JP2015025935A - Photocurable resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a photocurable resin composition having good adhesion to a substrate and being excellent in chemical resistance; and an insulation film for a touch panel, color filter protection film and photospacer using the same.SOLUTION: The problem is solved by a photocurable resin composition comprising (A) an alkali-soluble resin, (B) a compound having two or more (meth)acryloyl groups in the molecule, (C) a compound having only of an epoxy group or a β-hydroxyalkylamide group, (D) an organic silicon compound and (E) a photoradical polymerization initiator.

Description

  The present invention relates to a photocurable resin composition suitable as a material for forming a display panel such as a liquid crystal panel or a touch panel, and an interlayer insulating film, a touch panel, a color filter protective film, and a photospacer formed therefrom.

  In general, for liquid crystal display elements, integrated circuit elements, solid-state imaging elements, etc., a protective film for preventing deterioration and damage of electronic parts, a flattening film for flattening the element surface, and for maintaining electrical insulation An insulating film, a fine pattern for keeping the distance between elements constant, and the like are provided. In order to form these films and fine patterns, a photolithography method using a radiation-sensitive composition is often employed in addition to the case of using a thermosetting composition. These films and fine patterns are required to have heat resistance, transparency, substrate adhesion, flatness, chemical resistance, dimensional stability, etc., depending on their use, and radiation-sensitive compositions have storage stability. However, it has been difficult to obtain a radiation-sensitive composition that satisfies all of the requirements.

  As a material for forming the interlayer insulating film, an ITO electrode and a TFT are obtained by taking advantage of the fact that an interlayer insulating film having sufficient flatness can be obtained with a small number of steps for obtaining an interlayer insulating film having a required pattern shape. Photosensitive compositions capable of patterning contact holes that are opened in an interlayer insulating film for electrical connection with an element are widely used.

  For example, Patent Document 1 discloses a photosensitive composition for forming a photospacer of a liquid crystal display, and illustrates a photosensitive resin composition including a polymer having photosensitivity and alkali developability and a photosensitive monomer. Yes. However, since the carboxyl group incorporated for imparting alkali developability remains in the film cured by exposure, the formed product swells by chemicals such as acid and alkali, and stress is applied to the substrate interface. It had the problem that it took over and adhesiveness deteriorated.

  Examples in which the residual carboxyl group is reduced are disclosed in Patent Documents 2 to 4, but all use a polyfunctional epoxy compound, and curing shrinkage occurs upon heating, resulting in the prevention of ITO, Mo, etc. Adhesion will deteriorate.

JP 2002-020442 A JP-A-7-248625 JP 11-1331013 A JP-A-5-78453

  The present invention provides a photosensitive composition having excellent chemical resistance, heat resistance, transparency, substrate adhesion, flatness, and storage stability, a coating agent containing the same, and color filter protection using the same. An object is to provide a film, an interlayer insulating film, and a photospacer.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, in order to cap the carboxyl group incorporated in the resin to develop developability after heat treatment, 1 functional group capable of reacting with the carboxyl group is added. The present inventors have found that the above-mentioned problems can be solved by blending a compound having only one compound, and the present invention has been completed.

That is, this invention relates to the photocurable resin composition characterized by including the following component.
(A) Alkali-soluble resin (B) Compound having two or more (meth) acryloyl groups in the molecule (C) Compound having only one epoxy group or β-hydroxyalkylamide group (D) Organosilicon compound (E ) Photo radical polymerization initiator

In addition, the present invention relates to the photocurable resin composition, wherein (A) the alkali-soluble resin further has a radical polymerizable group.
Moreover, this invention relates to the said photocurable resin composition characterized by the (D) organosilicon compound containing a silane coupling agent.
In the present invention, the silane coupling agent has one or more functional groups selected from the group consisting of an amino group, a block amino group, an isocyanate group, a blocked isocyanate group, an isocyanurate group, a ureido group, and a mercapto group. It is related with the said photocurable resin composition characterized by the above-mentioned.

Moreover, this invention relates to the said photocurable resin composition characterized by including a (F) filler further.
The present invention also relates to the photocurable resin composition, wherein the filler (F) is silica.
The present invention also relates to (B) the photocurable resin composition, wherein the compound having two or more (meth) acryloyl groups in the molecule has an alkyleneoxy chain or a carbonylalkyleneoxy chain.

Moreover, this invention relates to the interlayer insulation film formed by hardening | curing the said photocurable resin composition.
The present invention also relates to a touch panel having the interlayer insulating film.
Moreover, this invention relates to the color filter protective film formed by hardening | curing the said photocurable resin composition.
Furthermore, this invention relates to the photospacer formed by hardening | curing the said photocurable resin composition.

  According to the present invention, a photosensitive composition having excellent chemical resistance and excellent heat resistance, transparency, substrate adhesion, flatness and storage stability, a coating agent containing the same, and color filter protection using the same A film, an interlayer insulating film, and a photospacer could be provided.

<(A) Alkali-soluble resin>
(A) of this invention is used in order to ensure the alkali developability of a photocurable resin composition. (A) As alkali-soluble resin, if it is a polymer which has alkali solubility, it will not specifically limit, For example, the acrylic resin etc. which have a carboxyl group are mentioned.

As an acrylic resin having a carboxyl group,
[I] (a1) a resin obtained by copolymerizing an unsaturated monomer having a carboxyl group with (a6) another copolymerizable unsaturated monomer,
[II] (a2) An unsaturated monomer having a hydroxyl group is copolymerized with (a6) another copolymerizable unsaturated monomer, and then an acid anhydride group and a hydroxyl group of a cyclic acid anhydride And a resin formed by reacting with a carboxyl group.

Moreover, it is preferable from the viewpoint of chemical resistance and hardness that the acrylic resin having a carboxyl group has a radical polymerizable group. As an acrylic resin having a carboxyl group and a radical polymerizable group,
[III] A resin obtained by reacting a part of the carboxyl group contained in the resin obtained by the method of [I] above with (a4) an unsaturated monomer having an epoxy group,
[IV] All the carboxyl groups contained by the method of [I] above are reacted with (a4) an unsaturated monomer having an epoxy group, and then hydroxyl formed by the reaction between the epoxy group and the carboxyl group. A resin formed by reacting a group with a cyclic acid anhydride and reacting a hydroxyl group with an acid anhydride group to form a carboxyl group,
[V] (a4) An unsaturated monomer having an epoxy group is copolymerized with (a6) another copolymerizable unsaturated monomer, and a part or all of the epoxy group is converted into (a1) a carboxyl group A resin formed by reacting a hydroxyl group produced by the reaction of an epoxy group and a carboxyl group with an acid anhydride group of a cyclic acid anhydride after reacting with an unsaturated monomer having a carboxyl group,
[VI] (a1) copolymerizing an unsaturated monomer having a carboxyl group and (a2) an unsaturated monomer having a hydroxyl group with (a6) another copolymerizable unsaturated monomer, A resin obtained by reacting a part or all of the hydroxyl group with an isocyanate group of an unsaturated monomer (a5) having an isocyanate group and introducing a radical polymerizable group;
Etc.

  In the resins [I] to [VI], (a6) the other copolymerizable unsaturated monomer contains (a3) an unsaturated monomer having an alicyclic skeleton, From the viewpoints of safety and chemical resistance.

((A1) unsaturated monomer having a carboxyl group)
(A1) Examples of the unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, maleic acid, maleic anhydride, fumaric acid, crotonic acid, α-hydroxymethylacrylic acid, and 3- (acryloyl). Oxy) propionic acid, p-vinylbenzoic acid, 2-[(meth) acryloyloxyethyl] succinic acid, 2-[(meth) acryloyloxyethyl] phthalic acid, 2-[(meth) acryloyloxyethyl] hexahydrophthal Acid, and the like.

((A2) Unsaturated monomer having hydroxyl group)
(A2) Examples of unsaturated monomers having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) ) Acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, ethyl-α-hydroxymethyl acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, 1,4-cyclohexanedimethanol mono (Meth) acrylate, monohydroxyethyl phthalate (meth) acrylate, p-hydroxyphenylethyl (meth) acrylate, 2,3-dihydroxypropyl (meth) acrylate,
((Meth) acrylates such as mono (meth) acrylates of polyols such as polyethylene glycol, polypropylene glycol, polybutylene glycol, polytetramethylene glycol, polyester, polycaprolactone, polybutadiene, etc.
Acrylamides such as N-methylol (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide,
Vinyl ethers such as 2-hydroxyethyl vinyl ether, 4-hydroxybutyl vinyl ether, diethylene glycol monovinyl ether, cyclohexanedimethanol monovinyl ether,
Etc.

((A4) unsaturated monomer having an epoxy group)
(A4) Examples of the unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4- (glycidyloxy) butyl (meth) acrylate, and 3-methyl-3,4- Epoxybutyl (meth) acrylate, 3-ethyl-3,4-epoxybutyl (meth) acrylate, 4-methyl-4,5-epoxypentyl (meth) acrylate, 5-methyl-5,6-epoxyhexyl (meth) Acrylate, glycidyl α-ethyl acrylate, allyl glycidyl ether, crotonyl glycidyl ale, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, N- (3,5-dimethyl-4 -Glycidyl) benzylacrylamide, o-vini Benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl glycidyl ether 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxymethylstyrene, 2,3,4-triglycidyloxy Methylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene, 2,4,6-triglycidyloxymethylstyrene Etc. I can get lost. Preferably, glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and (3,4-epoxycyclohexyl) methyl (meth) acrylate are mentioned from the viewpoint of easy availability of industrial products.

((A5) unsaturated monomer having an isocyanate group)
(A5) As an unsaturated monomer which has an isocyanate group, 2- (meth) acryloxyethyl isocyanate etc. are mentioned, for example.

((A6) Other copolymerizable unsaturated monomer)
(A6) Other copolymerizable unsaturated monomers include unsaturated monomers other than (a1) when the alkali-soluble resin is [I], and unsaturated monomers other than (a2) when [II]. Saturated monomer, unsaturated monomer other than (a1) in the case of [III], unsaturated monomer other than (a1) in the case of [IV], other than (a4) in the case of [V] In the case of an unsaturated monomer, [VI], examples include unsaturated monomers other than (a1) and (a2),
In addition to the unsaturated monomers listed in the above (a1) to (a5), for example, styrenes such as styrene, α-methylstyrene, chloromethylstyrene, 4-hydroxystyrene, vinylnaphthalene, methyl (meth) acrylate , Ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) ) Acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate Over DOO, dodecyl (meth) acrylate, tridecyl (meth) acrylate, hexadecyl (meth) acrylate, alkyl (meth) acrylates such as octadecyl (meth) acrylate, docosyl (meth) acrylate,
Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, rosin acrylate,
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, methoxypolypolyethylene glycol (meth) acrylate, Polyalkylene glycol-based macromonomers such as ethoxypolyethyleneglycol mono (meth) acrylate, phenoxypolyethyleneglycol (meth) acrylate, nonylphenoxypolyethyleneglycol (meth) acrylate, methoxypolypropyleneglycol (meth) acrylate,
(Meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N-butyl (meth) acrylamide, isobutyl (meth) acrylamide, t-butyl Unsubstituted or N-substituted (meth) acrylamides such as (meth) acrylamide, t-octyl (meth) acrylamide, N-butoxymethyl (meth) acrylamide and diacetone (meth) acrylamide;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate Nitriles such as (meth) acrylonitrile;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate and vinyl propionate;
Examples thereof include N-substituted maleimides such as maleimide, N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like.

  In addition, as described above, (a6) the other copolymerizable unsaturated monomer includes (a3) an unsaturated monomer having an alicyclic skeleton, so that adhesion to the substrate and chemical resistance are increased. From the viewpoint of

((A3) unsaturated monomer having alicyclic skeleton)
(A3) Examples of unsaturated monomers having an alicyclic skeleton include cyclohexyl (meth) acrylate, 3-cyclohexenylmethyl (meth) acrylate, 2,2,4-trimethylcyclohexyl (meth) acrylate, and tert- Butylcyclohexyl (meth) acrylate, isobornyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate, 2-ethyl-2-adamantyl (meth) acrylate, 3-hydroxy-1 -Adamantyl (meth) acrylate, perfluoro-1-adamantyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate,
3-methyl-3- (meth) acryloyloxymethyl-1-oxetane, 3-ethyl-3- (meth) acryloyloxymethyl-1-oxetane, 5-ethyl-5- (meth) acryloyloxymethyl-1,3 -Dioxane, tetrahydrofurfuryl (meth) acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, 1,4-dioxaspiro [4,5] dec-2- Yl) methyl (meth) acrylate, 3- (meth) acryloyloxy-1-oxolan-2-one,
N- (meth) acryloyloxyethyl hexahydrophthalimide, 1,2,2,6,6-pentamethyl-4-piperidyl (meth) acrylate, 2,2,6,6-tetramethyl-4-piperidyl (meth) acrylate , (Meth) acryloylmorpholine,
Etc. Cyclohexyl (meth) acrylate, tert-butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, and adamantyl (meth) acrylate are preferable in terms of adhesion, chemical resistance, hardness, etc., and in particular, tert-butylcyclohexyl. (Meth) acrylate is particularly preferable in terms of adhesion and chemical resistance, and adamantyl (meth) acrylate in terms of hardness.

  In the polymerization, it is preferable to arbitrarily use 0.001 to 15 parts by weight of a polymerization initiator with respect to 100 parts by weight of the total of ethylenically unsaturated monomers. As the polymerization initiator, a known polymerization initiator can be used, and it is preferable to use an azo compound and an organic peroxide. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like. These polymerization initiators can be used alone or in combination of two or more.

During the polymerization, a chain transfer agent may be used for the purpose of adjusting the molecular weight. It is preferable to arbitrarily use 0.001 to 15 parts by weight of a chain transfer agent with respect to 100 parts by weight of the total of ethylenically unsaturated monomers. The chain transfer agent is not particularly limited as long as it is a compound capable of adjusting the molecular weight, and a known chain transfer agent can be used. For example, octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, mercaptoethanol, thioglycerol, thioglycolic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, thioapple Mercaptans such as acids, octyl thioglycolate, octyl 3-mercaptopropionate, 2-mercaptoethanesulfonic acid, butylthioglycolate;
Disulfides such as dimethylxanthogen disulfide, diethylxanthogen disulfide, diisopropylxanthogen disulfide, tetramethylthiuram disulfide, tetraethylthiuram disulfide, tetrabutylthiuram disulfide;
Halogenated hydrocarbons such as carbon tetrachloride, methylene chloride, bromoform, bromotrichloroethane, carbon tetrabromide, ethylene bromide;
Secondary alcohols such as isopropanol, glycerin;
Phosphorous acid, hypophosphorous acid, and salts thereof (sodium hypophosphite, potassium hypophosphite, etc.), sulfurous acid, hydrogen sulfite, dithionite, metabisulfite, and salts thereof (sodium hydrogen sulfite) Lower oxides and salts thereof, such as potassium bisulfite, sodium dithionite, potassium dithionite, sodium metabisulfite, potassium metabisulfite);
And allyl alcohol, 2-ethylhexyl thioglycolate, α-methylstyrene dimer, terpinolene, α-terpinene, γ-terpinene, dipentene, anisole and the like. These may be used alone or in combination of two or more.

  In the polymerization, an organic solvent can be used as a polymerization solvent. As an organic solvent, it is preferable to use the solvent used for the photosensitive resin composition concerning this invention. For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene , Xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethoxydiethylene glycol, ethyl 3-ethoxypropionate, butanediol diacetate, and the like are used, but not particularly limited thereto. These polymerization solvents may be used as a mixture of two or more.

A catalyst for the reaction of the carboxyl group and the epoxy group used in the above methods [III] and [IV] and the reaction of the hydroxyl group and the cyclic acid anhydride used in the above methods [II], [IV] and [V]. Can be used. For example, trimethylamine, triethylamine, ethyldiisobutylamine, tributylamine, dimethylbenzylamine, pyridine, methylpyridine, tert-butylpyridine, 4-dimethylaminopyridine, imidazole, methylimidazole, 1,4-diazabicyclo [2.2.2. ] Amine catalysts such as octane;
Amidine-based catalysts such as 1,8-diazabicyclo [5.4.0] -7-undecene, 1,5-diazabicyclo [4.3.0] nonene;
Phosphine-based catalysts such as triphenylphosphine;
Quaternary ammonium salt catalysts such as tetramethylammonium chloride, tetramethylammonium bromide, tetraethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium bromide;
Is mentioned.

  A catalyst can be used in the reaction of the hydroxyl group and isocyanate group used in the above method [∨I]. For example, in addition to the catalyst as described above, dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, Tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate, dibutyltitanium dichloride, tetrabutyltitanate , Titanium such as butoxytitanium trichloride, lead such as lead oleate, lead 2-ethylhexanoate, lead benzoate, lead naphthenate, iron such as iron 2-ethylhexanoate, iron acetylacetonate Benzoate, cobalt-based, such as cobalt 2-ethylhexanoate, zinc naphthenate, zinc such as zinc 2-ethylhexanoate, zirconium naphthenate, and organic metal catalysts such as. These can be used alone or in combination.

  In introducing the radical polymerizable group in the above methods [III] to [VI], a gas having a polymerization inhibitory effect may be introduced into the reaction system, or a polymerization inhibitor may be added. By introducing a gas having a polymerization inhibition effect into the reaction system or adding a polymerization inhibitor, gelation during the addition reaction can be prevented. Examples of the gas having a polymerization inhibiting effect include a gas containing oxygen that does not enter the explosion range of the substance in the system, for example, air.

  A known polymerization inhibitor can be used and is not particularly limited. For example, hydroquinone, methoquinone, 2,6-di-t-butylphenol, 2,2′-methylenebis (4-methyl-6) -T-butylphenol), phenothiazine and the like. These polymerization inhibitors may be used alone or in combination of two or more. The amount of the polymerization inhibitor to be used is preferably 0.005 to 5 parts by weight, more preferably 0.03 to 3 parts by weight, more preferably 0.05 to 3 parts by weight with respect to 100 parts by weight of the total solids in the reaction system. Most preferred is 1.5 parts by weight. If the amount of the polymerization inhibitor is too small, the polymerization inhibition effect may not be sufficient. On the other hand, if the amount is too large, the exposure sensitivity may decrease. Further, it is more preferable to use a gas having a polymerization inhibitory effect in combination with a polymerization inhibitor because the amount of the polymerization inhibitor to be used can be reduced or the polymerization inhibitory effect can be enhanced.

  The reaction temperature is 40 to 150 ° C, preferably 50 to 110 ° C. If the temperature is lower than the above range, the addition reaction may not proceed sufficiently. On the other hand, if the temperature is higher than the above range, the radical polymerizable group will cause thermal polymerization and easily gel.

  (A) 20-200 mgKOH / g is preferable and, as for the acid value of alkali-soluble resin, 50-150 mgKOH / g is more preferable. If it is less than 20 mgKOH / g, sufficient developability may not be ensured. Moreover, when it exceeds 200 mgKOH / g, the viscosity of a composition is high and a malfunction may arise at the time of coating.

<(B) Compound having two or more (meth) acryloyl groups in the molecule>
(B) If the compound which has two or more (meth) acryloyl groups in a molecule | numerator is a well-known thing, it will not specifically limit.
Examples of the compound having two (meth) acryloyl groups in the molecule (bifunctional (meth) acrylate) include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and 1,3-butanediol di (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, 1,10-decanediol di (meth) acrylate Neopentyl glycol di (meth) acrylate, 3-methyl-1,5-pentanediol di (meth) acrylate, 2-butyl-2-ethyl-1,3-propanediol di (meth) acrylate, 2-methyl- 1,8-octanediol di (meth) acrylate, glycerin di (Meth) acrylate, hydroxypivalate neopentyl glycol di (meth) acrylate, [2- (meth) acryloyloxy-1,1-dimethyl] ethyl-4- (meth) acryloyloxymethyl-4-ethyl-1,3- And dioxane, tricyclodecane dimethanol di (meth) acrylate, 9,9-bis {4- [2- (meth) acryloyloxyethoxy] phenyl} fluorene, and the like.

  Examples of the compound having three (meth) acryloyl groups in the molecule (trifunctional (meth) acrylate) include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris [2- (meth) Acryloyloxyethyl] isocyanurate and the like.

  Examples of the compound having 4 or more (meth) acryloyl groups in the molecule (polyfunctional (meth) acrylate) include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth). ) Acrylate, tripentaerythritol octa (meth) acrylate, and the like.

  Examples also include oligomers having two or more (meth) acryloyl groups, such as polyether (meth) acrylate, polyester (meth) acrylate, epoxy (meth) acrylate, and urethane (meth) acrylate.

(B) The compound having two or more (meth) acryloyl groups in the molecule preferably has an alkyleneoxy chain or a carbonylalkyleneoxy chain. Examples thereof include an ethyleneoxy chain, a propyleneoxy chain, a butyleneoxy chain, and a carbonylpentamethyleneoxy chain.
Examples of the above compounds include those obtained by extending a chain of a polyfunctional alcohol with a cyclic ether such as ethylene oxide, propylene oxide, butylene oxide, or a cyclic ester such as ε-caprolactone (EO modified, PO modified, BO modified, CL modified, respectively). Can be obtained by esterification with (meth) acrylic acid.

As a (meth) acrylic acid ester of a polyol in which a polyfunctional alcohol is chain-extended with a cyclic ether or a cyclic ester, for example,
Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, EO modified 1,6-hexanediol di (meth) acrylate, EO modified neopentyl glycol di (meth) acrylate, PO modified neopentyl glycol di (meta ) Acrylate, EO-modified bisphenol A di (meth) acrylate, PO-modified bisphenol A di (meth) acrylate, CL-modified hydroxypivalic acid neopentyl glycol di (meth) acrylate, etc .;
EO-modified trimethylolpropane tri (meth) acrylate, PO-modified trimethylolpropane (meth) acrylate, CL-modified trimethylolpropane tri (meth) acrylate, EO-modified glycerol tri (meth) acrylate, PO-modified glycerol tri (meth) acrylate, Trifunctional (meth) acrylates such as CL-modified tris [2- (meth) acryloyloxyethyl] isocyanurate;
EO-modified polyglycerol poly (meth) acrylate, PO-modified polyglycerol poly (meth) acrylate, CL-modified polyglycerol poly (meth) acrylate, EO-modified pentaerythritol poly (meth) acrylate, PO-modified pentaerythritol propane poly (meth) acrylate 4 or more functional groups such as CL modified pentaerythritol poly (meth) acrylate, EO modified dipentaerythritol poly (meth) acrylate, PO modified dipentaerythritol poly (meth) acrylate, CL modified dipentaerythritol poly (meth) acrylate, etc. Polyfunctional (meth) acrylate;
Is mentioned.

  (B) The number of (meth) acryloyl groups contained in the compound having two or more (meth) acryloyl groups in the molecule is preferably 3 or more (trifunctional or more), 4 or more (4 functional or more) ) Is more preferable. As the number of functional groups increases, unreacted substances remaining when cured by heat or light are reduced, and chemical resistance is improved.

  (B) The double bond equivalent of the compound having two or more (meth) acryloyl groups in the molecule is preferably 400 or less, and more preferably 100 to 250. When it is 400 or more, curing may be insufficient and chemical resistance may deteriorate.

<(C) Compound having only one epoxy group or β-hydroxyalkylamide group>
(C) The compound having only one epoxy group or β-hydroxyalkylamide group is supposed to react with the carboxyl group contained in (A) the alkali-soluble resin. Since a hydroxyl group may be contained in (A) an alkali-soluble resin or (B) a compound having two or more (meth) acryloyl groups in the molecule, a carboxyl group is used in the present invention even in the presence of a hydroxyl group. And a compound having an epoxy group and a β-hydroxyalkylamide group that selectively react. Furthermore, a compound having an epoxy group is preferable from the viewpoint of reactivity with a carboxyl group, and a compound having a glycidyl group is more preferable among epoxy groups.

  For the above reasons, the compound (C) having only one epoxy group or β-hydroxyalkylamide group of the present invention is preferably a compound having no functional group that reacts with other carboxyl groups. In addition to the epoxy group and β-hydroxyalkylamide group, examples of the functional group that can further react with the carboxyl group include N-methylol group, vinyloxy group, isocyanate group, carbodiimide group, oxazoline group, alkoxysilyl group, silanol group, oxetane. Group and the like.

Examples of the compound having only one epoxy group include butyl glycidyl ether, 2-ethylhexyl glycidyl ether, lauryl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, allyl glycidyl ether, p-tert-butylphenyl glycidyl ether, nonyl Monoglycidyl ethers such as phenyl glycidyl ether, p-sec-butylphenyl glycidyl ether, o-phenylphenol glycidyl ether, 2,4-dibromophenyl glycidyl ether, phenoxy polyethylene glycol glycidyl ether, polyethylene glycol monoalkoxy monoglycidyl ether;
Monoglycidylamines such as N-glycidylphthalimide;
1,2-epoxyhexane, 1,2-epoxyoctane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, etc. Monoepoxyalkanes of
1,2-epoxy-4-vinylcyclohexane, 2,7,7-trimethyl-3-oxatricyclo [4.1.1.0 ^2,4 ] octane, 4,5-epoxycyclohexane-1,2-dicarboxylic Acid bis (2-ethylhexyl), 3,4-epoxycyclohexane-1-carboxylate allyl, 3,4-epoxycyclohexane-1-carboxylate 2-ethylhexyl, 1-methyl-4-isopropenyl-7-oxabicyclo [ 4.1.0] alicyclic monoepoxy such as heptane;
Styrene oxide, α-methylstyrene oxide;
Etc.

  Examples of the compound having only one β-hydroxyalkylamide group include N- (2-hydroxyethyl) acetamide, N-methyl-N- (2-hydroxyethyl) acetamide, N-ethyl-N- (2- Hydroxyethyl) acetamide, N-butyl-N- (2-hydroxyethyl) acetamide, N- (2-hydroxyethyl) acrylamide, N- (2-hydroxyethyl) propionamide, N- (2-hydroxyethyl) lactoamide, N- (2-hydroxyethyl) laurylamide, N- (2-hydroxyethyl) benzamide, 1- (2-hydroxyethyl) -2-pyrrolidone, N- (2-hydroxyethyl) phthalimide and the like can be mentioned.

  (C) The compound having only one epoxy group or β-hydroxyalkylamide group preferably has a boiling point of 150 ° C. or higher, preferably 200 ° C. or higher, and more preferably 230 ° C. or higher. A low boiling point is not preferable because it volatilizes during the steps of coating, drying and curing.

  (C) The compound having only one epoxy group or β-hydroxyalkylamide group is preferably blended in an amount of 0.2 to 2.0 mol with respect to 1 mol of the carboxyl group contained in the (A) alkali-soluble resin. . More preferably, it is 0.5-1.2 mol, More preferably, it is 0.8-1.0 mol.

<(D) Organosilicon compound>
(D) The organosilicon compound refers to a compound in which a carbon atom and a silicon atom are directly covalently bonded. (Silica, silazane, quartz, etc. are not included)
Examples of (D) organosilicon compounds include vinyltrimethoxysilane, vinyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycid. Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltrimethoxysilane, p-styryltrimethoxysilane, 3-methacryloyloxypropylmethyldimethoxysilane, 3-methacryloyloxypropyltrimethoxy Silane, 3-methacryloyloxypropylmethyldiethoxysilane, 3-methacryloyloxypropyltriethoxysilane, 3-acryloyloxypropyltrimethoxysilane, N-2- (aminoethyl)- -Aminopropylmethyldimethoxysilane, N-2- (aminomethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N- (1 , 3-dimethylbutylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis (triethoxysilylpropyl) tetrasulfide, 3-isocyanatopropyltriethoxysilane, N, N ′, N ″ -tris [3- (tri Methoxysilyl) propi ] Isocyanurate, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, decyltrimethoxysilane, trifluoro Examples include silane coupling agents such as propyltrimethoxysilane and hexamethyldisilazane.

  Further, polysiloxane obtained by partially hydrolyzing and condensing the organosilicon compound in advance is also included.

  The silane coupling agent preferably has one or more functional groups selected from an amino group, a blocked amino group, an isocyanate group, a blocked isocyanate group, an isocyanurate group and a ureido group from the viewpoint of chemical resistance and adhesion. An amino group is effective in terms of adhesion, and a blocked isocyanate group is effective in terms of heat resistance and developability. From the viewpoint of compatibility with other physical properties, it is particularly preferable to have a blocked isocyanate group.

<(E) Photoradical polymerization initiator>
(E) As a radical photopolymerization initiator, for example, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthyl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (4-ethoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-ethoxycarbonylnaphthyl) -4,6-bis (trichloromethyl) ) -Halomethylated triazine derivatives such as -s-triazine;
2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxa Diazole, 2-trichloromethyl-5-[[beta]-[2 '-(6 "-benzofuryl) vinyl]]-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1,3 Halomethylated oxadiazole derivatives such as 4-oxadiazole;
2- (2′-chlorophenyl) -4,5-diphenylimidazole dimer, 2- (2′-chlorophenyl) -4,5-bis (3′-methoxyphenyl) imidazole dimer, 2- ( 2'-fluorophenyl) -4,5-diphenylimidazole dimer, 2- (2'-methoxyphenyl) -4,5-diphenylimidazole dimer, (4'-methoxyphenyl) -4,5-diphenyl Imidazole derivatives such as imidazole dimer;
Benzoin ethers such as benzoin methyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether;
Anthraquinone derivatives such as 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1-chloroanthraquinone;
Benzophenone derivatives such as benzophenone, Michler's ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone;
2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p -Isopropylphenyl) ketone, 1-hydroxy-1- (p-dodecylphenyl) ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloro Acetophenone derivatives such as methyl- (p-butylphenyl) ketone;
Thioxanthone derivatives such as thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone;
benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate;
Acridine derivatives such as 9-phenylacridine, 9- (p-methoxyphenyl) acridine;
Phenazine derivatives such as 9,10-dimethylbenzphenazine;
Anthrone derivatives such as benzanthrone;
Di-cyclopentadienyl Ti-di-chloride, di-cyclopentadienyl Ti-bis-phenyl, di-cyclopentadienyl Ti-bis-2,3,4,5,6-pentafluorophenyl-1- , Di-cyclopentadienyl Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl Ti-bis-2,4,6-trifluorophen-1- Yl, di-cyclopentadienyl Ti-2,6-dipuruolophen-1-yl, di-cyclopentadienyl Ti-2,4-di-fluorophen-1-yl, di-methylcyclopentadi Enyl Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl Ti-bis-2,6-di-fluorophen-1-yl, di-cyclo Ntajieniru Ti-2,6-di - fluoro-3- (pill-1-yl) - titanocene derivatives of 1-yl and the like;
2-Methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1,2-benzyl 2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 4-dimethylaminoethylbenzoate, 4-dimethylaminoisoamylbenzoate, 4-diethylaminoacetophenone, 4-dimethylamino Propiophenone, 2-ethylhexyl-1,4-dimethylaminobenzoate, 2,5-bis (4-diethylaminobenzal) cyclohexanone, 7-diethylamino-3- (4-diethylaminobenzoyl) coumarin, 4- (diethylamino) chalcone Α-aminoalkylphenone compounds such as
1,2-octanedione, 1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3 And oxime ester compounds such as -yl] -1- (O-acetyloxime). In particular, acetophenone and oxime ester compounds are preferred in terms of sensitivity.

  (E) The amount of radical photopolymerization initiator used is preferably 0.01 to 10% by weight, more preferably 0.05 to 7% by weight, particularly preferably 100% by weight in total of the solid content of the photosensitive composition. Is 0.1 to 5% by weight. If it is less than 0.01% by weight, the photocuring reactivity may be poor and polymerization may not proceed, and if it exceeds 10% by weight, transparency may be deteriorated due to the yellowing of the initiator.

<(F) filler>
The resin composition of the present invention preferably further contains (F) a filler. (F) The filler may be surface-treated, and from the viewpoint of the colorlessness of the cured film of the resulting curable composition, oxidation of at least one element selected from the group consisting of silicon, aluminum, zirconium, titanium and zinc It is preferable that it is a physical particle. Of these, from the viewpoint of transmittance, oxide particles of silicon, zirconium, or aluminum are preferable, and silicon oxide particles are particularly preferable. (F) By using a filler, pencil hardness can be made higher and a coating film with high chemical resistance can be obtained.

  (F) The filler is a physical substance such as plasma discharge treatment or corona discharge treatment in order to stabilize dispersion in the dispersion or coating solution, or to increase the affinity and binding properties with the binder component. Surface treatment, chemical surface treatment with a surfactant, a coupling agent, or the like may be performed.

  (F) The average primary particle diameter of the filler 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 (F) filler is measured using the BET method. Specifically, the specific surface area of the inorganic oxide fine particles obtained by the BET method is obtained, the ratio of volume to surface area is calculated using the specific gravity of the inorganic oxide, and the particles are assumed to be true spheres. The particle diameter is obtained from these ratios and is taken as the average primary particle diameter.

(F) The filler is 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 organic solvents include alcohol solvents such as methanol, ethanol, isopropanol, butanol, and octanol; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ethyl acetate, butyl acetate, ethyl lactate, γ -Ester solvents such as butyrolactone, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; ether solvents such as ethylene glycol monomethyl ether and diethylene glycol monobutyl ether; aromatic hydrocarbon solvents such as benzene, toluene and xylene; dimethyl Examples include amide solvents such as formamide, dimethylacetamide, and 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 particularly preferably used in the present invention include PMA-ST, IPA-ST, IPA-ST-MS, IPA-ST-L, manufactured by Nissan Chemical Industries, Ltd. IPA-ST-ZL, IPA-ST-UP, EG-ST, NPC-ST-30, MEK-ST, MEK-ST-L, MIBK-ST, NBA-ST, XBA-ST, DMAC-ST, ST- Examples include UP, ST-OUP, ST-20, ST-40, ST-C, ST-N, ST-O, ST-50, ST-OL, etc., hollow silica CS60-IPA manufactured by Catalyst Kasei Kogyo Co., Ltd. be able to. As powder silica, Aerosil 130, Aerosil 300, Aerosil 380, Aerosil TT600, Aerosil OX50, Silex H31, H32, H51, H52, H121, H122, Asahi Glass 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 zirconia oxide fine particle dispersions preferably used in the present invention include ZR-40BL, ZR-30BS, ZR-30AL, ZR-30AH, etc. manufactured by Nissan Chemical Industries, Ltd., Sumitomo Osaka Cement ( HXU-110JC manufactured by Co., Ltd. can be mentioned.

  Commercially available products as aluminum oxide fine particle dispersions preferably used in the present invention include alumina sol-100, alumina sol-200, alumina sol-520 manufactured by Nissan Chemical Industries, Ltd. and AS- manufactured by Sumitomo Osaka Cement Co., Ltd. 150I, AS-150T.

  In addition, examples of the inorganic oxide fine particle dispersion preferably used in the present invention include oxide fine particle dispersions of titanium, zinc and the like, and examples of commercially available products include Nanotech manufactured by C-Kasei Co., Ltd.

  (F) The addition amount of the filler is preferably 5 to 40% by weight, more preferably 10 to 35% by weight, in the total solid content of 100% by weight in the resin composition. When the addition amount is less than 5% by weight, it is difficult to obtain effects such as improvement of pencil hardness and chemical resistance. On the other hand, when the addition amount exceeds 40% by weight, problems such as lowering of substrate adhesion may occur. is there.

  The following additives can be used for the photocurable resin composition of the present invention. For example, a surfactant such as a leveling agent, a silane coupling agent, an antioxidant, a light resistance stabilizer, a heat resistance stabilizer and the like can be added as necessary.

  The thickness of the color filter protective film, interlayer insulating film, photospacer, etc. formed from the photocurable resin composition of the present invention is preferably 0.005 to 30 μm, and 0.01 to 20 μm. Is more preferable, and 0.1 to 10 μm is particularly preferable. By setting the thicknesses of the color filter protective film, the interlayer insulating film, the photospacer, and the like in such ranges, an appropriate mechanical strength and heat resistance can be obtained, and there is little possibility of impairing the light transmittance.

  Further, the method for applying the photocurable resin composition of the present invention to a glass substrate or the like is not particularly limited, and for example, an immersion method, a spray method, a roll coating method, a spin coating method, and the like can be used. In addition, it can be applied by printing methods such as screen printing, offset printing, and gravure printing.

  Furthermore, the drying method after applying the photocurable resin composition of the present invention to a glass substrate or the like is not particularly limited, but for example, an oven or an infrared heater can be used. . And although the heating conditions can also be changed depending on the kind of each component used in the photosensitive composition, the addition amount (blending amount), etc., the temperature is usually in the range of 50 to 300 ° C. Heat curing is preferably performed under a condition of ˜60 minutes, and more preferably, the temperature is within a range of 80 to 250 ° C., and is a heat curing condition of 0.5 to 10 minutes.

The photocuring method is not particularly limited. For example, it is possible to irradiate ultraviolet rays using a high pressure mercury lamp, a metal halide lamp or the like as a light source. And although the irradiation conditions can also be changed according to the kind of each component used in the photosensitive composition, the addition amount (blending amount), etc., the irradiation amount of ultraviolet rays is usually 10 to 500 mJ / cm ^2. More preferably, it is 20-300 mJ / cm < ² >. After photocuring, it may be thermally cured by further heating.

  Regarding thermosetting performed after photocuring, although it can be changed depending on the type of each component used in the photocurable resin composition, the amount added (blending amount), etc., (A) the carboxyl group in the alkali-soluble resin and (C) A temperature at which the functional group in the compound having only one epoxy group or β-hydroxyalkylamide group reacts is preferable, and the heating is performed in the range of 50 to 300 ° C. for 0.1 to 10 hours. It is preferable to cure, more preferably, the temperature is in the range of 100 to 250 ° C. for 0.2 to 5.0 hours, and more preferably in the range of 150 to 250 ° C. for 0.3 to 2 hours under heat curing conditions. is there.

  By using the photocurable resin composition of the present invention, a coating film excellent in heat resistance, transparency, substrate adhesion, and insulation as an interlayer insulating film and a photospacer for liquid crystal panels and touch panels, particularly touch panels. Can be obtained. In addition, a color filter having a protective film excellent in adhesion to the black matrix, the RGB colored layer, the transparent electrode, the sealant, and the alignment film can be obtained.

  The photo-curable resin composition of the present invention can be used not only for insulating films for touch panels, photo spacers and color filter protective films, but also for optical hard coats, solder resists, photosensitive coverlays, dry film resists, various coatings, UV inks, It can be used for photosensitive lithographic printing plates.

  The present invention will be described more specifically with reference to the following examples. However, the following examples do not limit the scope of rights of the present invention. In the examples, “part” represents “part by weight” and “%” represents “% by weight”.

<(A) Example of production of alkali-soluble resin>
[Production Example of Alkali-Soluble Resin (A-1)] <Inert, No Alicyclic Production Method [I]>
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 and heated to 90 ° C. under a nitrogen stream. A mixture of 20 parts of acid, 48 parts of propylene glycol monomethyl ether acetate and 3 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) was added dropwise over 2 hours, and then 2 hours, 90 The reaction was carried out while maintaining the temperature. After cooling to room temperature, the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content was 30% to obtain a propylene glycol monomethyl ether acetate solution of (A) alkali-soluble resin A-1.

[Production Example of Alkali-Soluble Resin (A-2)] <Inert / Aliphalic / Production Method [II]>
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 123 parts of cyclohexanone, heated to 110 ° C. under a nitrogen stream, and 30 parts of butyl methacrylate, 20 parts of cyclohexyl methacrylate, A mixed solution in which 20 parts of 2-methoxyethyl acrylate, 30 parts of 2-hydroxyethyl methacrylate, 16 parts of cyclohexanone and 8 parts of dimethyl 2,2′-azobis (2-methylpropionate) were uniformly mixed in advance was taken over 2 hours. Then, the reaction was continued for 3 hours at 110 ° C. Then, 30 parts of 4-cyclohexene-1,2-dicarboxylic acid anhydride was added and reacted at 110 ° C. for 2 hours. After cooling to room temperature, the solution was diluted with cyclohexanone so that the solid content was 30% to obtain a cyclohexanone solution of (A) alkali-soluble resin A-2.

[Production Example of Alkali-Soluble Resin (A-3)] <Photo, Alicyclic Existence, Production Method [III]>
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 123 parts of cyclohexanone, heated to 110 ° C. under a nitrogen stream, and 4-tert-butylcyclohexyl methacrylate 61.45 from the dropping vessel. Parts, 10.45 parts of styrene, 21.0 parts of 2-methoxyethyl acrylate, 29.86 parts of methacrylic acid, 15.7 parts of cyclohexanone and 8.85 parts of dimethyl 2,2′-azobis (2-methylpropionate) Was added dropwise over 2 hours, and the reaction was continued for 3 hours at 110 ° C. Thereafter, the air flow was switched to a dry air flow, 27.1 parts of glycidyl methacrylate, 1.5 parts of N, N-dimethylbenzylamine, 0.15 parts of 4-methoxyphenol, and 11.4 parts of cyclohexanone were added and reacted at 110 ° C. for 4 hours. I let you. After cooling to room temperature, the solution was diluted with cyclohexanone so that the solid content was 30% to obtain a cyclohexanone solution of (A) alkali-soluble resin A-3.

[Production Example of Alkali-Soluble Resin (A-4)] <Photo, No Alicyclic Production Method [V]>
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 123 parts of cyclohexanone, heated to 110 ° C. under a nitrogen stream, and 30 parts of butyl methacrylate and 2-methoxyethyl acrylate from the dropping tank. 20 parts, 50 parts of glycidyl methacrylate, 16 parts of cyclohexanone and 8 parts of dimethyl 2,2′-azobis (2-methylpropionate) were mixed dropwise in advance over 2 hours, and then 3 hours, 110 The reaction was carried out while maintaining the temperature. Thereafter, the air flow was switched to a dry air stream, 25 parts of acrylic acid, 1.5 parts of N, N-dimethylbenzylamine, 0.15 part of 4-methoxyphenol, and 10 parts of cyclohexanone were added and reacted at 110 ° C. for 4 hours. Thereafter, 25 parts of succinic anhydride was added and further reacted at 110 ° C. for 2 hours. After cooling to room temperature, it was diluted with cyclohexanone so that the solid content was 30%, and a cyclohexanone solution of (A) alkali-soluble resin A-4 was obtained.

[Production Example of Alkali-Soluble Resin (A-5)] <Photo, No Alicyclic Production Method [III]>
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 123 parts of cyclohexanone, heated to 110 ° C. under a nitrogen stream, and 40 parts of methyl methacrylate, 60 parts of methacrylic acid, A mixed solution in which 16 parts of cyclohexanone and 8 parts of dimethyl 2,2′-azobis (2-methylpropionate) were uniformly mixed in advance was added dropwise over 2 hours, and the reaction was continued at 110 ° C. for 3 hours. Thereafter, the air flow was switched to a dry air flow, 50 parts of glycidyl methacrylate, 1.5 parts of N, N-dimethylbenzylamine, 0.15 part of 4-methoxyphenol, and 11.4 parts of cyclohexanone were added and reacted at 110 ° C. for 4 hours. . After cooling to room temperature, the solution was diluted with cyclohexanone so that the solid content was 30%, to obtain a cyclohexanone solution of (A) alkali-soluble resin A-5.

[Example of production of alkali-insoluble resin (A-6)]
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 100 parts of methyl methacrylate and propylene were added from the dropping tank. A mixed solution in which 48 parts of glycol monomethyl ether acetate and 3 parts of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed in advance was added dropwise over 2 hours, and the reaction was continued for 2 hours at 90 ° C. It was. After cooling to room temperature, the mixture was diluted with propylene glycol monomethyl ether acetate so that the solid content was 30% to obtain a propylene glycol monomethyl ether acetate solution of alkali-insoluble resin A-6.

Abbreviations in Table 1 are shown.
MAA: methacrylic acid HEMA: 2-hydroxyethyl methacrylate CHMA: cyclohexyl methacrylate TBCHMA: 4-tert-butylcyclohexyl methacrylate GMA: glycidyl methacrylate MMA: methyl methacrylate BMA: butyl methacrylate 2MTA: 2-methoxyethyl acrylate St: styrene V-65: 2,2'-azobis (2,4-dimethylvaleronitrile)
V-601: Dimethyl 2,2′-azobis (2-methylpropionate)
PGMAc: propylene glycol monomethyl ether acetate AA: acrylic acid DMBA: N, N-dimethylbenzylamine MEHQ: 4-methoxyphenol THPA: 4-cyclohexene-1,2-dicarboxylic acid anhydride SA: succinic anhydride

<(D) Production example of organosilicon compound>
[Production Example of Organosilicon Compound (D-1)] <Containing Blocked Isocyanate Group>
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of 3- (triethoxysilyl) propyl isocyanate (“KBE-9007” manufactured by Shin-Etsu Chemical Co., Ltd.) and 137 parts of ethanol are added, and nitrogen is added. The reaction was performed at 60 ° C. for 6 hours under an air stream. After cooling to room temperature, a 50% ethanol solution of ethyl = N- [3- (triethoxysilyl) propyl] carbamate (D-1), which is a blocked isocyanate group-containing silane coupling agent, was obtained.

<Adjustment of photocurable resin composition>
[Example 1]
After stirring the mixture of the following composition until it became uniform, it filtered with a 1 micrometer filter, and obtained photosensitive composition S-1.
(A) Alkali-soluble resin:
(A-1) Resin solution (solid content 30%) 152 parts (B) Compound having two or more (meth) acryloyl groups in the molecule:
ε-caprolactone-modified dipentaerythritol hexaacrylate (“KAYARAD DPCA-60” manufactured by Nippon Kayaku Co., Ltd.) 11.3 parts (C) Compound having only one epoxy group or β-hydroxyalkylamide group:
Phenyl glycidyl ether 7 parts (D) Organosilicon compound:
(D-1) Solution (solid content 50%) 35.8 parts (E) Photoradical polymerization initiator:
2-Methyl-1- [4- (methylthio) phenyl] -2-
(4-morpholinyl) -1-propanone ("IRGAGURE 907" manufactured by BASF) 3.0 parts (F) filler:
Silica fine particle 30% solid content propylene glycol monomethyl ether acetate dispersion (Nissan Chemical "PMA-ST", average primary particle size 15 nm) 50.3 parts leveling agent:
Polypropylene structure-containing polydimethylsiloxane 51% solid propylene glycol monomethyl ether acetate solution ("BYK-330" manufactured by Big Chemie) 0.2 parts Solvent:
Propylene glycol monomethyl ether acetate 240.4 parts

[Examples 2 to 28, Comparative Examples 1 to 6]
After stirring and mixing the mixture with the blending compositions shown in Tables 2 to 6 so as to be uniform, the mixture was filtered with a 1 μm filter, and the photocurable resin compositions S-2 to S-28 and H-1 to H-6 were obtained. Got.

<Evaluation of photocurable resin composition>
Glass substrate (Corning glass “Eagle 2000”), ITO substrate (Geomatec ITO film), Mo substrate (Toho Kaken Co. Mo film), each finished at 230 ° C. for 20 minutes using a spin coater The obtained photosensitive composition was applied so that the film thickness was 2.0 μm, held on a hot plate heated to 110 ° C. for 2 minutes, and then exposed to 20 mJ / cm using an ultrahigh pressure mercury lamp. Ultraviolet light exposure was performed so as to be ² . This substrate was heated at 230 ° C. for 20 minutes to prepare a coating film on each substrate. The actual film thickness of the coating film was measured with a stylus type film thickness meter DEKTAK-150 manufactured by ULVAC.
The following evaluation was performed about the obtained cured film. The results are shown in Tables 2-6.

(Measurement of transmittance)
The transmittance | permeability in wavelength 400nm of the coating film on a glass substrate was measured using the spectrophotometer (Hitachi "U-3310"). The determination was made according to the following criteria.
Transmittance 97% or higher: Good level (Judgment ◎)
Transmittance 95% or more and less than 97%: Practical level (judgment ○)
Transmittance <95%: Level not suitable for practical use (judgment x)

(Heat resistance: Measurement of transmittance after additional baking)
The substrate whose transmittance was measured was further heated at 280 ° C. for 1 hour, and the transmittance of the coating film at a wavelength of 400 nm was measured using a spectrophotometer (“U-3310” manufactured by Hitachi, Ltd.). The determination was made according to the following criteria.
Transmittance 95% or higher: Good level (Judgment ◎)
Transmittance 90% or more and less than 95%: Practical level (judgment ○)
Transmittance less than 90%: Level not suitable for practical use (judgment ×)

(Surface hardness measurement: pencil hardness)
The surface hardness of the coating film on the glass substrate was measured by a scratch hardness (pencil method) test according to JIS K5600-5-4. The determination was made according to the following criteria.
6H or higher: Very good level (Judgment ◎)
4H, 5H: Good level (judgment)
H to 3H: Practical level (determination Δ)
F or less: Level not suitable for practical use (judgment ×)

(Measurement of adhesion to glass substrate, ITO substrate, Mo substrate)
The substrate adhesion of the coating film was evaluated by an adhesion (cross-cut method) test in accordance with JIS K5600-5-6, and the number of peels in the grid 100 was counted. The determination was made according to the following criteria.
Number of peeled 0: Very good level (Judgment ◎)
Number of peeled 1-4: Good level (judgment ○)
Number of peeled 5 to 10: Practical level (determination △)
Peeling number More than 10: Level not suitable for practical use (judgment ×)

(Chemical resistance: adhesion after chemical immersion, film thickness measurement)
The coating film on the ITO substrate was immersed in a chemical at 45 ° C. for 5 minutes, washed with ion-exchanged water and allowed to stand for 30 minutes. The following three chemicals were used.
-Hydrochloric acid / nitric acid mixed solution (nitric acid / hydrochloric acid / water = 0.1 / 1/1)
-Mixed acid aluminum (Wako Pure Chemical Industries, Ltd.)
・ N-300 (manufactured by Nagase ChemteX Corporation)

The substrate adhesion of the coating film was evaluated by an adhesion (cross-cut method) test according to JIS K5600-5-6, and the number of peels in the grid 100 was counted. The determination was made according to the following criteria.
Number of peeled 0: Very good level (Judgment ◎)
Number of peeled 1-4: Good level (judgment ○)
Number of peeled 5 to 10: Practical level (determination △)
Peeling number More than 10: Level not suitable for practical use (judgment ×)

Moreover, the film thickness after immersion was measured and the change rate with respect to the film thickness before immersion was calculated | required. The determination was made according to the following criteria.
Change in film thickness ± 2% or less: Very good level (judgment ◎)
Film thickness change ± 2% or more and less than 3.5%: Good level (judgment)
Change in film thickness ± 3.5% or more and less than 7%: Practical level (determination Δ)
Change in film thickness ± 7% or more: Level not suitable for practical use (judgment x)

(Developability: Development speed measurement)
Separately from the above, the obtained photosensitive composition was applied on a glass substrate with a spin coater so that the finished film thickness was 2.0 μm, and held on a hot plate heated to 110 ° C. for 2 minutes. Using a high pressure mercury lamp, ultraviolet light exposure was performed through the mask pattern so that the exposure amount was 20 mJ / cm ² . This substrate is spray-developed at a pressure of 0.05 MPa using a 0.045% aqueous potassium hydroxide solution (developer temperature: 25 ° C.), and the time until the unexposed film is dissolved and the substrate surface is exposed (Development time) was measured. The determination was made according to the following criteria.
Development time Less than 30 seconds: Very good level (Judgment ◎)
Development time 30 seconds or more and less than 120 seconds: Good level (judgment)
Development time 120 seconds or more: Level not suitable for practical use (judgment x)

Abbreviations used in Tables 2 to 6 are as follows.
B-1: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (“Aronix M-402” manufactured by Toagosei Co., Ltd.)
B-2: Mixture of tripentaerythritol octaacrylate, tetrapentaerythritol decaacrylate, pentapentaerythritol dodecaacrylate (“Biscoat # 802” manufactured by Osaka Organic Chemical Industry Co., Ltd.)
B-3: ε-caprolactone-modified dipentaerythritol hexaacrylate (“KAYARAD DPCA-60” manufactured by Nippon Kayaku Co., Ltd.)
B-4: ε-caprolactone-modified dipentaerythritol hexaacrylate (“KAYARAD DPCA-120” manufactured by Nippon Kayaku Co., Ltd.)
B-5: Cyclohexyl acrylate (monofunctional monomer)

C-1: Phenyl glycidyl ether (boiling point 245 ° C.)
C-2: 2-ethylhexyl glycidyl ether (boiling point 248-251 ° C.)
C-3: Butyl glycidyl ether (boiling point 164 ° C.)
C-4: Lauryl glycidyl ether (boiling point 293-297 ° C.)
C-5: p-nonylphenyl glycidyl ether (boiling point 300 ° C. or higher)
C-6: N-glycidylphthalimide (boiling point 300 ° C. or higher)
C-7: 1,2-epoxydecane (boiling point 260 ° C.)
C-8: 1,2-epoxy-4-vinylcyclohexane (boiling point 169 ° C.)
C-9: Bis (2-ethylhexyl) 4,5-epoxy-1,2-dicarboxylate (boiling point 300 ° C. or higher)
C-10: N- (2-hydroxyethyl) laurylamide (boiling point 300 ° C. or higher)
C-11: 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol ("EHPE3150" manufactured by Daicel, polyfunctional epoxy compound)

D-1: Ethyl = N- [3- (triethoxysilyl) propyl] carbamate in 50% ethanol solution D-2: 3-aminopropyltrimethoxysilane D-3: 3-mercaptopropyltrimethoxysilane D-4: 3-Methacryloyloxypropyltrimethoxysilane

E-1: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (“IRGAGURE 907” manufactured by BASF)
E-2: 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (“IRGACURE OXE01” manufactured by BASF Corporation)

F-1: Propylene glycol monomethyl ether acetate dispersion having a solid content of silica fine particles of 30% ("PMA-ST" manufactured by Nissan Chemical Co., Ltd.)
F-2: Tetramethylammonium hydroxide aqueous solution dispersion of 40% solid content of zirconia fine particles (“ZR-40BL” manufactured by Nissan Chemical Co., Ltd.)

BYK330: Polypropylene structure-containing polydimethylsiloxane having a solid content of 51% propylene glycol monomethyl ether acetate solution ("BYK-330" manufactured by BYK Chemie)
PGMAc: Propylene glycol monomethyl ether acetate

As in Examples 1 to 28, the photocurable composition of the present invention balances necessary physical properties such as transmittance, heat resistance, pencil hardness, adhesion to glass, ITO, and Mo substrates, chemical resistance, and developability. The result was well met.
Comparative Example 1 is an example in which an alkali-insoluble resin is used, but alkali development cannot be performed and patterning cannot be performed.
Comparative Example 2 is an example in which a compound having only one acryloyl in the molecule was used as a curing component, but the crosslinking density was considered to be insufficient, such as low pencil hardness and poor resistance to chemicals. It was.
Although the comparative example 3 is an example which does not contain the compound which has only one (C) epoxy group or (beta) -hydroxyalkylamide group, the tolerance with respect to a chemical | drug | medicine was inadequate.
Comparative Example 4 is an example using a compound having two or more epoxy groups, but the change in film thickness during the chemical resistance test is suppressed as compared with Comparative Example 3, but conversely the adhesion deteriorates. It was.
Although the comparative example 5 is an example which does not add the (D) organosilicon compound, it resulted in that the adhesiveness with respect to a base material deteriorated.
Comparative Example 6 was an example in which (E) the photoradical polymerization initiator was not added, but it was not cured at the time of exposure, and no pattern was formed.

  By using the photocurable resin composition of the present invention, a coating film excellent in heat resistance, transparency, substrate adhesion, and insulation as an interlayer insulating film and a photospacer for liquid crystal panels and touch panels, particularly touch panels. Can be obtained. In addition, a color filter having a protective film excellent in adhesion to the black matrix, the RGB colored layer, the transparent electrode, the sealant, and the alignment film can be obtained. Moreover, it can be used not only for the above applications but also for optical hard coats, solder resists, photosensitive coverlays, dry film resists, various coatings, UV inks, photosensitive lithographic printing plates and the like.

Claims (11)

The photocurable resin composition characterized by including the following component.
(A) Alkali-soluble resin (B) Compound having two or more (meth) acryloyl groups in the molecule (C) Compound having only one epoxy group or β-hydroxyalkylamide group (D) Organosilicon compound (E ) Photo radical polymerization initiator The photocurable resin composition according to claim 1, wherein the alkali-soluble resin (A) further has a radical polymerizable group. (D) The photocurable resin composition according to claim 1, wherein the organosilicon compound contains a silane coupling agent. The silane coupling agent has one or more functional groups selected from the group consisting of amino groups, blocked amino groups, isocyanate groups, blocked isocyanate groups, isocyanurate groups, ureido groups, and mercapto groups. Item 4. The photocurable resin composition according to Item 3. The photocurable resin composition according to claim 1, further comprising (F) a filler. (F) The photocurable resin composition according to claim 5, wherein the filler is silica. (B) The photocurable resin composition according to claim 1, wherein the compound having two or more (meth) acryloyl groups in the molecule has an alkyleneoxy chain or a carbonylalkyleneoxy chain. . The interlayer insulation film formed by hardening | curing the photocurable resin composition in any one of Claims 1-7. A touch panel having the interlayer insulating film according to claim 8. A color filter protective film obtained by curing the photocurable resin composition according to claim 1. A photospacer formed by curing the photocurable resin composition according to claim 1.