imparting solvent resistance is hardly obtained, and if it is more than 80% by mass, the transmittance decreases and adhesion Sex decline may occur. More preferably, it is 10 to 50% by mass.

<Solvent>
The photosensitive resin composition of the present invention may further contain a solvent.
As the solvent, for example, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2- Methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butane Diol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dibenzene Chlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butylamine Coal, n-butylbenzene, n-propylacetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert -Butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene Glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl Ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, cyclopentanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Ter, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene Glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol , Methyl isobutyl ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic esters, ethylene carbonate and propylene carbonate.
These solvents may be used alone or in combination of two or more at an arbitrary ratio as needed.

In particular, in consideration of the drying property of the solvent, it is preferable to include a high boiling point solvent having a temperature of 160 ° C. or higher in a die coating or printing method, for example, 3-methoxy-3-methyl-1-butanol (bp 174 ° C.), 1, 3-butanediol (bp 203 ° C), 3-methyl-1,3-butanediol (bp 203 ° C), 2-methyl-1,3-propanediol (bp 213 ° C), diisobutyl ketone (bp 168.1 ° C), ethylene glycol Monobutyl ether (bp 171.2 ° C.), ethylene glycol monohexyl ether (bp 208.1 ° C.), ethylene glycol monobutyl ether acetate (bp 191.5 ° C.), ethylene glycol dibutyl ether (bp 203.3 ° C.), diethylene glycol monomethyl ether (bp 194. 0 ° C), Glycol monoethyl ether (bp 202.0 ° C.), diethylene glycol diethyl ether (bp 188.4 ° C.), diethylene glycol monoisopropyl ether (bp 207.3 ° C.), propylene glycol monobutyl ether (bp 170.2 ° C.), propylene glycol diacetate (bp 190) .0 ° C.), dipropylene glycol monomethyl ether (bp 187.2 ° C.), dipropylene glycol monoethyl ether (bp 197.8 ° C.), dipropylene glycol monopropyl ether (bp 212.0 ° C.), dipropylene glycol dimethyl ether (bp 175 ° C.) ), Tripropylene glycol monomethyl ether (bp 206.3 ° C.), ethyl 3-ethoxypropionate (bp 169.7 ° C.), 3-methoxy Ethyl acetate (bp 172.5 ° C.), 3-methoxy-3-methylbutyl acetate (bp 188 ° C.), γ-butyrolactone (bp 204 ° C.), N, N-dimethylacetamide (bp 166.1 ° C.), N-methylpyrrolidone (bp 202) ° C), p-chlorotoluene (bp 162.0 ° C), o-diethylbenzene (bp 183.4 ° C), m-diethylbenzene (bp 181.1 ° C), p-diethylbenzene (bp 183.8 ° C), o-dichlorobenzene (bp 180) .5 ° C), m-dichlorobenzene (bp 173.0 ° C), n-butylbenzene (bp 183.3 ° C), sec-butylbenzene (bp 178.3 ° C), tert-butylbenzene (bp 169.1 ° C), cyclo Hexanol (bp 161.1 ° C), cyclohexyl acetate (b 173 ° C.), include such methylcyclohexanol (bp174 ℃), preferably high-boiling solvent or 160 ° C. 5 to 50 wt% based on the total amount of solvent.
The content of the solvent can be used in an amount of 200 to 4000 parts by mass with respect to a total of 100 parts by mass of solid content in the resin composition.

<Other ingredients>
In the photosensitive resin composition of the present invention, a silane compound, a heat-curable catalyst, inorganic oxide fine particles, an antioxidant, a surfactant, a storage stabilizer, a leveling agent, a light stabilizer, etc. are used as needed. You can also

<Silane compound>
The photosensitive resin composition of the present invention may further contain a silane compound. The inclusion of a silane compound is preferable because adhesion with a glass substrate, ITO or the like is improved.

  Examples of the silane compound include an amide or urethane skeleton, an imidazole group, an isocyanate group, an isocyanate group, a vinyl group, a glycidyl group, a (meth) acryloyloxy group, an amino group, a ureido group, a mercapto group, and a silane compound having a sulfide group. Among the silane compounds, a silane compound having an amide or urethane skeleton, more preferably a silane compound represented by General Formula (6), or a silane compound (D2) having an imidazole group, more preferably represented by Chemical Formula (7) Silane compounds are preferable because they are more excellent in adhesion.

[Silane compound having an amide or urethane skeleton]
As a silane compound (D1), the silane compound shown by General formula (6) is mentioned.

[In general formula (6), R ³¹ represents an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, carbon 7 to 30 aralkyl or C 7 to 30 alkaryl,
X is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, or an alkoxylene group having 1 to 20 carbon atoms,
R ³² _, R ³³ and R ³⁴ are each independently an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an alkyl group having 1 to 20 carbon atoms, and an aryl having 6 to 20 carbon atoms A group, an aralkyl group having 7 to 30 carbon atoms, an alkaryl group having 7 to 30 carbon atoms, a siloxane group having a substituent, a halogen atom, a hydroxy group or a hydrogen atom. ]

When R ³¹ is an alkyl group, aryl group, aralkyl group or alkaryl group, it is a silane compound having an amide skeleton, and when R ³¹ is an alkoxy group or aryloxy group, it is a silane compound having a urethane skeleton.

  Examples of the silane compound represented by the general formula (6) include (3-carbamate ethyl) propyltriethoxysilane, (3-carbamate ethyl) propyltrimethoxysilane, (3-carbamate ethyl) propyltripropoxysilane, (3 -Carbamate propyl) propyl triethoxysilane, (3-carbamate propyl) propyl trimethoxysilane, (3-carbamate propyl) propyl tripropoxysilane, (3-carbamate butyl) propyl triethoxysilane, (3-carbamate butyl) propyl Trimethoxysilane, (3-Carbamate butyl) propyl tripropoxysilane, (3-Carbamate butyl) butyl tripropoxysilane, (3-Carbamate butyl) propyl methyl diethoxysilane, (3-carbene Mate pentyl) propyl triethoxysilane, (3-carbamate hexyl) propyl triethoxysilane, 3- carbamate octyl) pentyl tributoxysilane, (3- carbamate ethyl) propyl silyl trichloride, (3- carbamate ethyl) propyl trimethylsilane, Examples include 3-carbamate ethyl) propyldimethylsilane, 3-carbamate ethyl) propyltributylsilane, 3-carbamate ethyl) ethyl-p-xylenetriethoxysilane, 3-carbamate ethyl) -p-phenylenetriethoxysilane and the like. It is not restricted to these. The silane compound (D1) represented by the general formula (6) may be a silanol compound produced by hydrolysis thereof or a polyorganosiloxane compound obtained by dehydration condensation of them.

  Since the silane compound represented by the general formula (6) is excellent in heat resistance, the coating film is unlikely to turn yellow and is also chemically stable, so the stability over time is excellent, and the developability is impaired even after time There is no

[Silane compound having an imidazole group]
The silane compound having an imidazole group is a silane compound having an imidazole group, and one type selected from an imidazole group as a first functional group in one molecule, an alkoxysilyl group as a second functional group, a chlorosilyl group and an acetoxysilyl group The compound is, for example, a compound having both of the above, and the imidazole ring may have a substituent such as a saturated hydrocarbon group or an unsaturated hydrocarbon group. Specifically, a reaction product of imidazole, 2-alkylimidazole, 2,4-dialkylimidazole, 4-vinylimidazole, etc. with a 3-glycdoxypropylsilane compound, 2-ethyl-4-methylimidazopropylsilane, and salts thereof And intramolecular condensates, intermolecular condensates and the like.

Among the silane compounds having an imidazole group, more preferred are silane compounds represented by the chemical formula (7). Further, it may be a silane compound represented by the chemical formula (7), a silanol compound produced by hydrolysis of the silane compound, or a polyorganosiloxane compound produced by dehydration condensation reaction of the silanol compound, and a mixture thereof It is good.

  Commercially available silane compounds represented by chemical formula (7) include IM-1000 (manufactured by JX Nippon Mining & Metals Corp.).

Other silane compounds include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidone Xypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxy Silane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) 3-aminopropyltrimethoxysilane, N-2- (aminoethyl) -3-aminopropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- ( 1,3-Dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-ureidopropyl Triethoxysilane, 3-chloropropyltrimethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, etc. It is.
These silane compounds can be used alone or in combination of two or more at any ratio as required.

  The weight average molecular weight (Mw) of the silane compound is more preferably 200 or more and less than 5,000 from the viewpoint of developability. The content of the silane compound is more preferably 1% by mass or more and less than 20% by mass in 100% by mass of the total solid content of the resin composition, from the viewpoint of developability. More preferably, it is 1% by mass or more and less than 10% by mass.

  When the weight average molecular weight (Mw) of the silane compound is 200 or more, it is preferable from the viewpoint of availability, and less than 5000 is preferable because the developability becomes good. Moreover, when content is 1 mass% or more, since it is excellent in the transmittance | permeability and developability and less than 20 mass%, since it is excellent not only in adhesiveness and hardness to a base material, and developability.

<Heating curing catalyst>
The photosensitive resin composition in the present invention can also contain a heat-curable catalyst.
The heat-curable catalyst is a compound or a composition that exhibits a catalytic ability with respect to an episulfide compound and an epoxy resin by being heated to 80 to 200 ° C. or more. These can be blended alone or appropriately dispersed in another resin such as an epoxy resin. Examples of such a heat-curable catalyst include the following.

Dicyandiamide: As a commercial product, jER cure DICY7, 15, 20, 7A (the above is Japan Epoxy Resins Co., Ltd./trade name), Omicure DDA10, DDA50, DDA100, DDA5, CG-325, CG-1200, CG-1400 DICYNEX 325, DICY-F, DICY-M (the above are CVC Specialty Chemicals, Inc./trade name), and the like.
Amine adduct: Commercially available products include Amicure PN-23, MY-24, PN-D, MY-D, PN-H, and MY-H (the above are Ajinomoto Fine Techno Co., Ltd./trade names), etc. .
Imidazole: Cuazole 2MZ, 2PZ, 2PHZ, 2MZ-OK, 2PZ-OK, 2P4 MHZ, 2PH4, 2E4MZ, C11Z, C17Z, 2MA-OK, 1B2MZ (all are manufactured by Shikoku Kasei Kogyo Co., Ltd./trade name) , JER cure IBMI-12, EMI-24, BMI-12 (the above are made by Japan Epoxy Resins Co., Ltd. / trade name), Nichigo imidazole 2PI, 2MI, 2E4MI, 1B2MI (the above are manufactured by Japan Synthetic Chemical Industry Co., Ltd. / Trade name) etc. Further, a type in which a functional group of these compounds is appropriately substituted with an inactive group cyanoethyl group, a type in which salt formation is made with trimellitic acid or the like, and a type in which dicyandiamide is modified can be used similarly. Examples of these commercially available products include 2E4MZ-CN, 2PHZ-CN, C11Z-CNS, 2MZ-AZINE (the above are manufactured by Shikoku Kasei Kogyo Co., Ltd./trade name), and the like.
Urea-type adduct type, aromatic urea: Commercially available products Fujicure FXR 1020, 1030, 1081 (the above are made by Fuji Kasei Kogyo Co., Ltd./trade name), DCMU (Hodogaya Chemical Industry Co., Ltd.), 3- (3, 4-dichlorophenyl) -1, 1-dimethylurea / trade name), Omicure 24, 52, 94 (The above are CVC Specialty Chemicals, Inc. make / brand name), etc. are mentioned.
Iridoid type: Epicure YPH-101, 102, 103, 104, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210 (commercially available from Japan Epoxy Resin Co., Ltd./trade name) Can be mentioned.
Salts of p-toluenesulfonic acid: Commercially available products include Anchor 1786B, Catalyst 2134 (above, Air Products Japan Co., Ltd./trade name), Adeka Hardener EH-3293S (trade name, ADEKA / trade name), etc. It can be mentioned.
Microcapsulated latent curing agent: Examples of commercially available products include Novac HX-3721, 3272, 3741, 3742, 3748, 3613, 3088, 3921 HP, 3941 HP (all manufactured by Asahi Kasei Chemicals Corporation / trade name).
In addition, diaminomaleonitrile and derivatives thereof, Schiff bases, melamine and derivatives thereof, amine imides synthesized by carboxylic acid ester, dimethylhydrazine and epoxy compounds, amine imide imidazole compounds, and the like can be appropriately used.

  Among these, imidazole compounds or dicyandiamides and modified products thereof are preferable from the viewpoint of curability and availability. The content of the heat-curable catalyst is preferably 0.5 to 30% by mass, and more preferably 0.7 to 15% by mass in 100% by mass in total of the solid content of the photosensitive resin composition. If this range is exceeded, a problem may occur that curing does not proceed sufficiently or adhesion is not sufficiently developed.

<Acid anhydride curing agent>
The photosensitive resin composition of the present invention may further contain an acid anhydride curing agent. The acid anhydride curing agent can accelerate the thermal curing by mixing with the episulfide compound and the epoxy resin. The difference from the above-mentioned thermosetting catalyst is that there is no catalytic action.

As an acid anhydride curing agent,
Aliphatic carboxylic acid anhydrides such as acetic anhydride, propionic acid anhydride, butyric anhydride, hexanoic acid anhydride, acetic acid propionic acid anhydride, etc. Aliphatic dicarboxylic acid anhydrides such as succinic acid anhydride, maleic acid anhydride, cyclo Aromatic cyclic carboxylic acid anhydrides such as hexanoic acid carboxylic acid, aromatic carboxylic acid anhydrides such as benzoic acid anhydride, phthalic acid anhydride etc., aromatics such as pyromellitic acid anhydride, trimellitic acid anhydride etc. Group dicarboxylic acid anhydride and the like.

  More specifically, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 3-methyl-1,2,3,6-tetrahydrophthalic anhydride, 4 -Methyl-1,2,3,6-tetrahydrophthalic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methyl-3,6 endomethylene-1,2 It is preferable to use 3,3,6-tetrahydrophthalic anhydride 3,3 ', 4,4'-biphenyltetracarboxylic acid dianhydride.

As a commercial item,
RIKACID TH, RIKACID HT-1A, RIKACID HH, RIKACID MH-700, RIKACID MH-700 G, RIKACID MH (all from Nippon Nippon Co., Ltd.), HN-2200, HN-2000, HN-5500, anhydrous methyl hymic Acid (MHAC-P) (all are manufactured by Hitachi Chemical Co., Ltd.),
YH-306, YH-307 (both from Mitsubishi Chemical Corporation)
Etc.

  The acid anhydride curing agent is preferably used in an amount of 0.1 to 40% by mass in the total 100% by mass of the solid content of the episulfide compound (B1) or the epoxy compound, and it is 5 to 5 from the viewpoint of chemical resistance. More preferably, it is used in an amount of 30% by weight.

<Inorganic oxide fine particles>
Inorganic oxide fine particles can be used for the photosensitive resin composition of the present invention. The inorganic oxide fine particles are at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium, zinc, indium, tin, antimony and cerium from the viewpoint of the colorlessness of the cured film of the curable composition obtained. It is preferable that it is an oxide particle of Among them, oxide particles of silicon, zirconium, titanium or aluminum are preferable from the viewpoint of transmittance, and oxide particles of silicon are particularly preferable.

  The inorganic oxide fine particles can be physically dispersed, such as plasma discharge treatment or corona discharge treatment, in the dispersion liquid or in the coating liquid, in order to achieve dispersion stabilization or to enhance the affinity and bondability with the alkali-soluble component. Chemical surface treatment may be carried out with a chemical surface treatment, a surfactant, a coupling agent or the like.

  1 nm-1000 nm are preferable, as for the average primary particle diameter of oxide particle, 3 nm-100 nm are more preferable, and 5 nm-30 nm are especially preferable. When the average primary particle diameter exceeds 1000 nm, the transparency of the cured product tends to decrease, and the surface state of the film tends to deteriorate. In addition, various surfactants and amines may be added to improve the dispersibility of the particles.

  The average primary particle size of the inorganic oxide fine particles is measured, for example, using the BET method. Specifically, the specific surface area of the inorganic oxide fine particles obtained by the BET method is obtained, the ratio of the volume to the surface area is calculated using the specific gravity of the inorganic oxide, and the particles are assumed to be true spheres, There is a method of obtaining the particle diameter from these ratios and setting it as an average primary particle diameter.

  The inorganic oxide particles are preferably used as an organic solvent dispersion. When used as an organic solvent dispersion, the dispersion medium is preferably an organic solvent from the viewpoint of compatibility with other components and dispersibility. Examples of such an organic solvent include alcohols such as methanol, ethanol, isopropanol, butanol and octanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ-butyrolactone Esters such as propylene glycol monomethyl ether acetate and propylene glycol monoethyl ether acetate; Ethers such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; Aromatic hydrocarbons such as benzene, toluene and xylene; Dimethylformamide, dimethylacetamide, Amides such as N-methyl pyrrolidone can be mentioned. Among them, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferable.

  As a commercial item marketed as a fine oxide particle dispersion of silicon, Nissan Chemical Industries, Ltd. PMA-ST, PMA-ST-MS, IPA-ST, IPA-ST-MS, IPA-ST-L, IPA -ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-L, MIBK-ST, NBA-ST, XBA-ST, DMAC-ST, ST-UP , ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, MEK-AC-2140C, PGM-AC-2140Y, MIBK-AC-2140Z And MEK-EC-2130Y, etc., Catalysts and Chemicals Industries Ltd. hollow silica CS60-IPA etc. can be mentioned. As powder silica, Aerosil 130 manufactured by Nippon Aerosil Co., Ltd., Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, manufactured by Asahi Glass Co., Ltd. Sildex H31, H32, H51, H52, H52, H121, H122, Nippon Silica Industries E220A and E220 manufactured by Co., Ltd., SYLYSIA 470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

  Commercial products of aluminum oxide fine particle dispersion include alumina sol-100, alumina sol-200, alumina sol-520 manufactured by Nissan Chemical Industries, Ltd., AS-150I manufactured by Sumitomo Osaka Cement Co., Ltd., and AS-150T manufactured by Sumitomo Osaka Cement Co., Ltd. It can be mentioned.

  Commercially available products as zirconia fine particle oxide dispersions include Nissan Chemical Industries, Ltd. ZR-40BL, ZR-30BS, ZR-30AL, ZR-30AH, etc., Sumitomo Osaka Cement Co., Ltd. HXU-110JC. Can be mentioned. In addition, the oxide particle dispersion liquid of zirconia can be obtained by the method described in Japanese Patent No. 469 2630 or the like.

  As a commercial item marketed as a titanium oxide fine particle dispersion, Nanotech manufactured by CI Kasei Co., Ltd. and D-962 manufactured by Sakai Chemical Industry Co., Ltd. can be mentioned. In addition, titanium oxide fine particle dispersion can be obtained by the method described in Japanese Patent No. 469 2630 and the like.

  In addition, as a commercial item of oxide fine particle dispersions, such as zinc, Nanotech etc. made by CI Kasei Co., Ltd. can be mentioned.

  When the inorganic oxide fine particles are contained, the content is preferably 10 to 80% by mass, and more preferably 20 to 70% by mass in 100% by mass of the total solid content in the photosensitive resin composition. When the addition amount is 10% by mass or more, the effect of improving the hardness and acid resistance is high, and when it is 80% by mass or less, excellent developability and transmittance can be obtained.

<Antioxidant>
The resin composition of the present invention can contain an antioxidant. An antioxidant can suppress the fall of the transmittance | permeability by yellowing etc. by passing through a heating process. Therefore, yellowing at the time of a heating process can be prevented by containing an antioxidant, and the coating film with high transmittance | permeability can be obtained.

  In the present invention, the "antioxidant" may be a compound having an ultraviolet absorbing function, a radical trapping function, or a peroxide decomposing function, and specifically, hindered phenol type or hindered amine type as an antioxidant. And phosphorus, sulfur, benzotriazole, benzophenone, hydroxylamine, salicylic acid ester, and triazine compounds, and known ultraviolet light absorbers, antioxidants and the like can be used. Among these antioxidants, phenol-based antioxidants, phosphorus-based antioxidants and sulfur-based antioxidants are preferable from the viewpoint of achieving both the transmittance of the coating film and the sensitivity. Among phenol-based ones, hindered phenol-based antioxidants having high steric hindrance are particularly preferable.

[Phenolic antioxidant]
For example, 2,6-di-tert-butyl-4-ethylphenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-tert-butylanilino) -1,3. 5-triazine, 2,2-thio-diethylene bis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, N, N'-hexamethylene bis (3,5-di- t-Butyl-4-hydroxy-hydrocinnamide), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris- (3,5-di-t-butyl-4-hydroxybenzyl) -Isocyanurate, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butyl-4-methoxyphenol, triethylene glycol Bis {3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) Propionate}, pentaerythrityl-tetrakis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) Propionate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxyphenyl) benzene, etc. may be mentioned, and may be used alone or in combination of two or more. .

  Among them, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3, 3, 5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert- Hindered phenolic antioxidants selected from the group consisting of butyl-4-hydroxybenzyl phosphonate-diethyl ester and tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate are It is preferable from the viewpoint of photocurability.

[Phosphorus antioxidant]
As a phosphorus antioxidant, although what is marketed can be used, tris [2,4-di- (tert) -butylphenyl] phosphine tris [2-[[2,4,8,10-tetrakis ( 1,1-Dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphepin-6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11- Tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphepin-2-yl) oxy] ethyl] amine, ethyl phosphite bis (2,4-ditert-butyl-6-) Methylphenyl) is mentioned, It is preferable that it is at least 1 sort (s) of compound selected from the group which consists of these, and 1 or 2 types can be used for these.

[Sulfur-based antioxidants]
Sulfur-based antioxidants are antioxidants that contain sulfur in the molecule. As such sulfur-containing antioxidants, commercially available ones can be used, but dioctadecyl 3,3'-thiodipropanoate, dimyristyl-3,3'-thiodipropionate, dipalmityl-3,3'- Thiodipropionate, distearyl-3,3′-thiodipropionate, 4,4′-thiobis-3-methyl-6-tert-butylphenol, thiodiethylenebis [3- (3,5-di-tert- Butyl 4-hydroxyphenyl) propionate] is preferable and it is preferable that it is at least 1 type of compound chosen from the group which consists of these, and 1 type or 2 types or more can be used for these.

  These antioxidants can be used alone or in combination of two or more at an arbitrary ratio as required.

  The content of the antioxidant is preferably 0.1% by mass or more and less than 4% by mass in 100% by mass of the total solid content of the resin composition. If the amount is less than 0.1% by mass, the effect of preventing yellowing is difficult to obtain because the antioxidant is insufficient, and if it is more than 4% by mass, radicals generated at the time of ultraviolet light exposure are captured. Curing of the composition may be insufficient.

<Storage stabilizer>
Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organics such as t-butylpyrocatechol, triethylphosphine and triphenylphosphine Phosphine, phosphite and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 5% by mass in the total 100% by mass of the resin composition.

<Leveling agent>
It is preferable to add a leveling agent to the photosensitive resin composition of the present invention in order to improve the leveling property of the composition on a transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in its main chain is preferred. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-330 manufactured by BYK Chemie, and the like. As a specific example of dimethylsiloxane which has a polyester structure in a principal chain, BYK-310 by BYK-Chemie company, BYK-370, etc. are mentioned. The dimethylsiloxane having a polyether structure in the main chain and the dimethylsiloxane having a polyester structure in the main chain can also be used in combination. In general, the content of the leveling agent is preferably 0.003 to 0.5% by mass in 100% by mass of the total of the resin composition.

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a low solubility in water while having a hydrophilic group, and when it is added to a coloring composition, It is characterized by low surface tension reduction ability, and in addition to low surface tension reduction ability, it is useful that the wettability to the glass plate is good, and the addition amount at which defects of the coating film due to foaming do not appear. Those which can sufficiently suppress the chargeability can be preferably used. As a leveling agent which has such a preferable characteristic, dimethylpolysiloxane which has a polyalkylene oxide unit can use it preferably. The polyalkylene oxide unit may be a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit to dimethylpolysiloxane is a pendent type in which the polyalkylene oxide unit is bonded to a repeating unit of dimethylpolysiloxane, a terminal-modified type bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane It may be any of linear block copolymer types alternately and repeatedly bonded. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2203. -2-207, but not limited thereto.

The leveling agent may be supplemented with an anionic, cationic, nonionic or amphoteric surfactant. The surfactant may be used as a mixture of two or more.
Examples of anionic surfactants to be added to leveling agents include polyoxyethylene alkyl ether sulfate, sodium dodecyl benzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearic acid, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphoric acid Ester etc. are mentioned.

  Examples of the cationic surfactant added to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. As a nonionic surfactant which is added to the leveling agent as auxiliaries, polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearate And alkylbetaines such as alkyldimethylaminoacetic acid betaines; amphoteric surfactants such as alkylimidazolines; and fluorine-based and silicone-based surfactants.

<Manufacturing method of resin composition>
The photosensitive resin composition of the present invention comprises a photocationic polymerization initiator (A), a cationically polymerizable compound (B), an alkali-soluble resin, and, if necessary, a photoradical polymerization initiator, a solvent, a thermosetting catalyst, Inorganic oxide fine particles, a silane compound, an antioxidant, a leveling agent, other components, etc. can be obtained by stirring and mixing. The photosensitive resin composition of the present invention can be coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, by means of centrifugation, sintered filter, membrane filter, etc. It is preferable to remove the mixed dust and foreign matter.

<Cured film>
The cured film of the present invention can be formed by spin coating such as spin coating, die coating, etc. on the glass substrate, ITO, molybdenum, other metal films, organic films, using the photosensitive resin composition of the present invention. It can be formed by cast coating, coating by roll coating, coating by a roll transfer method, or the like. The cured film of the present invention has high hardness and high transmittance, and is excellent in pattern linearity, adhesion, and chemical resistance, so it is particularly suitable for an overcoat used for a touch panel.

  The overcoat is used, for example, in applications of metal wiring protective films used for touch panels, applications of insulating films for insulating between X electrodes and Y electrodes of touch sensors, and the like, and may be used in any way.

  A cured film can be manufactured by the printing method or the photolithographic method using the photosensitive resin composition of this invention, and it is preferable to use the photolithographic method.

  In the case of manufacturing by a photolithography method, for example, after a photosensitive resin composition is applied on a substrate, it is exposed through a mask, developed, a pattern is formed, and a cured film can be manufactured by a process of heating and baking. .

  In the case of forming a cured film, first, a photosensitive resin composition is spray-coated, spin-coated, slit-coated, roll-coated, etc. on a substrate such as a glass substrate, ITO film, molybdenum, other metal film, or organic film. After coating by the coating method, prebaking is performed to evaporate the solvent to form a coating film. Next, the coated film is exposed to light using a super high pressure mercury lamp through a mask, and then it is immersed in a solvent or an alkaline developer, or is developed by spraying a developer by spraying, etc. A cured film can be formed by dissolving and removing the exposed portion and forming a desired pattern, followed by heating and baking.

  In the development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as an alkali developing solution, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.

  As a developing method, a shower developing method, a spray developing method, a dip (immersion) developing method, a paddle (liquid buildup) developing method or the like can be applied.

The heating and baking temperature is often obtained through a high temperature baking process at a temperature exceeding 200 ° C., and the high temperature baking process is a coating obtained by low temperature baking at 200 ° C. or less to promote thermal curing of the coating. Chemical resistance and the like are superior to films. However, the photosensitive resin composition of the present invention does not require high temperature baking, and can obtain a cured film excellent in necessary characteristics such as chemical resistance even when baking at a low temperature of 100 ° C. or less. Therefore, an excellent cured film can be obtained at a low temperature of 100 ° C. or less even when low-temperature baking is required because the structure of an organic electroluminescent display device or a touch panel includes a film with low heat resistance. It is.
However, when the heating and firing temperature is less than 80 ° C., sufficient chemical resistance and the like can not be obtained, so it is preferable to perform heating and firing at 80 ° C. or higher.

  The invention will now be described by way of example. In addition, "part" and "%" in an Example respectively represent "mass part" and "mass%." Also, "PGMEA" means propylene glycol monomethyl ether acetate. Prior to the examples, methods for measuring the weight average molecular weight of the resin and the acid value will be described.

(Weight average molecular weight of resin)
The weight average molecular weight (Mw) of the resin was measured using a TSK gel column (manufactured by Tosoh Corporation) and a GPC equipped with a RI detector (HLC-8120GPC manufactured by Tosoh Corporation), using polystyrene as the developing solvent and polystyrene conversion It is a weight average molecular weight (Mw).

(Acid number)
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the resin solution, and the mixture is stirred and uniformly dissolved, using a 0.1 mol / L KOH aqueous solution as a titration solution, an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) ) And the acid value of the resin solution was measured. And the acid value per solid content of resin was computed from the acid value of resin solution, and solid content concentration of resin solution.

  Then, the manufacturing method of an alkali-soluble resin solution and an oxetane compound is demonstrated.

<Method of Producing Alkali-Soluble Resin Solution>
(Alkali-soluble resin solution (F-1))
Add 100 parts of propylene glycol monomethyl ether acetate to a reaction vessel equipped with a separable 4-neck flask, a thermometer, a condenser, a nitrogen gas inlet pipe, and a stirrer, and heat it at 120 ° C while injecting nitrogen gas into the vessel. From the dropping tube at temperature, a mixture of styrene 5.2 parts glycidyl methacrylate 35.5 parts dicyclopentanyl methacrylate 41.0 parts azobisisobutyronitrile 1.0 part is added dropwise over 2.5 hours to carry out a polymerization reaction The Next, replace the inside of the flask with air,
Acrylic acid 17.0 parts Trisdimethylaminomethylphenol 0.3 parts Hydroquinone 0.3 parts is added, and the reaction is continued for 5 hours at 120 ° C. When the acid value of the solid content reaches 0.8, the reaction is completed and the weight is A resin solution having an average molecular weight of about 12,000 (measured by GPC) was obtained. further,
Tetrahydrophthalic anhydride 30.4 parts 0.5 part of triethylamine is added and reacted at 120 ° C for 4 hours, and propylene glycol monomethyl ether acetate is added so that the nonvolatile content becomes 40% to prepare a resin solution (F-1) did.

(Alkali-soluble resin solution (F-2))
196 parts of cyclohexanone is charged into a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer are attached to a separable four-necked flask, the temperature is raised to 80 ° C., and the inside of the reaction vessel is purged with nitrogen and then dropped. From the tube
n-Butyl methacrylate 37.2 parts 2-Hydroxyethyl methacrylate 12.9 parts Methacrylic acid 12.0 parts Paracumyl phenol ethylene oxide modified acrylate (Toon Gosei Co., Ltd. "ALONIX M110") 20.7 parts 2,2'- A mixture of 1.1 parts of azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, approximately 2 parts of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and methoxypropyl acetate is made so that non-volatile content is 20% by mass in the resin solution synthesized above. Were added to prepare an acrylic resin solution (F-2). The weight average molecular weight (Mw) was 26,000.

(Alkali-soluble resin solution (F-3))
Charge 207 parts of cyclohexanone into a reaction vessel in which a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer are attached to a separable four-necked flask, raise the temperature to 80 ° C, replace the inside of the reaction vessel with nitrogen, and drop From the tube
Methacrylic acid 20.0 parts Paracumylphenol ethylene oxide modified acrylate (Alonix M110 manufactured by TOAGOSEI CO., LTD.) 20.0 parts methyl methacrylate 45.0 parts 2-hydroxyethyl methacrylate 8.5 parts 2,2'-azobisisobutyric acid A mixture of 1.33 parts of ronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, with respect to the total amount of the obtained copolymer solution, after stopping nitrogen gas and stirring while pouring dry air for 1 hour, after cooling to room temperature,
A mixture of 2-methacryloyloxyethyl isocyanate (Kalores MOI manufactured by Showa Denko K. K.) 6.5 parts dibutyltin laurate 0.08 parts cyclohexanone 26.0 parts was dropped at 70 ° C over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain a solution of acrylic resin. After cooling to room temperature, approximately 2 parts of the resin solution is sampled, dried by heating at 180 ° C. for 20 minutes, non-volatile content is measured, and cyclohexanone is added to the previously synthesized resin solution so that the non-volatile content is 20% by mass. Thus, an acrylic resin solution (F-3) was prepared. The weight average molecular weight (Mw) was 18,000.

<Method for producing oxetane compound>
(Oxetane compound solution (B2-A))
In a reaction vessel equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, 100 parts of propylene glycol monomethyl ether acetate is charged, and the temperature is raised to 90 ° C. under a nitrogen stream. A mixed solution in which 100 parts of 3-yl) methyl methacrylate, 48 parts of propylene glycol monomethyl ether acetate and 3 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) are uniformly mixed in advance is added dropwise over 2 hours, Then, the temperature was maintained at 90 ° C. for 2 hours for reaction. After cooling to room temperature, it was diluted with propylene glycol monomethyl ether acetate so that the solid content was 20%, to obtain a propylene glycol monomethyl ether acetate solution (B2-A) of a trifunctional or higher functional oxetane compound.

Example 1
(Photosensitive resin composition (R-1))
After stirring and mixing the mixture of the following composition so that it might become uniform, it filtered with a 1 micrometer filter, and obtained resin composition (R-1).
Irg. 250: 1.60 parts (Iodonium, (4-methylphenyl) [4- (2 methylpropyl) phenyl] hexafluorophosphate: "IRGACURE 250" (manufactured by BASF))
B1-A: 5.00 parts (2,2-bis (4- (2,3-epithiopropoxy) cyclohexyl) propane)
OXE-01: 0.80 parts (1,2-octanedione-1- [4- (phenylthio) phenyl-2- (o-benzoyloxime)] 1,2-octanedione-1- [4- (phenylthio) Phenyl-2- (o-benzoyl oxime: “IRGACURE OXE-01” (manufactured by BASF))
OXT-221: 5.00 parts (Di [1-ethyl (3-oxetanyl)] methyl ether: "Aron oxetane OXT-221" (manufactured by Toagosei Co., Ltd.)
Alkali-soluble resin solution (F-1): 39.90 parts Leveling agent BYK-330: 1.00 parts (Polyether structure-containing dimethylsiloxane in PGMEA solution (adjusted to 1% of solid content): "BYK-330" ( Made by Big Chemie)
PGMEA: 46.70 parts

[Examples 2 to 26, Comparative Examples 1 to 5]
(Photosensitive composition (R-2 to 31))
Hereinafter, a photosensitive resin composition (R-2 to 31) is prepared in the same manner as the photosensitive resin composition (R-1) except that the composition and the blending amount (parts by mass) are changed as shown in Tables 1 to 4. Got).

  The abbreviations in Tables 1 to 4 are described below.

<Photo cationic polymerization initiator (A)>
[Aromatic sulfonium salt (a1)]
· CPI-100P: (manufactured by San-Apro Ltd.) "CPI-100P"; 50% propylene carbonate solution of triarylsulfonium · PF ₆ salt [aromatic iodonium salt (a2)]
Irg 250: “IRGACURE 250” (manufactured by BASF AG); 75% propylene carbonate solution of iodonium, (4-methylphenyl) [4- (2 methylpropyl) phenyl] hexafluorophosphate (1-) [aromatic diazonium salt]
・ 4-nitrobenzene diazonium tetrafluoroborate

<Photo radical polymerization initiator (C)>
[Oxime ester type]
OXE-01: "IRGACURE OXE-01" (manufactured by BASF AG); 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (o-benzoyloxime)]
[Acetophenone series]
Irg. 369 E: “IRGACURE 369 E” (manufactured by BASF AG); 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one [thioxanthone system]
-DETX-S: "Kayacure DETX-S" (manufactured by Nippon Kayaku Co., Ltd.); 2,4-diethylthioxanthone [acyl phosphine oxide type]
-IrgTPO: "IRGACURE TPO" (manufactured by BASF); 2-4-6-trimethylbenzoyl-diphenyl-phosphine oxide

<Cationically Polymerizable Compound (B)>
[Episulfide compound (B1)]
B1-A: 2,2-bis (4- (2,3-epithiopropoxy) cyclohexyl) propane B1-B: bis (3,5-dimethyl-4- (2,3-epithiopropoxy) phenyl ) Methane · B 1 -C: 2, 2-bis (4- (2,3-epithiopropoxy) phenyl) propane [oxetane compound]
-OXT-221: "Aron oxetane OXT-221" (manufactured by Toagosei Co., Ltd.): di [1-ethyl (3-oxetanyl)] methyl ether (difunctional oxetane compound: corresponding to formula (3-5))
-OXBP: "OXBP" (manufactured by Ube Industries, Ltd.); 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl (corresponding to bifunctional oxetane compound: Formula (3-4))
-B2-A: The above trifunctional or higher functional oxetane compound [vinyl ether compound]
-DVE-3: "DVE-3" (manufactured by BASF Corporation); triethylene glycol divinyl ether [epoxy compound]
・ JER152: “jER152” (Mitsubishi Chemical Co., Ltd.); Phenolic novolac epoxy resin

<Leveling agent>
-BYK-330: "BYK-330" (manufactured by Bick Chemie Co., Ltd.); PGMEA solution of dimethylsiloxane containing polyether structure (adjusted to 1% solid content)
<Solvent>
PGMEA: Propylene glycol monomethyl ether acetate

<Evaluation of photosensitive resin composition>
The obtained photosensitive resin composition was evaluated by the evaluation method shown below. The results are shown in Table 5.

[Pencil hardness]
The obtained photosensitive resin composition is applied to a glass substrate (Glass Eagle 2000 manufactured by Corning Co., Ltd.) of 100 mm × 100 mm and 0.7 mm thickness using a spin coater, and a hot plate (“EC-1200 N (manufactured by As One Corporation) Pre-baked at 95 ° C. for 2 minutes using the trade name). Thereafter, ultraviolet exposure was performed with an illuminance of 20 mW / cm ² and an exposure amount of 200 mJ / cm ² using an extra-high pressure mercury lamp. The coated substrate was heated at 95 ° C. for 60 minutes and allowed to cool to obtain a cured film having a thickness of 2.0 μm. The film thickness was measured by a stylus type film thickness meter DECTAC-3 manufactured by ULVAC.
The pencil hardness of the obtained cured film having a thickness of 2.0 μm was measured in accordance with “JIS K5600-5-4 (1999)”. When this value is a hardness of 4H or more, the surface hardness can be said to be good. When the hardness is 3H, the minimum practical hardness is 2H or less is not suitable for practical use.
○; Pencil hardness is 4H or more △; Pencil hardness is 3H
×; Pencil hardness is 2H or less

[Adhesion (adhesion to ITO)]
A cured film with a film thickness of 2.0 μm is formed on a glass substrate (“0007 (trade name)” manufactured by Geomatec; hereinafter “ITO substrate”) sputtered with ITO on the surface in the same manner as pencil hardness evaluation. The adhesiveness of ITO and a cured film was evaluated according to "K5600-5-6 (established on April 20, 1999)". In order to reach the substrate of the glass plate with a cutter knife, on the ITO surface on the glass substrate, parallel straight lines of 11 vertical and 11 horizontal were drawn at intervals of 1 mm to produce 100 squares of 1 mm × 1 mm. Attach a cellophane adhesive tape (width = 18 mm, adhesive force = 3.7 N / 10 mm) to the surface of the cured film that has been cut, rub with an eraser (JIS S 6050 pass product) to make a close contact, hold one end of the tape, and make a right angle to the plate The remaining number of squares at the time of holding instantaneously was evaluated by visual observation. It judged as follows by the peeling area of a square, and made 3 or more the pass.
5: Peeling area = 0%
4: Peeling area = more than 0%, less than 5% 3: Peeling area = 5% or more, less than 15% 2: Peeling area = 15% or more, less than 35% 1: Peeling area = 35% or more, less than 65% 0 : Peeling area = 65% or more

[Adhesiveness (adhesion to metal)]
For a cured film spin-coated on a substrate with copper deposited on the surface and produced under the same conditions as the above adhesion evaluation with ITO, evaluation of adhesion with metal is carried out in the same manner as adhesion with ITO. Did.

[Chemical resistance (acid resistance)]
The ITO substrate having the cured film prepared in the ITO adhesion evaluation was treated for 80 seconds in a 35 ° C. aqueous solution mixed with HCl / HNO ₃ / H ₂ O = 18/4/78 (mass ratio). The adhesion of the treated substrate was evaluated in the same manner as the ITO adhesion evaluation.

[Chemical resistance (alkali resistance)]
The ITO substrate having a cured film, which was prepared in the ITO adhesion evaluation, was treated for 5 minutes in a 60 ° C. solution mixed with monoethanolamine / diethylene glycol monobutyl ether = 30/70 (mass ratio). The adhesion of the treated substrate was evaluated in the same manner as the ITO adhesion evaluation.

  As shown in Table 5, a photosensitive resin composition containing a cationic photopolymerization initiator (A), a cationically polymerizable compound (B) and an alkali-soluble resin, wherein the cationically polymerizable compound (B) is at least The photosensitive resin composition containing the episulfide compound (B1) and the cationically polymerizable compound (B2) other than the episulfide compound has excellent curability and high hardness even at a low temperature of 100 ° C. or lower. , Adhesion and chemical resistance were excellent.

  From the above results, the photosensitive resin composition of the present invention can provide a coating having excellent curability, high hardness, and excellent adhesion and chemical resistance, and the coating has organic electroluminescence. It was confirmed that the insulating film used for display devices and touch panels, and a high-quality cured film suitable for overcoating.

Claims (15)

A photosensitive resin composition comprising a cationic photopolymerization initiator (A), a cationically polymerizable compound (B) and an alkali-soluble resin,
The photosensitive resin composition in which a cationically polymerizable compound (B) contains at least an episulfide compound (B1) and a cationically polymerizable compound (B2) other than an episulfide compound. The photosensitive resin composition according to claim 1, wherein the cationically polymerizable compound (B2) other than the episulfide compound contains at least one selected from the group consisting of an oxetane compound, a vinyl ether compound and an epoxy compound. The photosensitive resin composition according to claim 1 or 2, wherein the cationically polymerizable compound (B2) other than the episulfide compound contains at least an oxetane compound. The photosensitive resin composition according to any one of claims 1 to 3, wherein the cationically polymerizable compound (B2) other than the episulfide compound contains at least an oxetane compound and a vinyl ether compound. The content ratio of the episulfide compound (B1) and the cationically polymerizable compound (B2) other than the episulfide compound is (B1) :( B2) = 20: 80 to 80:20. Photosensitive resin composition as described. The oxetane compound includes a compound represented by the following chemical formula (3-5) or a polymer obtained by polymerizing (3-ethyl oxetan-3-yl) methyl (meth) acrylate Photosensitive resin composition as described.
The photosensitive resin composition according to any one of claims 1 to 6, wherein the photocationic polymerization initiator (A) contains an aromatic sulfonium salt (a1) or an aromatic iodonium salt (a2). The photosensitive resin composition according to any one of claims 1 to 7, further comprising a photo radical polymerization initiator (C). The photosensitivity according to claim 8, wherein the photoradical polymerization initiator (C) contains at least one selected from the group consisting of oxime ester photopolymerization initiators, thioxanthone photopolymerization initiators and acetophenone photopolymerization initiators. Resin composition. The photosensitivity according to claim 8 or 9, wherein the content ratio of the photocationic polymerization initiator (A) and the photoradical polymerization initiator (C) is (A): (C) = 30: 70 to: 80: 20. Resin composition. The cured film formed using the photosensitive resin composition of any one of Claims 1-10. After apply | coating the photosensitive resin composition of any one of Claims 1-10 on a base material, exposing through a mask, developing and forming a pattern, manufacture of the cured film which has the process of heat-baking Method. The method for producing a cured film according to claim 12, wherein the temperature of heating and firing is 100 ° C or less. The cured film according to claim 11, which is an interlayer insulating film or an overcoat film. The cured film according to claim 11, which is for a touch panel.