JP2017126074A - Photosensitive resin composition and cured film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an alkali-developable photosensitive resin composition having excellent low-temperature curability, from which a cured film having high hardness, high transmittance, and excellent pattern linearity and chemical resistance can be formed, and to provide a high-quality cured film suitable for overcoating to be used for a touch panel, by using the photosensitive resin composition.SOLUTION: There is provided a photosensitive resin composition which contains a photo-radical polymerization initiator (A), a photo-cationic polymerizable initiator (B), a cationic polymerizable compound (C) and an alkali-soluble resin (F), where the cationic polymerizable compound (C) contains two or more kinds of cationic polymerizable compounds containing a vinyl ether compound (C1).SELECTED DRAWING: None

Description

  The present invention relates to a photosensitive resin composition and a cured film suitable for a touch panel formed using the same.

  In recent years, as electronic devices have become more sophisticated, diversified, and smaller and lighter, a transparent touch panel is mounted on the front surface of a display element such as a liquid crystal, and characters, symbols, patterns, etc. displayed on the display element through this transparent touch panel Those that perform visual recognition and selection and switch each function of the device by operating a transparent touch panel have rapidly spread.

  The touch panel is mounted on, for example, a bank ATM, a vending machine, a personal digital assistant (PDA, UMPC), a copying machine, a facsimile, a portable game machine, a guide board, a car navigation, a smartphone, a tablet, and the like.

Existing touch panel systems can be classified into a resistive film system, an optical system, an electrostatic capacity system, an ultrasonic system, a pressure system, an electromagnetic wave induction system, an image recognition system, a vibration detection system, and the like.
Specific examples of a touch panel arranged on a display device such as a liquid crystal include a resistance film method and a capacitance method. The resistance film method is a method of detecting a pressed position by voltage, and a capacitance method. Detects the position by capturing the change in capacitance caused by pressing.
As for the electrostatic capacity method, Patent Documents 1 to 3 and the like are disclosed, and an insulating film and a protective film are provided in the laminated structure in order to prevent erroneous recognition of a contact position.

  Capacitive touch panels, which are currently the mainstream, use many configurations that use transparent conductive films that are advantageous in terms of weight reduction and workability, including the GFF method in which two ITO films are bonded to a cover glass. (For example, Patent Document 4). However, since a film having low heat resistance is used, high-temperature baking is not possible and thermosetting is not required, or a UV-curable protective film that can obtain a cured film even by low-temperature baking is preferably used (see, for example, Patent Document 5). ).

  Since the capacitive touch panel does not have a layer having a function of mitigating external impacts like the resistive touch panel, higher hardness is required for the surface protective film. Furthermore, since processing for circuit connection is performed, in addition to photosensitivity, higher substrate adhesion in chemical treatment is required. Low-temperature firing is less likely to proceed with heat curing than firing, and it is necessary to improve the curing characteristics by UV.

  Examples of the low-temperature curable resin composition include an alkali-soluble copolymer described in Patent Document 6, a polymerizable compound having an ethylenically unsaturated bond, a photo radical generator, a compound having two or more oxetanyl groups in a molecule, and A radiation-sensitive resin composition containing an acid generator, a resin composition containing a carboxyl group-containing polysiloxane described in Patent Document 7, a solvent, a compound having a double bond and / or a triple bond, and a photopolymerization initiator ( For example, Patent Document 7) has been proposed. However, although these compositions improve adhesion to Si atoms-containing glass and silicon nitride substrates, substrates that do not have Si atoms such as ITO and molybdenum have insufficient adhesion after heat treatment and chemical treatment. It is.

JP 2008-65748 A JP 2009-15490 A JP 2010-44453 A JP 2013-003952 A JP 2001-330707 A JP 2009-3366 A JP 2008-208342 A

  The present invention is an alkali-developable photosensitive resin composition capable of forming a cured film having excellent low-temperature curability, high hardness, high transmittance, and excellent pattern linearity 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 photosensitive resin composition of the present invention contains a photo radical polymerization initiator (A), a photo cationic polymerization initiator (B), a cationic polymerizable compound (C), and an alkali-soluble resin (F). Formation of a cured film having high hardness, high transparency, and excellent pattern linearity and chemical resistance by the cationic polymerizable compound (C) containing two or more cationic polymerizable compounds including the vinyl ether compound (C1). And has been found to be excellent in low-temperature curability.

  That is, the present invention relates to a photosensitive resin composition comprising a photo radical polymerization initiator (A), a photo cationic polymerization initiator (B), a cationic polymerizable compound (C), and an alkali-soluble resin (F). In addition, the present invention relates to a photosensitive resin composition, wherein the cationically polymerizable compound (C) includes two or more kinds of cationically polymerizable compounds including a vinyl ether compound (C1).

  The present invention also relates to the photosensitive resin composition, wherein the cationic polymerizable compound (C) contains at least one selected from an epoxy compound (C2) and an oxetane compound (C3).

  The present invention is also characterized in that the epoxy compound (C2) contains at least one selected from a phenol novolac type epoxy resin (C2-a) and a cresol novolac type epoxy resin (C2-b). The present invention relates to a resin composition.

  The present invention also relates to the photosensitive resin composition, wherein the cationically polymerizable compound (C) includes an epoxy compound (C2) and an oxetane compound (C3).

  In the present invention, the photoradical polymerization initiator (A) is an oxime ester photopolymerization initiator (A1), a thioxanthone photopolymerization initiator (A2), an acetophenone photopolymerization initiator, or a benzoin photopolymerization initiator. Benzophenone photopolymerization initiator, triazine photopolymerization initiator, borate photopolymerization initiator, carbazole photopolymerization initiator, and at least two selected from the group consisting of imidazole photopolymerization initiators It relates to the photosensitive resin composition.

  The present invention also relates to the photosensitive resin composition, wherein the radical photopolymerization initiator (A) contains an oxime ester radical photopolymerization initiator (A1).

The present invention also relates to the photosensitive resin composition, wherein the photoradical polymerization initiator (A) includes a thioxanthone photoradical polymerization initiator (A2).

  The present invention also relates to the photosensitive resin composition, wherein the cationic photopolymerization initiator (B) includes an aromatic sulfonium salt (B1).

Moreover, this invention contains the polymer which an oxetane compound (C3) superposes | polymerizes the compound shown by Chemical formula (3-5), or (3-ethyloxetane-3-yl) methyl (meth) acrylate. Said photosensitive resin composition characterized by these. About.

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

  The present invention also relates to the cured film for a touch panel.

  In addition, the present invention includes a step of applying the photosensitive resin composition according to any one of claims 1 to 9 on a substrate, exposing through a mask, developing and forming a pattern, followed by heating and baking. A method for producing a cured film, comprising:

  In addition, the present invention provides the method for producing a cured film as described above, wherein the temperature for heating and baking is 150 ° C. or lower.

  The photosensitive resin composition of the present invention is excellent in low-temperature curability, has high hardness and high transmittance, and can form a cured film having excellent pattern linearity, adhesion, and chemical resistance. Hardness, high transmittance, and excellent pattern linearity, adhesion, and chemical resistance make it particularly suitable for overcoats used in touch panels.

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

  The photosensitive resin composition of the present invention contains a photo radical polymerization initiator (A), a photo cationic polymerization initiator (B), a cationic polymerizable compound (C), and an alkali-soluble resin (F). The cationic polymerizable compound (C) includes two or more cationic polymerizable compounds including the vinyl ether compound (C1).

<Photoradical polymerization initiator (A)>
In the photosensitive resin composition of the present invention, a photo-radical polymerization initiator is added to the photosensitive resin composition of the solvent development type or alkali development type in order to cure the composition by ultraviolet irradiation and form a coating film by a photolithography method. Can be prepared in the form of an adhesive resin composition. Any conventionally known radical photopolymerization initiator can be used.

  Examples of the photo radical polymerization initiator (A) include oxime ester photopolymerization initiator (A1), thioxanthone photopolymerization initiator, acetophenone photopolymerization initiator, benzoin photopolymerization initiator, benzophenone photopolymerization initiator, Examples include triazine photopolymerization initiators, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazole photopolymerization initiators, and acylphosphine oxide photopolymerization initiators.

  Among these, the photo radical polymerization initiator (A) is an oxime ester photopolymerization initiator (A1), a thioxanthone photopolymerization initiator, an acetophenone photopolymerization initiator, a benzoin photopolymerization initiator, and a benzophenone photopolymerization initiator. Including a radical photoinitiator selected from the group consisting of an initiator, a triazine photopolymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, and an imidazole photopolymerization initiator It is preferable for imparting, and more preferably, when it contains at least two kinds, it can be excellent in chemical resistance.

  Further, preferably, when the oxime ester-based photoradical polymerization initiator (A1) is included, the sensitivity can be high and the addition amount can be small, so that the transmittance can be high, and further, the thioxanthone-based photoradical polymerization initiator. When (A2) is included, since the curing of the coating film is further promoted by the interaction, the adhesion to the substrate can be further improved.

Specifically, for example, 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) and other oxime ester photopolymerization initiators (A1),
Thioxanthone photopolymerization initiators (A2) such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone,
4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Acetophenone series such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one Photopolymerization initiator,
Acylphosphine oxide photopolymerization initiators such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide,
Benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyldimethyl ketal,
Benzophenone-based photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide,
2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-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)- Triazine photopolymerization initiators such as 6-triazine,
Borate photopolymerization initiator, carbazole photopolymerization initiator,
Examples include imidazole-based photopolymerization initiators.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

Among the oxime ester photopolymerization initiators (A1),
1,2-octanedione-1- [4- (phenylthio) phenyl-2- (o-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 -Yl]-, 1- (o-acetyloxime), especially 1,2-octanedione-1- [4- (phenylthio) phenyl-2- (o-benzoyloxime)], is yellowed during the heating step. A photosensitive resin composition that is smaller, has a high transmittance as an insulating film, and particularly has a high transmittance around a wavelength of 400 nm is more preferable.

  Further, among the thioxanthone photopolymerization initiators (A2), isopropylthioxanthone and 2,4-diisopropylthioxanthone are preferable, and 2,4-diisopropylthioxanthone is particularly preferable from the viewpoint of availability.

As a commercial item of an oxime ester photoinitiator (A1),
For example, Irgacure OXE-01, Irgacure OXE-02 (all manufactured by BASF), N-1919 (manufactured by ADEKA), TRONLY TR-PBG-304, TRON
LY TR-PBG-305, TRONLY TR-PBG-309 (both manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) and the like.

As a commercial product of the thioxanthone photopolymerization initiator (A2),
Examples thereof include Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.).

The radical photopolymerization initiator (A) is preferably used in an amount of 1 to 15% by weight in a total of 100% by weight of the solid content of the resin composition from the viewpoint of transmittance, and is used in an amount of 1 to 10% by weight. It is more preferable.
When the oxime ester-based photopolymerization initiator (A1) is contained, the total amount of the photoradical polymerization initiator (A) is 40 to 95% by weight based on the standard (100% by weight), It is preferable in terms of hardness and substrate adhesion.

  Further, when the thioxanthone photopolymerization initiator (A2) is used in combination, 5 to 100 parts by weight of the thioxanthone photopolymerization initiator (A2) with respect to 100 parts by weight of the oxime ester photopolymerization initiator (A1). It is preferable because the substrate adhesion is improved, and it is particularly preferable because the substrate adhesion is further improved when used in an amount of 20 to 50 parts by weight.

<Sensitizer>
The photosensitive resin composition of the present invention further includes α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone as sensitizers. 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, and the like can be used in combination.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.
The content of the sensitizer can be used in an amount of 0.1 to 150 parts by weight with respect to 100 parts by weight of the photopolymerization initiator (A).

<Photocationic polymerization initiator (B)>
The cationic photopolymerization initiator (B) generates a strong acid such as tetrafluoroboric acid or hexafluorophosphoric acid by UV irradiation or heating, and the strong acid protonates an oxygen atom of a cationically polymerizable compound described later to form a cationic active species. Is formed and the polymerization reaction is started, and any known compound can be used without particular limitation.

As the cationic photopolymerization initiator (B), 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 thianthrium, and the anion moiety is BF ₄ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , or [BX ₄ ] ⁻ (where X is a phenyl group An aromatic sulfonium salt (B1), an aromatic iodonium salt (B2), an aromatic diazonium salt, wherein two or more hydrogen atoms represent a functional group substituted by a fluorine atom or a trifluoromethyl group. , Aromatic ammonium salts, thioxanthonium salts, or (2,4-cyclopentadien-1-yl) [(1- (Methylethyl) benzene] -iron salt and the like These photocationic polymerization initiators can be used alone or in admixture of two or more at any ratio as required.

  Among these, aromatic sulfonium salt (B1) or aromatic iodonium salt (B2) is preferable for improving the remaining film ratio and adhesion, and more preferably aromatic iodonium salt from the viewpoint of improving the remaining film ratio. (B2).

Examples of the aromatic sulfonium salt (B1) include bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluorophosphate, bis [4- (diphenylsulfonio) phenyl] sulfide bishexafluoroantimonate, and bis [4- (Diphenylsulfonio) phenyl] sulfide bistetrafluoroborate, 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- (phenylthio) phenyl Sulfonium 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 bishexafluoroantimonate, bis [4- (di (4- (2-hydroxyethoxy)) phenylsulfonio) phenyl] sulfide bistetrafluoroborate, bis [ 4- (di (4
-(2-Hydroxyethoxy)) phenylsulfonio) phenyl] sulfide tetrakis (pentafluorophenyl) borate and the like can be used.

Examples of the aromatic iodonium salt (B2) include diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, diphenyliodonium tetrafluoroborate, diphenyliodonium tetrakis (pentafluorophenyl) borate, and 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- Tilethyl) phenyliodonium hexafluoroantimonate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrafluoroborate, 4-methylphenyl-4- (1-methylethyl) phenyliodonium tetrakis (pentafluorophenyl) borate Etc. can be used.

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

Examples of aromatic ammonium salts include 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- (
Naphtylmethyl) -2-cyanopyridinium hexafluoroantimonate, 1- (naphthylmethyl) -2-cyanopyridinium tetrafluoroborate, 1- (naphthylmethyl) -2-cyanopyridinium tetrakis (pentafluorophenyl) borate, etc. are used. be able to.

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

  (2,4-Cyclopentadien-1-yl) [(1-methylethyl) benzene] -iron salt includes (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 or the like can be used.

Examples of the cationic photopolymerization initiator (B) include CPI-100P, CPI-200K, CPI-101A (manufactured by San Apro Co., Ltd.), Syracure photocuring initiator UVI-6990, Syracure photocuring initiator UVI- 6992, Cyracure photocuring initiator UVI-6976 (above, manufactured by Dow Chemical Japan Co., Ltd.), Adeka optomer SP-150, Adeka optomer SP-152, Adeka optomer SP-170, Adeka optomer SP-172 (Asahi Denka Kogyo Co., Ltd.), CI-5102, CI-2855 (Nippon Soda Co., Ltd.), Sun-Aid SI-60L, Sun-Aid SI-80L, Sun-Aid SI-100L, Sun-Aid SI-110L, Sun-Aid SI-180L, Sun-Aid SI-110, Sun-Aid SI-145 Sun-Aid SI-150, Sun-Aid SI-160, Sun-Aid SI-180 (manufactured by Sanshin Chemical Industry Co., Ltd.), Esacure 1064, Esacure 1187 (manufactured by Lamberti), Omnicat 432, Omnicat 440, Omni Cat 445, Omni Cat 550, Omni Cat 650, Omni Cat BL-550 (manufactured by IG Resin), Irgacure 250 (manufactured by BASF Corporation), Rhodosil Photo Initiator 2074 (RHODORSIL PHOTOINITIATOR 2074 (Rhodia Japan Co., Ltd.) Manufactured), WPI-113, WPI-
116, WPI-169, WPI-170 (manufactured by Wako Pure Chemical Industries, Ltd.) and the like are commercially available.

  Among these, CPI-100P, CPI-101A, CPI-200K, CPI-210S manufactured by San Apro, which are aromatic sulfonium salts (B1), or Irgacure 250 manufactured by BASF, which is an aromatic iodonium salt, Wako Pure Chemical Industries, Ltd. WPI-113, WPI-116, WPI-169, and WPI-170 manufactured by KK are preferred.

  The cationic photopolymerization initiator (B) is preferably used in an amount of 0.1 to 30% by weight in a total of 100% by weight of the solid content of the photosensitive resin composition, and has a residual film rate, chemical resistance, and transmittance. From the viewpoint of, it is more preferable to use in an amount of 1 to 20% by weight.

<Cationically polymerizable compound (C)>
The cationically polymerizable compound in the present invention 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 (B), and a cationically active species is obtained. It is the resulting compound.
Examples of the cationic polymerizable compound include a vinyl ether compound (C1), an epoxy compound (C2), an oxetane compound (C3), a styrene derivative, and a diene compound.

  As the cationically polymerizable compound (C) of the present invention, known compounds can be used without particular limitation as long as they are two or more kinds of cationically polymerizable compounds including the vinyl ether compound (C1).

  Further, it is preferable that an epoxy compound (C2) or an oxetane compound (C3) is further contained for hardness, residual film ratio, adhesion, and chemical resistance, and more preferably a vinyl ether compound (C1), an epoxy. By including the compound (C2) and the oxetane compound (C3), it is preferable for the hardness and the remaining film ratio.

  Thus, the content in the case of including the vinyl ether compound (C1), the epoxy compound (C2), and the oxetane compound (C3) is based on the solid content of the photosensitive resin composition (100% by weight) as a vinyl ether compound ( When C1) is in the range of 0.5 to 20% by weight, epoxy compound (C2) is in the range of 3 to 40% by weight, and oxetane compound (C3) is in the range of 5 to 50% by weight, the hardness, remaining film ratio, adhesion, It is preferable because it has high chemical properties and an excellent coating film can be obtained.

[Vinyl ether compound (C1)]
The vinyl ether compound (C1) can be used without particular limitation as long as it is a known compound, but preferably has 3 to 35 carbon atoms, 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 two or more vinyl groups.
Examples of the monofunctional vinyl ether 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 Cyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxyethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxypolyethylene glycol vinyl ether , Tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexyl 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 2- (vinyloxyethoxy) ethyl acrylate, methacrylate Acid 2- (vinyloxy) ethyl, and the like.

Examples of the polyfunctional vinyl ether 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-added trimethylolpropane trivinyl ether, PO-added trimethylolpropane trivinyl ether, EO-added ditrimethylolpropane tetravinyl ether, PO-added ditrimethylolpropane tetravinyl ether, EO-added pentaerythritol tetravinyl ether, PO-added penta Examples include erythritol tetravinyl ether, EO-added dipentaerythritol hexavinyl ether, and PO-added dipentaerythritol hexavinyl ether.
These vinyl ethers can be used singly or in combination of two or more in any ratio as necessary.

  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 (C1) used in the photosensitive resin composition of the present invention is usually 0.5 to 30% by weight, preferably 1 based on the solid content of the photosensitive resin composition (100% by weight). -10% by weight. When the content of the vinyl ether compound (C1) is in the above range, the residual film ratio and chemical resistance are high, and an excellent coating film is obtained, which is preferable.

[Epoxy compound (C2)]
As an epoxy compound (C2) 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 (C2) include phenol novolac type epoxy resin (C2-a), cresol novolac type epoxy resin (C2-b), trishydroxyphenylmethane type epoxy resin, dicyclopentadiene phenol type epoxy resin, bisphenol. -A type epoxy resin, bisphenol-F type epoxy resin, 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 (C2) is a phenol novolac type epoxy resin (
C2-a) or a cresol novolac type epoxy resin (C2-b) is preferable from the viewpoint of the remaining film ratio and chemical resistance.

  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 viewpoints of fast curability and chemical resistance.

(Phenol novolac type epoxy resin (C2-a))
As the phenol novolac type epoxy resin (C2-a), for example, Epicron N-
740, Epicron N-770, Epicron N-775 (Dainippon Ink Chemical Co., Ltd.), D.I. E. N438 (manufactured by Dow Chemical), RE-306 (manufactured by Nippon Kayaku Co., Ltd.), jER152, jER154 (both manufactured by Mitsubishi Chemical Corporation) and the like.

(Cresol novolac type epoxy resin (C2-b))
As the cresol novolac type epoxy resin (C2-b), for example, Epicron N-
660, Epicron N-665, Epicron N-670, Epicron N-673, Epicron N-680, Epicron N-695, Epicron N-665-EXP, Epicron N-672-EXP (all manufactured by DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S (all manufactured by Nippon Kayaku Co., Ltd.), UVR-6650 (manufactured by Union Carbide Co., Ltd.), ESCN-195 (manufactured by Sumitomo Chemical Co., Ltd.), etc. It is done.

As the trishydroxyphenylmethane type epoxy resin, for example, EPPN-503, EPPN-502H, EPPN-501H (all manufactured by Nippon Kayaku Co., Ltd.), TACTIX-742 (manufactured by Dow Chemical Co., Ltd.), jERE1032H60 ( Mitsubishi Chemical Co., Ltd.).

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

  Examples of the bisphenol type epoxy resin include jER828, jER1001 (all manufactured by Mitsubishi Chemical Corporation), UVR-6410 (manufactured by Union Carbide Corporation), D.I. E. Bisphenol-A type epoxy resins 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 (manufactured by Toto Kasei ( Bisphenol-F type epoxy resin, etc.).

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

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

  Examples of the naphthalene skeleton-containing epoxy resin include NC-7000, NC-7300 (all manufactured by Nippon Kayaku Co., Ltd.), EXA-4750 (manufactured by DIC Corporation), and the like.

  Examples of the alicyclic epoxy resin include EHPE-3150 (manufactured by Daicel Corporation).

  Examples of the heterocyclic epoxy resin include TEPIC-L, TEPIC-H, and TEPIC-S (all manufactured by Nissan Chemical Industries, Ltd.).

  These epoxy compounds can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the epoxy compound (C2) used in the photosensitive resin composition of the present invention is usually 0.5 to 50% by weight, preferably 1 based on the solid content of the photosensitive resin composition (100% by weight). -40% by weight. It is preferable that the content of the epoxy compound (C2) is in the above range because chemical resistance is high and an excellent coating film can be obtained.

[Oxetane compound (C3)]
As the oxetane compound (C3), a known compound having an oxetane group is not particularly limited and can be used. Examples of the oxetane compound (C3) include those in which the oxetane group is monofunctional, those in which the oxetane group is bifunctional, and those in which the oxetane group is bifunctional or more.

As an oxetane group that is monofunctional,
(3-ethyloxetane-3-yl) methyl acrylate (for example, OXE-10 manufactured by Osaka Organic Chemical Industry Co., Ltd.), (3-ethyloxetane-3-yl) methyl methacrylate (for example, OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd.) ), 3-ethyl-3-hydroxymethyloxetane (for example, OXT-212 manufactured by Toagosei Co., Ltd.), 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane , 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 (3-2): Alternatively, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane is preferable.

As an oxetane group having a bifunctional group,
4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl (eg, OXBP manufactured by Ube Industries, Ltd.), 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.) Di [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-oxetanyl) -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, tetra Ethylene 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, ethylene oxide (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis (3-ethyl-3- Oki Tanylmethyl) 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. OXT-191, etc. are mentioned.

Among those in which the oxetane group is bifunctional, a compound represented by the following general formula (3-3), general formula (3-4), or chemical formula (3-5) is preferable. In particular, the use of the compound represented by the chemical formula (3-5) is preferable because the hardness, the remaining film ratio, and the 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. R ³ represents a divalent organic group having 1 to 30 carbon atoms. n ¹ is an integer of from 1 to 20. ]

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

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

As an oxetane group having two or more functional groups,
Pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol penta Kis (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, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, oxy Resin (e.g., described in Japanese Patent No. 3783462 oxetane-modified phenol novolak resin, etc.) containing the Tan group and the above-mentioned (3-ethyloxetane -
Examples include polymers obtained by polymerizing (meth) acrylic monomers such as 3-yl) methyl (meth) acrylate. Such a polymer can be obtained using a known polymerization method.

Among those having an oxetane group having two or more functional groups, the oxetane compound (C3) is a polymer obtained by polymerizing (3-ethyloxetane-3-yl) methyl (meth) acrylate. It is preferable from the viewpoint.

  The content of the oxetane compound (C3) used in the photosensitive resin composition of the present invention is usually 0.5 to 50% by weight, preferably 1 based on the solid content of the photosensitive resin composition (100% by weight). -40% by weight. When the content of the oxetane compound (C3) is in the above range, the chemical resistance is high, and an excellent coating film is obtained, which is preferable.

<Radically polymerizable compound having (meth) acrylic group>
The photosensitive resin composition of this invention may contain the radically polymerizable compound which has a (meth) acryl group, and can thereby obtain the coating film which was excellent in hardness. The radically polymerizable compound having a (meth) acrylic group is preferably at least trifunctional or more from the viewpoint of hardness and remaining film ratio.

  Specific examples of the radical polymerizable compound having a (meth) acryl group include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol pentaacrylate, dipenta 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 pentaerythritol homopolymer and acrylic acid.

In addition, it may have an acid group, for example, an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polyvalent carboxylic acid, Examples thereof include esterified products with hydroxyalkyl (meth) acrylates. Specific examples include monohydroxy oligoacrylates or monohydroxy oligomethacrylates such as pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, malonic acid, succinic acid, glutaric acid, terephthalate. Monoesterified product containing free carboxyl group with dicarboxylic acid such as acid; propane-1,2,3,4-tetracarboxylic acid, butane-1,2,3,4-tetracarboxylic acid, benzene-1,2,3 Tetracarboxylic acids such as 1,4-tetracarboxylic acid, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate It can be given free carboxyl group-containing oligo ester of monohydroxy monoacrylate or monohydroxy monomethacrylate and the like.
These radically polymerizable compounds having a (meth) acryl group can be used singly or as a mixture of two or more at any ratio as required.

Commercially available radically polymerizable compounds having such a (meth) acryl group include, for example, Aronix M-400, Aronix M-460, Aronix M-402, Aronix M-510, Aronix M-520 (Toa Gosei Co., Ltd.) Made), KAYARAD
T-1420, KAYARAD DPHA, KAYARAD DPCA20, KAYAR
AD DPCA30, KAYARAD DPCA60, KAYARAD DPCA120 (
Nippon Kayaku Co., Ltd.), Biscoat # 802, Biscoat # 2500, Biscoat # 1000, Biscoat # 1080 (Osaka Organic Chemical Industry Co., Ltd.).

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

<Alkali-soluble resin (F)>
Examples of the alkali-soluble resin contained in the photosensitive resin composition of the present invention include thermoplastic resins. 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 region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type photosensitive composition, it is preferable to use the alkali-soluble acrylic resin which copolymerized the acidic substituent containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, and polyurethane resin. 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 copolymerized with an acidic substituent-containing ethylenically unsaturated monomer include resins having an acidic substituent such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic substituent, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, Or an isobutylene / (anhydrous) maleic acid copolymer etc. are mentioned. 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 of its high heat resistance and transparency. It is done.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, 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 is used. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and further reacting a polybasic acid anhydride with the generated hydroxyl group to convert an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce. The resin thus obtained is preferable because of its excellent 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, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

As a method similar to 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 a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

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

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl methacrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. In addition, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate added with poly-12-hydroxystearic acid or the like can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl methacrylate or glycerol methacrylate is preferable.

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

The weight average molecular weight in terms of polystyrene of the alkali-soluble resin is preferably 3000 to 100,000, more preferably 5000 to 50000. When the weight average molecular weight of the alkali-soluble resin is in the above range, the coating property is good, and when used as an alkali-soluble resin, film loss does not easily occur during development, and the developability of the unexposed part during development. Tends to be good, which is preferable.
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. The molecular weight distribution in the above range is preferable because the developability is excellent.

  The content of the alkali-soluble resin (F) is usually 5 to 90% by weight, preferably 10 to 70% by weight, based on the solid content of the photosensitive resin composition (100% by weight). When the content of the alkali-soluble resin (F) is in the above-mentioned range, it is preferable because it is excellent in solubility in a developing solution, hardly causes a development residue, and does not easily reduce the film thickness of an exposed portion during development.

<Solvent>
Examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, and 2-methyl. -1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene N, N-dimethylacetamide, N, N-dimethylformamide, n-butylal N-butylbenzene, n-propyl acetate, 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 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 acetate Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene 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 can be used singly or in combination of two or more at any ratio as required.

Particularly considering the drying property of the solvent, it is preferable to include a high boiling point solvent of 160 ° C. or higher in 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.degree. C.) 0 ℃), Jie Ren 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 0.0 ° 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 Tyl 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 (bp162.0 ° C), o-diethylbenzene (bp183.4 ° C), m-diethylbenzene (bp181.1 ° C), p-diethylbenzene (bp183.8 ° C), o-dichlorobenzene (bp180) 0.5 ° C), m-dichlorobenzene (bp 173.0 ° C), n-butylbenzene (bp183.3 ° C), sec-butylbenzene (bp178.3 ° C), tert-butylbenzene (bp169.1 ° 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.
Content of a solvent can be used in the quantity of 200-4000 weight part with respect to a total of 100 weight part of solid content in a resin composition.

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

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

Examples of the silane compound include silane compounds having an amide or urethane skeleton, an imidazole group, an isocyanate group, a vinyl group, a glycidyl group, a (meth) acryloyloxy group, an amino group, a ureido group, a mercapto group, or a sulfide group.
Among silane compounds, a silane compound (D1) having an amide or urethane skeleton, more preferably a silane compound represented by the general formula (6), or a silane compound (D2) having an imidazole group, more preferably a chemical formula (7). The silane compound represented is preferable because it is more excellent in adhesion.

[Silane Compound (D1)]
As a silane compound (D1), the silane compound shown by General formula (6) is mentioned.


[In General Formula (6), R ³¹ is 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 An aralkyl group having 7 to 30 carbon atoms, an alkaryl group having 7 to 30 carbon atoms,
X is an alkylene group having 1 to 20 carbon atoms, an arylene group having 6 to 20 carbon atoms, 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, or an aryl having 6 to 20 carbon atoms. 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, an aryl group, an aralkyl group, or an alkaryl group, the silane compound has an amide skeleton, and when R ³¹ is an alkoxy group or an aryloxy group, the silane compound has a urethane skeleton.

Examples of the silane compound represented by the general formula (6) include (3-carbamateethyl) propyltriethoxysilane, (3-carbamateethyl) propyltrimethoxysilane, (3-carbamateethyl) propyltripropoxysilane, (3 -Carbamatepropyl) propyltriethoxysilane, (3-carbamatepropyl) propyltrimethoxysilane, (3-carbamatepropyl) propyltripropoxysilane, (3-carbamatebutyl) propyltriethoxysilane, (3-carbamatebutyl) propyl Trimethoxysilane, (3-carbamatebutyl) propyltripropoxysilane, (3-carbamatebutyl) butyltripropoxysilane, (3-carbamatebutyl) propylmethyldiethoxysilane, (3-cal Matepentyl) propyltriethoxysilane, (3-carbamatehexyl) propyltriethoxysilane, 3-carbamateoctyl) pentylriboxysilane, (3-carbamateethyl) propylsilyltrichloride, (3-carbamateethyl) propyltrimethylsilane, 3-carbamateethyl) propyldimethylsilane, 3-carbamateethyl) propyltributylsilane, 3-carbamateethyl) ethyl-p-xylenetriethoxysilane, 3-carbamateethyl) -p-phenylenetriethoxysilane, etc. It is not limited to these. Further, 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 thereof.

  Since the silane compound (D) represented by the general formula (6) is excellent in heat resistance, the coating film is hardly yellowed, and is chemically stable, so that it is excellent in stability over time, and developability after aging. It will not be damaged.

[Silane Compound (D2)]
The silane compound (D2) is a silane compound having an imidazole group, and one or more kinds selected from an imidazole group as a first functional group and an alkoxysilyl group, a chlorosilyl group, and an acetoxysilyl group as a second functional group in one molecule. And the imidazole ring may have a substituent such as a saturated hydrocarbon group or an unsaturated hydrocarbon group.
Specifically, imidazole, 2-alkylimidazole, 2,4-dialkylimidazole, a reaction product of 4-vinylimidazole and the like with 3-gridoxypropylsilane compound, 2-ethyl-4-methylimidazopropylsilane, and salts thereof , Intramolecular condensates, intermolecular condensates, and the like.

Among the silane compounds having an imidazole group, a silane compound represented by the chemical formula (7) is more preferable.
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 a dehydration condensation reaction of the silanol compound, and a mixture thereof. May be.

  As a silane compound (D2) represented by the chemical formula (7), IM-1000 (manufactured by JX Nippon Mining & Metals) may be mentioned as a commercial product.

Other silane compounds include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycid Xylpropylmethyldiethoxysilane, 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, and the like. It is.
These silane compounds can be used alone or in admixture of two or more at any ratio as required.

The weight average molecular weight (Mw) of the silane compound (D) is more preferably 200 or more and less than 5000 from the viewpoint of developability.
The content of the silane compound (D) is more preferably 1% by weight or more and less than 20% by weight in the total solid content of the resin composition of 100% by weight from the viewpoint of developability. More preferably, they are 1 weight% or more and less than 10 weight%.

  When the weight average molecular weight (Mw) of the silane compound (D) is 200 or more, it is preferable from the viewpoint of availability, and when the weight average molecular weight (Mw) is less than 5000, the developability is good. Moreover, when the content is 1% by weight or more, the transmittance and developability are excellent, and when it is less than 20% by weight, not only the adhesion to the substrate and the hardness but also the developability is preferable.

<Heat-curing catalyst>
A thermosetting catalyst can also be used for the photosensitive resin composition in the present invention.
A thermosetting catalyst is a compound or composition that exhibits catalytic ability for an epoxy resin when heated to 80 to 200 ° C. or higher. These can be blended alone or in appropriate dispersion in another resin such as an epoxy resin. Examples of such a thermosetting catalyst include those shown below.

Dicyandiamide: Commercially available products are jER Cure DICY 7, 15, 20, 7A (the above is Japan Epoxy Resin Co., Ltd./trade name), Omicure DDA10, DDA50, DDA100, DDA5, CG-325, CG-1200, CG-1400 , DICYNEX 325, DICY-F, and DICY-M (the above is a product name / product name, manufactured by CVC Specialty Chemicals, Inc.).
Amine Adduct: Amicure PN-23, MY-24, PN-D, MY-D, PN-H, MY-H (above / manufactured by Ajinomoto Fine Techno Co., Ltd./trade name) and the like are listed as commercial products. .
Imidazole: Commercially available products include Curesol 2MZ, 2PZ, 2PHZ, 2MZ-OK, 2PZ-OK, 2P4MHZ, 2PHZ, 2E4MZ, C11Z, C17Z, 2MA-OK, 1B2MZ (the above are manufactured by Shikoku Kasei Kogyo Co., Ltd./trade names) , JER Cure IBMI-12, EMI-24, BMI-12 (above Japan Epoxy Resin Co./trade name), Nichigoimidazole 2PI, 2MI, 2E4MI, 1B2MI (above Japan Synthetic Chemical Co., Ltd./ Product name). Further, a type in which the functional group of these compounds is appropriately substituted with an inert group cyanoethyl group, a type salted with trimellitic acid, or a type modified with dicyandiamide can be used in the same manner. Examples of these commercially available products include 2E4MZ-CN, 2PHZ-CN, C11Z-CNS, 2MZ-AZINE (the above is a product name manufactured by Shikoku Kasei Kogyo Co., Ltd.).
Urea-type adduct system, aromatic urea: As commercially available products, Fujicure FXR1020, 1030, 1081 (the above is manufactured by Fuji Kasei Kogyo Co., Ltd./trade name), DCMU (manufactured by Hodogaya Chemical Co., Ltd.), 3- (3 4-dichlorophenyl) -1,1-dimethylurea / trade name), Omicure 24, 52, 94 (the above is CVCCS Specialty Chemicals, Inc./trade name) and the like.
Irido type: As a commercial product, EpiCure YPH-101, 102, 103, 104, 201, 202, 203, 204, 205, 206, 207, 208, 209, 210 (the above is made by Japan Epoxy Resin Co., Ltd./trade name) ).
Salts of p-toluenesulfonic acid: As commercial products, there are Anchor 1786B, Catalyst 2134 (the above is manufactured by Air Products Japan Co., Ltd./trade name), Adeka Hardener EH-3293S (manufactured by ADEKA Co., Ltd./trade name), and the like. Can be mentioned.
Microencapsulated latent curing agent: NovaCure HX-3721, 3722, 3741, 3742, 3748, 3613, 3088, 3921HP (above / made by Asahi Kasei Chemicals Co., Ltd.)
In addition, diaminomaleonitrile and its derivatives, Schiff base, melamine and its derivatives, amine imide synthesized by carboxylic acid ester, dimethylhydrazine and epoxy compound, amine imide imidazole compound and the like can be used as appropriate.

Among these, imidazole compounds or dicyandiamides and modified products thereof are preferable from the viewpoint of curability and availability.
The content of the thermosetting catalyst is preferably 0.5 to 30% by weight, more preferably 0.7 to 15% by weight, in the total solid content of 100% by weight of the photosensitive resin composition. When deviating from this range, there may be a problem that the curing does not proceed sufficiently or the adhesiveness is not sufficiently developed.

<Acid anhydride curing agent>
The photosensitive resin composition of the present invention may further use an acid anhydride curing agent. The acid anhydride curing agent can promote thermal curing by mixing with an epoxy resin. The difference from the aforementioned thermosetting catalyst is that there is no catalytic action.

As an acid anhydride curing agent,
Acetic anhydride, propionic anhydride, butyric acid anhydride, hexanoic acid anhydride, aliphatic carboxylic acid anhydride such as acetic acid propionic acid anhydride, aliphatic dicarboxylic acid anhydride such as succinic acid anhydride, maleic acid anhydride, cyclohexane Aromatic carboxylic anhydrides such as aliphatic cyclic carboxylic anhydrides such as hexanoic acid carboxylic acid, benzoic anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic 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 , 3,6-Tetrahydrophthalic anhydride 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride can be preferably used.

As a commercial item,
Ricacid TH, Ricacid HT-1A, Ricacid HH, Ricacid MH-700, Ricacid MH-700G, Ricacid MH (all manufactured by Shin Nippon Co., Ltd.), HN-2200, HN-2000, HN-5500, anhydrous methyl hymic Examples include acid (MHAC-P) (all manufactured by Hitachi Chemical Co., Ltd.), YH-306, YH-307 (all manufactured by Mitsubishi Chemical Corporation), and the like.

  The acid anhydride curing agent is preferably used in an amount of 0.1 to 40% by weight in a total of 100% by weight of the solid content of the epoxy compound (C2), and 5 to 30% by weight from the viewpoint of chemical resistance. More preferably, it is used in an amount.

<Inorganic oxide fine particles>
The photosensitive resin composition of the present invention can use inorganic oxide fine particles. As the inorganic oxide fine particles, 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 resulting curable composition The oxide particles are preferred. Among these, from the viewpoint of transmittance, oxide particles of silicon, zirconium, titanium or aluminum are preferable, and oxide particles of silicon are particularly preferable.

  Inorganic oxide fine particles are used in physical solutions such as plasma discharge treatment and corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to increase affinity and binding properties with alkali-soluble components. Surface treatment, chemical surface treatment with a surfactant, a coupling agent or the like may be performed.

  The average primary particle diameter of the oxide particles is preferably 1 nm to 1000 nm, more preferably 3 nm to 100 nm, and particularly preferably 5 nm to 30 nm. When the average primary particle diameter exceeds 1000 nm, the transparency when cured is reduced, or the surface state when coated is liable to deteriorate. Various surfactants and amines may be added to improve the dispersibility of the particles.

  The average primary particle diameter of the inorganic oxide fine particles is measured using, for example, the BET method. Specifically, the specific surface area of the inorganic oxide fine particles obtained by the BET method is obtained, the ratio of volume to 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 to obtain the 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, and 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, Examples thereof include amides such as N-methylpyrrolidone. Of these, methanol, isopropanol, butanol, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, toluene and xylene are preferred.

  Commercially available products as silicon oxide fine particle dispersions include PMA-ST, PMA-ST-MS, IPA-ST, IPA-ST-MS, IPA-ST-L, IPA manufactured by Nissan Chemical Industries, Ltd. -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, etc., and hollow silica CS60-IPA manufactured by Catalyst Kasei Kogyo Co., Ltd. Can do. As the powdered silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122, Asahi Glass Co., Ltd., Nippon Silica Industry, Nippon Aerosil Co., Ltd. Examples include E220A and E220 manufactured by Fuji Electric, SYLYSIA470 manufactured by Fuji Silysia Co., Ltd., SG flake manufactured by Nippon Sheet Glass Co., Ltd., and the like.

  Commercially available products as aluminum oxide fine particle dispersions include Alumina Sol-100, Alumina Sol-200, Alumina Sol-520 manufactured by Nissan Chemical Industries, Ltd., AS-150I and AS-150T manufactured by Sumitomo Osaka Cement Co., Ltd. Can be mentioned.

  Commercially available products as zirconia oxide fine particle dispersions include ZR-40BL, ZR-30BS, ZR-30AL, ZR-30AH, etc., manufactured by Nissan Chemical Industries, Ltd., HXU-110JC, manufactured by Sumitomo Osaka Cement Co., Ltd. Can be mentioned. In addition, the oxide fine particle dispersion of zirconia can be obtained by the method described in Japanese Patent No. 469630.

  Examples of products that are commercially available as titanium oxide fine particle dispersions include Nanotec manufactured by CI Chemical Co., Ltd., and D-962 manufactured by Sakai Chemical Industry Co., Ltd. In addition, a titanium oxide fine particle dispersion can be obtained by a method described in Japanese Patent No. 469630.

  In addition, as a commercially available product of oxide fine particle dispersions such as zinc, nanotech manufactured by CI Kasei Co., Ltd. can be exemplified.

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

<Antioxidant>
The resin composition of the present invention can contain an antioxidant. The antioxidant can suppress a decrease in transmittance due to yellowing or the like due to the heating process. Therefore, by including an antioxidant, yellowing during the heating step can be prevented, and a coating film having a high transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet 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 transmittance and sensitivity of the coating film. Among phenol-based compounds, hindered phenol-based antioxidants having high steric hindrance are particularly preferable.

[Phenolic antioxidant]
For example, 2,6-di-t-butyl-4-ethylphenol, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3 , 5-triazine, 2,2-thio-diethylenebis {3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate}, N, N'-hexamethylenebis (3,5-di- t-
Butyl-4-hydroxy-hydrocinnamide), 3,5-di-tert-butyl-4-hydroxybenzylphosphonate-diethyl ester, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanate Nurate, 2,6-di-t-butylphenol, 2,6-di-t-butyl-p-cresol, 2,6-di-t-butyl-4-methoxyphenol, triethylene glycol-bis {3- ( 3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate}, 1,6-hexanediol-bis {3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate}, pentaerythris Lityl-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, and the like. You may use individually or 2 or more types.

Among them, 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3 5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), 3,5-di-t- A hindered phenolic antioxidant selected from the group consisting of butyl-4-hydroxybenzylphosphonate-diethyl ester and tris- (3,5-di-t-butyl-4-hydroxybenzyl) -isocyanurate is: It is preferable from the viewpoint of photocurability.

[Phosphorus antioxidant]
Although what is marketed can be used as phosphorus antioxidant, Tris [2,4-di- (tert) -butylphenyl] phosphinetris [2-[[2,4,8,10-tetrakis ( 1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosphin-6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11- Tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosphin-2-yl) oxy] ethyl] amine, ethylbisphosphite (2,4-ditert-butyl-6-) It is preferable that it is at least one compound selected from the group consisting of these, and these may be used alone or in combination of two or more.

[Sulfur antioxidants]
A sulfur-based antioxidant is an antioxidant containing sulfur in the molecule. As such a sulfur-containing antioxidant, 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], and at least one selected from the group consisting of these It is preferable that it is a seed | species compound, and these can use 1 type (s) or 2 or more types.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  The content of the antioxidant is preferably 0.1 wt% or more and less than 4 wt% in the total solid content of the resin composition of 100 wt%. When the amount is less than 0.1% by weight, it is difficult to obtain a yellowing prevention effect due to insufficient antioxidant, and when the amount is more than 4% by weight, the radicals generated at the time of UV exposure are captured. Curing of the composition may be insufficient.

<Storage stabilizer>
Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and organic acids such as methyl ether, t-butylpyrocatechol, triethylphosphine, and triphenylphosphine. Examples thereof include phosphine and phosphite. The storage stabilizer can be used in an amount of 0.1 to 5% by weight in a total of 100% by weight of the resin composition.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the photosensitive resin composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. 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. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight in a total of 100% by weight 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, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207,
It is not limited to these.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene 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 stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

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

<Curing film>
The cured film of the present invention is prepared by spin coating such as spin coating, die coating, etc. on a glass substrate, ITO, molybdenum, other metal film, or organic film using the photosensitive resin composition of the present invention. It can be formed by casting, roll coating, roll transfer, 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, and is particularly suitable for an overcoat used for a touch panel.

  The overcoat is used for, for example, a metal wiring protective film used for a touch panel, an insulating film for insulating between the X electrode and the Y electrode of the touch sensor, and any of them may be used.

  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 producing by a photolithography method, for example, after a photosensitive resin composition is applied onto a substrate, it is exposed through a mask, developed, a pattern is formed, and then a cured film can be produced by a process of heating and baking. .

  When 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 this coating method, pre-baking is performed to evaporate the solvent to form a coating film. Next, the coated film is exposed using a super high pressure mercury lamp through a mask, and then immersed in a solvent or an alkaline developer, or developed by spraying a developer with a spray or the like. A cured film can be formed by dissolving and removing the exposed portion and forming a desired pattern, followed by heating and baking.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. An antifoaming agent or a surfactant can also be added to the developer.

  As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development 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 promotes the thermal curing of the coating film. Compared to the membrane, the chemical resistance is excellent. However, the photosensitive resin composition of the present invention does not require high-temperature baking, and a cured film excellent in necessary properties such as chemical resistance can be obtained even at low-temperature baking of 150 ° C. or lower. Therefore, an excellent cured film can be obtained at a low temperature of 150 ° C. or lower even when low-temperature baking is required, for example, when the touch panel configuration includes a film having low heat resistance.
However, when the heating and baking temperature is less than 100 ° C., sufficient chemical resistance or the like cannot be obtained, and thus it is preferable to heat and burn at 100 ° C. or higher.

  Hereinafter, the present invention will be described by way of examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. “PGMEA” means propylene glycol monomethyl ether acetate.

Prior to the examples, the weight average molecular weight of the resin and the method for measuring the acid value will be described.
(Weight average molecular weight of resin)
The weight average molecular weight (Mw) of the resin was measured in terms of polystyrene measured using TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as a developing solvent. It is a weight average molecular weight (Mw).

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

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

<Method for producing alkali-soluble resin (F) solution>
(Preparation of alkali-soluble resin solution (F-1))
Place 100 parts of propylene glycol monomethyl ether acetate in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. 5.2 parts of styrene from the dropping tube at temperature,
35.5 parts glycidyl methacrylate,
41.0 parts dicyclopentanyl methacrylate,
A mixture of 1.0 part of azobisisobutyronitrile was added dropwise over 2.5 hours to carry out a polymerization reaction.
Next, the inside of the flask was purged with air,
Add 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone to 17.0 parts of acrylic acid, and continue the reaction at 120 ° C for 5 hours. When the solid content acid value becomes 0.8, the reaction is terminated. Thus, a resin solution having a weight average molecular weight of about 12000 (measured by GPC) was obtained.
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added and reacted at 120 ° C. for 4 hours. Propylene glycol monomethyl ether acetate was added so that the non-volatile content was 40%, and the resin solution (F1-1) Was prepared.

(Preparation of alkali-soluble resin solution (F-2))
A synthetic reaction is performed in the same manner as the resin solution (F1-1) except that dicyclopentanyl methacrylate in the alkali-soluble resin solution (F-1) is changed to dicyclopentenyl methacrylate, and the resin solution (F1-2) is obtained. Prepared. The weight average molecular weight was 12500.

(Preparation of alkali-soluble resin solution (F-3))
A synthetic reaction is carried out in the same manner as in the resin solution (F-1) except that dicyclopentanyl methacrylate in the alkali-soluble resin solution (F-1) is changed to dicyclopentanyloxyethyl methacrylate. 3) was prepared. The weight average molecular weight was 12500.

(Preparation of alkali-soluble resin solution (F-4))
A synthetic reaction is performed in the same manner as the resin solution (F-1) except that dicyclopentanyl methacrylate in the alkali-soluble resin solution (F-1) is changed to dicyclopentenyloxyethyl methacrylate. ) Was prepared. The weight average molecular weight was 12500.

(Preparation of alkali-soluble resin solution (F-5))
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of PGMEA, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen.
18 parts of paracylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Gosei Co., Ltd.)
10 parts of benzyl methacrylate,
18.2 parts glycidyl methacrylate,
25 parts of methyl methacrylate,
A mixture of 2.0 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, replace the inside of the container with air replacement,
9.3 parts of acrylic acid (equivalent of glycidyl group)
Into the vessel, 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added, and the reaction was continued at 120 ° C. for 6 hours. When the solid content acid value became 0.5, the reaction was terminated. A solution was obtained. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (equivalent of generated hydroxyl group),
0.5 parts of triethylamine was added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and PGMEA was added to the previously synthesized resin solution so that the nonvolatile content was 20 wt%. An acrylic resin solution (F-5) was prepared. The weight average molecular weight (Mw) was 19000.

(Preparation of alkali-soluble resin solution (F-6))
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes, and the nonvolatile content was measured. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. Was added to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26000.

(Preparation of alkali-soluble resin solution (F-7))
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile 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, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20% by mass. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

<Method for producing oxetane compound>
(Oxetane compound solution (C3-1))
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 100 parts of propylene glycol monomethyl ether acetate, heated to 90 ° C. under a nitrogen stream, and (3-ethyloxetane- 3-yl) methyl methacrylate 100 parts, propylene glycol monomethyl ether acetate 48 parts and 2,2′-azobis (2,4-dimethylvaleronitrile) 3 parts in advance were mixed dropwise over 2 hours, Thereafter, the reaction was continued at 90 ° C. for 2 hours. After cooling to room temperature, the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content was 20% to obtain a propylene glycol monomethyl ether acetate solution of the oxetane compound (C3-1).

<Method for producing silane compound>
(Silane compound (D-3))
Prepare a flask equipped with a cooling tube as a reaction tank, and thoroughly stir and mix 100 g of 3-isocyanatopropyltriethoxysilane (“KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.) and 100 g of ethanol (manufactured by Kishida Chemical Co., Ltd.). After substituting with nitrogen, the temperature of the reaction vessel was raised to 60 ° C. by heating in an oil bath while stirring. After the temperature of the reaction vessel was stabilized at 60 ° C., the mixture was stirred for 6 hours. After confirming the completion of the reaction by FT-IR spectrum, the temperature of the reaction vessel was lowered to room temperature, and the sample was taken out and stored in a container purged with nitrogen.

[Example 1]
(Photosensitive resin composition (R1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to obtain a resin composition (R-1).

-Photoradical polymerization initiator (A)
OXE-01: 2.00 parts “Irgacure OXE-01” (manufactured by BASF);
1,2-octanedione-1- [4- (phenylthio) phenyl-2
-(O-benzoyloxime)]
-Cationic polymerization initiator (B)
Irg250: 2.86 parts “Irgacure 250” (manufactured by BASF);
Iodonium, (4-methylphenyl) [4- (2methylpropyl) phenyl]
-Hexafluorophosphate (1-)
・ Cationically polymerizable compound (C)
DVE-3: 1.00 part “DVE-3” (manufactured by BASF); triethylene glycol divinyl ether styrene: 1.00 part, alkali-soluble resin (F)
F-1: 79.95 parts Leveling agent BYK-330: 1.00 part “BYK-330” (manufactured by BYK-Chemie); polyether structure-containing PGMEA solution of dimethylsiloxane (adjusted to 1% solid content)
Solvent PGMEA: 12.19 parts

[Examples 2 to 74, Comparative Example 1]
(Photosensitive composition (R-2 to 75))
Hereinafter, the photosensitive resin composition (R-2 to 75) was the same as the photosensitive resin composition (R-1) except that the composition and the blending amount (parts by weight) were changed as shown in Tables 1 to 12. )

Table 1. ~ Table 12. The following abbreviations are used.
<Photoradical polymerization initiator (A)>
[Oxime ester photoradical polymerization initiator (A1)]
OXE-01: “Irgacure OXE-01” (manufactured by BASF);
1,2-octanedione-1- [4- (phenylthio) phenyl-2- (o-benzoyloxime)]
OXE-02: “Irgacure OXE-02” (manufactured by BASF); ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o- Acetyl oxime)
・ PBG-304: “TRONLY TR-PBG-304” (manufactured by Changzhou Power Electronics New Materials Co., Ltd.)
・ PBG-305: “TRONLY TR-PBG-305” (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.)
・ PBG-309: "TRONLY TR-PBG-309" (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.)
・ N-1919 (made by ADEKA)

[Thioxanthone photoradical polymerization initiator (A2)]
DETX-S: “Kayacure DETX-S” (manufactured by Nippon Kayaku Co., Ltd.); 2,4-diethylthioxanthone • 2-isopropylthioxanthone (manufactured by Tokyo Chemical Industry Co., Ltd.)
[Other photo radical polymerization initiators]
Irg369: “Irgacure 369” (manufactured by BASF); 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one

<Photocationic polymerization initiator (B)>
[Aromatic sulfonium salt (B1)]
CPI-100P: “CPI-100P” (manufactured by San Apro); 50% propylene carbonate solution of triarylsulfonium / PF 6 salt • CPI-101A: “CPI-101A” (manufactured by San Apro); triaryl sulfonium / SbF 6 salt 50% propylene carbonate solution / CPI-210K: “CPI-210K” (manufactured by San Apro); 50% propylene carbonate solution of triarylsulfonium / special phosphorus anion salt [aromatic iodonium salt (B2)]
Irg250: “Irgacure 250” (manufactured by BASF); iodonium, (4-methylphenyl) [4- (2methylpropyl) phenyl] -hexafluorophosphate (
1-) 75% propylene carbonate solution / WPI-113: “WPI-113” (manufactured by Wako Pure Chemical Industries); 50% propylene carbonate solution of diphenyliodonium / PF6 salt / WPI-116: “WPI-116” (Japanese sum) 50% propylene carbonate solution of diphenyliodonium / SbF6 salt / WPI-169: “WPI-169” (manufactured by Wako Purechemical); 50% of diphenyliodonium / bis (perfluorobutanesulfonyl) imide salt Propylene carbonate solution / WPI-170: “WPI-170” (manufactured by Wako Pure Chemical Industries); 50% propylene carbonate solution of diphenyliodonium / PF6 salt

<Cationically polymerizable compound (C)>
[Vinyl ether compound (C1)]
HEVE: “HEVE” (manufactured by Maruzen Petrochemical Co., Ltd.); 2-hydroxyethyl vinyl ether; DEGV: “DEGV” (manufactured by Maruzen Petrochemical Co., Ltd.); diethylene glycol monovinyl ether; 4-hydroxybutyl vinyl ether / EOXTVE: “EOXTVE” (manufactured by Maruzen Petrochemicals); ethyl oxetane methyl vinyl ether / CHDMVG: “CHDMVG” (manufactured by Maruzen Petrochemicals); cyclohexanedimethanol vinyl glycidyl ether / DVE-2: “DVE” -2 "(manufactured by BASF); diethylene glycol divinyl ether / DVE-3:" DVE-3 "(manufactured by BASF); triethylene glycol divinyl ether / VEEA:" VEEA "(manufactured by Nippon Shokubai Co.); acrylic acid 2- (Vini Kishietokishi) ethyl

[Epoxy compound (C2)]
JER152: “jER152” (Mitsubishi Chemical Corporation); PGMEA solution of phenol novolac type epoxy resin (adjusted to 20% solid content)
JER154: “jER154” (Mitsubishi Chemical Corporation); PGMEA solution of phenol novolac type epoxy resin (adjusted to 20% solid content)
N-660: “Epiclon N-660” (manufactured by DIC); PGMEA solution of cresol novolac type epoxy resin (adjusted to 20% solid content)
N-673: “Epiclon N-673” (manufactured by DIC); PGMEA solution of cresol novolac type epoxy resin (adjusted to 20% solid content)
N-695: “Epiclon N-695” (manufactured by DIC); PGMEA solution of cresol novolac type epoxy resin (adjusted to 20% solid content)
N-740: “Epiclon N-740” (manufactured by DIC); PGMEA solution of phenol novolac type epoxy resin (adjusted to 20% solid content)
N-770: “Epiclon N-770” (manufactured by DIC); PGMEA solution of phenol novolac type epoxy resin (adjusted to 20% solid content)
N-775: “Epiclon N-775” (manufactured by DIC); PGMEA solution of phenol novolac type epoxy resin (adjusted to 20% solid content)
EHPE-3150: “EHPE-3150” (manufactured by Daicel); PGMEA solution of 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol ( Adjusted to 20% solid content)
Celoxide 2021P: “Celoxide 2021P” (manufactured by Daicel): PGMEA solution of 3,4-epoxycyclohexenyl (adjusted to 20% solid content)
EXA-7200: “Epiclon EXA-7200” (manufactured by DIC); PGMEA solution of dicyclopentadienephenol type epoxy resin (adjusted to 20% solid content)
JER E157S75: “jER E157S75” (manufactured by Mitsubishi Chemical); PGMEA solution of bisphenol A type epoxy resin (adjusted to 20% solid content)
JER828: “jER828” (Mitsubishi Chemical Corporation); PGMEA solution of bisphenol type epoxy resin (adjusted to 20% solid content)
JER YX-4000: “jER YX-4000” (Mitsubishi Chemical Corporation); PGMEA solution of biphenol type epoxy resin (adjusted to 20% solid content)
-TEPIC-S: “TEPIC-S” (manufactured by Nissan Chemical Industries); PGMEA solution of heterocyclic epoxy resin (adjusted to 20% solid content)

[Oxetane compound (C3)]
OXT-221: “Aron oxetane OXT-221” (manufactured by Toagosei Co., Ltd.): di [1-ethyl (3-oxetanyl)] methyl ether OXBP: “OXBP” (manufactured by Ube Industries); 4,4′- Bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl · OXTP: “OXTP” (manufactured by Ube Industries); 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] benzene · OXT- 101: “Aron oxetane OXT-101” (manufactured by Toagosei Co., Ltd.): 3-ethyl 3-hydroxymethyl oxetane / OXT-212: “Aron oxetane OXT-212” (manufactured by Toagosei Co., Ltd.): 2-ethylhexyl oxetane / OXT- 121: “Aron Oxetane OXT-121” (manufactured by Toagosei Co., Ltd.): Xylylenebisoxetane / OXT-221: “Aron oxetane OXT-221” (manufactured by Toagosei Co., Ltd.): 3-ethyl-3 {[(3-ethyloxetane-3-yl) methoxy] methyl} oxetane

<Radically polymerizable compound having (meth) acrylic group>
M-402: “Aronix M-402” (manufactured by Toagosei Co., Ltd.): a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate. V # 802: “V # 802” (manufactured by Osaka Organic Chemical Industry Co., Ltd.): Reaction product of acrylic acid with pentaerythritol homopolymer based on tripentaerythritol heptaacrylate and tripentaerythritol octaacrylate

<Inorganic oxide fine particle dispersion>
PMA-ST: “PMA-ST” (manufactured by Nissan Chemical Industries, Ltd.): PGMEA dispersion of silicon oxide fine particles (non-volatile content: 30% by weight)
<Heat curable catalyst>
2E4MZ: “2E4MZ” (manufactured by Shikoku Kasei Co., Ltd.): 2-ethyl-4-methylimidazole <anhydride curing agent>
BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride (Mitsubishi Chemical Corporation)
<Silane compound>
IM-1000: “IM-1000” (manufactured by JX Nippon Mining & Metals): having an imidazole group

<Leveling agent>
BYK-330: “BYK-330” (by Big Chemie); PGMEA solution of polyether structure-containing dimethylsiloxane (adjusted to 1% solid content)
<Solvent>
・ PGMEA: Propylene glycol monomethyl ether acetate

<Evaluation of photosensitive resin composition>
The photosensitive resin compositions obtained by the evaluation methods shown below were each evaluated. The results are shown in Tables 12-14.

(1) Measurement of transmittance Using the obtained photosensitive resin composition, a substrate coated with a finished film thickness of 1.5 μm was obtained by heating at 150 ° C. for 60 minutes.
First, a 100 mm × 100 mm, 0.7 mm thick glass substrate (Corning Glass
The obtained photosensitive resin composition was applied to Eagle 2000) using a spin coater, and prebaked at 100 ° C. for 2 minutes using a hot plate (“EC-1200N (trade name)” manufactured by ASONE).
Using an ultrahigh pressure mercury lamp, ultraviolet exposure was performed with an illuminance of 20 mW / cm ² and an exposure amount of 200 mJ / cm ² .
The coated substrate was heated at 150 ° C. for 60 minutes and allowed to cool to obtain a cured film having a thickness of 1.5 μm. The film thickness was measured with a stylus type film thickness meter DECTAC-3 manufactured by ULVAC.
Using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), the transmittance of the obtained coating film at a wavelength of 400 nm was measured.
It can be said that the transmittance is good at 95% or more. Below that, the transmittance is not suitable for practical use.

(2) Measurement of pencil hardness Pencil hardness was measured according to "JIS K5600-5-4 (1999)" about the cured film with a film thickness of 1.5 micrometers obtained by the method of said (1) description.
When this value is 4H or higher, the surface hardness is good. When the hardness is 3H, the minimum practical hardness, 2H or less is not suitable for practical use.

◎; 5H or more ○; 4H
△; 3H
×: 2H or less

(3) Pattern linearity The board | substrate apply | coated so that a final film thickness might be set to 1.5 micrometers was obtained by heating at 150 degreeC for 60 minute (s) using the obtained photosensitive resin composition.

First, a 100 mm × 100 mm, 0.7 mm thick glass substrate (Corning Glass
The obtained photosensitive resin composition was applied to Eagle 2000) using a spin coater, and prebaked at 100 ° C. for 2 minutes using a hot plate (“EC-1200N (trade name)” manufactured by ASONE).
Using an ultra-high pressure mercury lamp, UV exposure was performed at an illuminance of 20 mW / cm ² and an exposure amount of 100 mJ / cm ² through a mask capable of forming a 50 μm line and space pattern.
Subsequently, using an automatic developing device (“(trade name)”, manufactured by Actes Co., Ltd.), spray development was performed for 90 seconds with a 0.045 wt% aqueous potassium hydroxide solution, followed by rinsing with water for 30 seconds.
The substrate after development was heated at 150 ° C. for 60 minutes and allowed to cool, and then the linearity of the pattern was evaluated.

○: Good linearity ×: Poor linearity due to jaggedness or peeling

(4) Residual film ratio Using the obtained photosensitive resin composition, a substrate coated so as to have a finished film thickness of 1.5 μm was obtained by heating and heating at 230 ° C. for 20 minutes.

First, a 100 mm × 100 mm, 0.7 mm thick glass substrate (Corning Glass
After applying the obtained photosensitive resin composition to Eagle 2000) using a spin coater and prebaking at 100 ° C. for 2 minutes using a hot plate (“EC-1200N (trade name)” manufactured by ASONE). The film thickness was measured with a stylus type film thickness meter DECTAC-3 manufactured by ULVAC (film thickness 1).
Subsequently, using an ultrahigh pressure mercury lamp, ultraviolet exposure was performed at an illuminance of 20 mW / cm ² and an exposure amount of 100 mJ / cm ² through a mask capable of forming a 50 μm line and space pattern.
Further, using an automatic developing device (“ADE-3000S (trade name)”, manufactured by Actes Co., Ltd.), spray development was performed for 90 seconds with a 0.045 wt% aqueous potassium hydroxide solution, followed by rinsing with water for 30 seconds.
The substrate after development was heated at 150 ° C. for 30 minutes and allowed to cool, and then the film thickness was measured with a stylus-type film thickness meter DECTAC-3 manufactured by ULVAC (film thickness 2).
The remaining film ratio was calculated from the obtained film thickness using the following formula.

(Residual film ratio) = (film thickness 2) / (film thickness 1) × 100 (%)
○: Remaining film ratio 80% or more Δ; Remaining film ratio 70% or more and less than 80% ×: Remaining film ratio less than 70%

(5) Evaluation of ITO adhesion (adhesion)
A cured film having a film thickness of 1.5 μm is formed on a glass substrate (“0007 (trade name)”, manufactured by Geomatec; hereinafter referred to as “ITO substrate”) on which ITO is sputtered in the same manner as described in (1) above. Then, the adhesion between ITO and the cured film was evaluated according to JIS “K5600-5-6 (established on April 20, 1999)”.
On the ITO surface on the glass substrate, 11 parallel straight lines of 11 vertical and horizontal directions were drawn at 1 mm intervals so as to reach the substrate of the glass plate with a cutter knife, and 100 squares of 1 mm × 1 mm were produced. A cellophane adhesive tape (width = 18 mm, adhesive strength = 3.7 N / 10 mm) is applied to the cut cured film surface, and it is rubbed with an eraser (JISS6050-accepted product) to hold it, holding one end of the tape, and maintaining a right angle to the plate The remaining number of squares when peeled instantaneously was visually evaluated. Judgment was made as follows according to the peeled area of the cells, and 3 or more was determined to be acceptable.

5: Peel area = 0%
4: Peel area = <5%
3: Peel area = 5-14%
2: Peel area = 15-34%
1: Peeling area = 35% -64%
0: peeling area = 65% to 100%

(6) Chemical solution processing method (chemical resistance)
(6-1) An ITO substrate having a cured film prepared by the acid treatment method (5) is mixed with an aqueous solution at 35 ° C. mixed with HCl / HNO ₃ / H ₂ O = 18/4/78 (weight ratio). Processed for seconds. About the board | substrate after a process, it evaluated adhesiveness like (5).

(6-2) An ITO substrate having a cured film produced by the alkali treatment method (5) was treated for 5 minutes in a 60 ° C. solution mixed with monoethanolamine / diethylene glycol monobutyl ether = 30/70 (weight ratio). . About the board | substrate after a process, it evaluated adhesiveness like (5).

  As shown in Tables 13 to 15, photosensitivity containing a photo radical polymerization initiator (A), a photo cation polymerization initiator (B), a cation polymerizable compound (C), and an alkali-soluble resin (F). It is a resin composition, and the cationically polymerizable compound (C) is a photosensitive resin composition containing two or more kinds of cationically polymerizable compounds including a vinyl ether compound (C1). Also in the case, it had excellent curability, high hardness, high transmittance, and excellent pattern linearity and chemical resistance.

  In addition, even when the heating and baking temperature is changed to 230 ° C. using the photosensitive resin composition of the present invention, it has excellent curability, high hardness, high transmittance, pattern linearity, and chemical resistance. It was excellent.

  From the above results, the photosensitive resin composition of the present application can provide a coating film having excellent curability, high hardness, high transmittance, excellent resolution, and chemical resistance. Was confirmed to be a high-quality cured film suitable for an overcoat used for a touch panel.

[Examples 2 to 74, Comparative Example 1]
(Photosensitive composition (R-2 to 75))
Hereinafter, the photosensitive resin composition (R-2 to 75) was the same as the photosensitive resin composition (R-1) except that the composition and the blending amount (parts by weight) were changed as shown in Tables 1 to 12. )
However, Examples 53 to 55 are reference examples.

Claims (13)

  A photosensitive resin composition comprising a photo radical polymerization initiator (A), a photo cationic polymerization initiator (B), a cationic polymerizable compound (C), and an alkali-soluble resin (F), wherein the cationic polymerization The photosensitive resin composition, wherein the photosensitive compound (C) includes two or more cationically polymerizable compounds including the vinyl ether compound (C1).   The photosensitive resin composition according to claim 1, wherein the cationic polymerizable compound (C) contains at least one selected from an epoxy compound (C2) and an oxetane compound (C3). The photosensitive resin composition according to claim 2, wherein the epoxy compound (C2) contains at least one selected from a phenol novolac type epoxy resin (C2-a) and a cresol novolak type epoxy resin (C2-b). object.   The photosensitive resin composition according to claim 1, wherein the cationic polymerizable compound (C) contains an epoxy compound (C2) and an oxetane compound (C3).   The radical photopolymerization initiator (A) is an oxime ester photopolymerization initiator (A1), a thioxanthone photopolymerization initiator (A2), an acetophenone photopolymerization initiator, a benzoin photopolymerization initiator, or a benzophenone photopolymerization initiator. The composition comprises at least two selected from the group consisting of an agent, a triazine photopolymerization initiator, a borate photopolymerization initiator, a carbazole photopolymerization initiator, and an imidazole photopolymerization initiator. 4. The photosensitive resin composition according to any one of 4 above.   The photosensitive resin composition according to claim 1, wherein the radical photopolymerization initiator (A) contains an oxime ester radical photopolymerization initiator (A1).   The photosensitive resin composition according to claim 1, wherein the photo radical polymerization initiator (A) contains a thioxanthone photo radical polymerization initiator (A 2).   The photosensitive resin composition according to claim 1, wherein the cationic photopolymerization initiator (B) contains an aromatic sulfonium salt (B1) or an aromatic iodonium salt (B2). The oxetane compound (C3) contains a polymer obtained by polymerizing a compound represented by the chemical formula (3-5) or (3-ethyloxetane-3-yl) methyl (meth) acrylate. The photosensitive resin composition of any one of 2-4.
  The cured film formed using the photosensitive resin composition of any one of Claims 1-9.   The cured film according to claim 10, which is for a touch panel.   It has the process of applying the photosensitive resin composition of any one of Claims 1-9 on a base material, exposing through a mask, developing, forming a pattern, and baking by heating. A method for producing a cured film.   The method for producing a cured film according to claim 12, wherein the temperature for heating and baking is 150 ° C. or lower.