JP2011043806A - Photosensitive composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a photosensitive composition superior in storage stability, heat resistance, transparency, base material adhesion, and flatness, and to provide a coating agent containing the photosensitive composition and a color filter protective film, an interlayer dielectric, and a photospacer using it. <P>SOLUTION: The photosensitive composition includes: an acrylic curable resin (A) having a linear/branched-chain 1-4C alkyl group, a carboxyl group, and an ethylenic unsaturated group; at least one epoxy compound (B) selected from the group consisting of an epoxy compound having a monocyclic ring, an epoxy compound having a bicyclic ring, and an epoxy compound having a tricyclic ring; a polymerizable compound (C) having an ethylenic unsaturated group; and a solvent (D). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

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

  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, and flatness according to their use, and radiation sensitive compositions are required to have storage stability. It was difficult to obtain a satisfactory radiation sensitive composition. Specific examples will be described below.

  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 permanent film such as an interlayer insulating film or a protective film of a liquid crystal display, and a copolymer of an unsaturated carboxylic acid and an epoxy group-containing polymerizable compound. Is used. However, since this technique requires a considerable amount of carboxylic acid or an acid component in place of it in order to impart alkali developability, the epoxy group present in the composition reacts with the carboxylic acid and is stored during storage. It has the disadvantage of thickening and solidifying.

  A spacer is provided between the color filter constituting the display device, such as a liquid crystal display device or a touch panel, and the array substrate in order to maintain the distance between the two substrates. As the spacer, a photospacer method has been proposed in which a spacer is formed using a photosensitive composition instead of dispersing spherical particles.

  Examples of the photosensitive composition used for forming the photospacer include methacrylic acid / allyl methacrylate copolymer as a binder resin, dipentaerythritol hexaacrylate as a photopolymerizable compound, and 2,4 as a photopolymerization initiator. -Bis- (trichloromethyl) -6- [4- (N, N-diethoxycarbonylmethylamino) -3-bromophenyl] -s-triazine as solvents, methyl ethyl ketone, 1-methoxy-2-propyl acetate and methanol There has been proposed a photosensitive composition for forming a photospacer comprising, for example, Patent Document 2.

  In Patent Document 2, it is said that a liquid crystal display element capable of displaying a high-quality image without liquid crystal display unevenness can be provided by defining the plastic deformation amount of the spacer within an appropriate range. There is a problem that light transmittance due to heat curing is poor.

  In addition, Patent Document 3 proposes a photospacer using a photosensitive composition in which a methacryloyl group is incorporated in a resin. However, as described above, it is poor in transparency and heat-resistant yellowing. This causes a problem of lowering.

  A color liquid crystal display device, a color image pickup tube element, etc. are subjected to a dipping process of the display element with a solvent, an acid or an alkali solution during the manufacturing process, and when the wiring electrode layer is formed by sputtering, The surface is locally exposed to high temperatures. Therefore, in order to prevent the element from being deteriorated or damaged by such treatment, a protective film made of a thin film having resistance to these treatments is provided on the surface of the element.

  Such a protective film has high adhesion to the substrate or lower layer on which the protective film is to be formed, and further to the layer formed on the protective film, the film itself is smooth and tough, transparent It has excellent heat resistance and light resistance, does not cause deterioration such as coloring, yellowing, and whitening over a long period of time, and has excellent water resistance, solvent resistance, acid resistance, and alkali resistance. Performance is required. As a material for forming a protective film satisfying these various properties, for example, a thermosetting composition containing a polymer having an epoxy group is known (see Patent Document 4 and Patent Document 5). However, since the composition contains a polymer having an epoxy group and a polyvalent carboxylic acid anhydride and a polyvalent carboxylic acid as the curing agent, the storage stability is poor.

  Further, the color filter protective film needs to have hardness for protecting the RGB colored layer, and exhibiting heat resistance and pressure resistance when liquid crystal is sealed. In order to express hardness, an active energy ray-curable resin composition having a high crosslinking density has been studied (see Patent Document 6). However, these curable resin compositions, particularly the active energy ray curable composition, have a problem that the adhesiveness to the substrate is not sufficient due to shrinkage upon curing and generation of residual stress.

Japanese Laid-Open Patent Publication No. 7-248625 Japanese Laid-Open Patent Publication No. 2003-302639 JP 2002-020442 A JP-A-4-202418 JP 11-1331013 A JP-A-5-78453

  The present invention relates to a photosensitive composition having excellent storage stability and heat resistance, transparency, substrate adhesion, and flatness, a coating agent containing the same, a color filter protective film using the same, and an interlayer insulating film The purpose is to provide a photo spacer.

  In order to solve the above-mentioned problems, the present inventors have intensively studied, and as a result, a photosensitive composition containing an acrylic curable resin having a specific functional group and an epoxy compound having a cyclo ring structure solves the above problems. As a result, the present invention has been completed.

That is, the first invention is an acrylic curable resin (A) having a linear or branched alkyl group having 1 to 4 carbon atoms, a carboxyl group, and an ethylenically unsaturated group,
At least one epoxy compound (B) selected from the group consisting of an epoxy compound having a monocyclo ring, an epoxy compound having a bicyclo ring, and an epoxy compound having a tricyclo ring,
A polymerizable compound (C) having an ethylenically unsaturated group, and
The present invention relates to a photosensitive composition comprising a solvent (D).

Moreover, 2nd invention is related with the photosensitive composition of 1st invention whose epoxy compound (B) is a compound represented by following General formula (1).
General formula (1)

Wherein, n ¹ is an integer of 0. ]

Moreover, 3rd invention is related with the photosensitive composition of 1st invention whose epoxy compound (B) is a compound represented by following General formula (2).
General formula (2)

[Wherein, R ¹ is a hydrogen atom or a methyl group, and n ² is an integer of 1-20. ]

  Moreover, 4th invention is the molar ratio of the number of moles (a) of the carboxyl group in acrylic curable resin (A), and the number of moles (b) of the epoxy group in epoxy compound (B), ( It relates to the photosensitive composition of any one of the 1st-3rd invention which is a) / (b) = 0.5-2.

In the fifth invention, the acrylic curable resin (A) comprises an ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms and a carboxyl group-containing ethylene. After copolymerizing an ethylenically unsaturated monomer (M) containing a polymerizable unsaturated monomer (m2) to obtain a carboxyl group-containing polymer (E),
The photosensitive composition of any one of the first to fourth inventions, wherein the epoxy group in the epoxy group-containing ethylenically unsaturated monomer (F) is reacted with the carboxyl group in the polymer (E). .

The sixth invention is an acrylic curable resin (A) in which an ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms and a carboxyl group-containing ethylene An ethylenically unsaturated monomer (M) containing a polymerizable unsaturated monomer (m2) to obtain a carboxyl group-containing polymer (E),
After reacting the epoxy group in the epoxy group-containing ethylenically unsaturated monomer (F) with the carboxyl group in the polymer (E) to obtain a hydroxyl group-containing polymer (G),
The present invention relates to the photosensitive composition according to any one of the first to fourth inventions, wherein the acid anhydride group in the polybasic acid anhydride (H) is reacted with the hydroxyl group in the polymer (G).

In addition, according to a seventh invention, the acrylic curable resin (A) comprises an ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms and an epoxy group-containing ethylene. An epoxy group-containing polymer (P) by copolymerizing an ethylenically unsaturated monomer (N) containing a polymerizable unsaturated monomer (m3),
After reacting the carboxyl group in the carboxyl group-containing ethylenically unsaturated monomer (Q) with the epoxy group in the polymer (P) to obtain a hydroxyl group-containing polymer (K),
The present invention relates to the photosensitive composition according to any one of the first to fourth inventions, wherein the hydroxyl group in the polymer (K) is reacted with the acid anhydride group in the polybasic acid anhydride (H).

The eighth invention relates to an ethylenically unsaturated monomer (m4) in which the ethylenically unsaturated monomer (M) or the ethylenically unsaturated monomer (N) is represented by the following general formula (3): ) In any one of the fifth to seventh inventions.
General formula (3)

[Wherein R ² represents a hydrogen atom or a methyl group, and R ³ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group, or an aromatic carbon group. A hydrogen group, and n ³ is an integer of 1 to 10. ]

  Moreover, 9th invention is related with the photosensitive composition of the 1st-8th invention whose acid value of acrylic curable resin (A) is 20-200 mgKOH / g.

  The tenth invention relates to the photosensitive composition of any one of the first to ninth inventions, wherein the acrylic curable resin (A) has a weight average molecular weight of 2000 to 25000.

The eleventh invention relates to the photosensitive composition according to any one of the first to tenth inventions, wherein the solvent (D) contains a solvent represented by the following general formula (4).
General formula (4)

[Wherein, R ⁴ is an alkyl group having 1 to 3 carbon atoms, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

  The twelfth invention relates to the photosensitive composition of any one of the first to eleventh inventions containing the photopolymerization initiator (I).

  The thirteenth invention relates to the photosensitive composition of any one of the first to twelfth inventions containing a thermal polymerization initiator (J).

  The fourteenth invention relates to a coating agent for a color filter protective film comprising the photosensitive composition of any one of the first to thirteenth inventions.

  The fifteenth invention relates to a color filter protective film formed from the coating agent for the color filter protective film of the fourteenth invention.

  Furthermore, the sixteenth invention relates to an interlayer insulating film for a touch panel formed using the photosensitive composition of any one of the first to thirteenth inventions.

  Furthermore, the seventeenth invention relates to a photo spacer for a touch panel formed using the photosensitive composition of any one of the first to thirteenth inventions.

  According to the present invention, a photosensitive composition having excellent storage stability and excellent heat resistance, transparency, substrate adhesion, and flatness, a coating agent containing the same, and a color filter protective film and interlayer insulating film using the same We were able to provide photo spacers.

The present invention is described in detail below. First, the photosensitive composition of the present invention is a highly transparent acrylic curable resin (A) having a linear or branched alkyl group having 1 to 4 carbon atoms, a carboxyl group, and an ethylenically unsaturated group. When,
At least one highly transparent and rigid epoxy compound (B) selected from the group consisting of an epoxy compound having a monocyclo ring, an epoxy compound having a bicyclo ring, and an epoxy compound having a tricyclo ring; When used and cured, films and patterns such as a color filter protective film, an interlayer insulating film, and a photospacer excellent in heat resistance, transparency, substrate adhesion, and flatness can be obtained.

  The acrylic curable resin (A) is characterized by having a linear or branched alkyl group having 1 to 4 carbon atoms, a carboxyl group, and an ethylenically unsaturated group.

  The linear or branched alkyl group having 1 to 4 carbon atoms in the acrylic curable resin (A) is an ethylenically unsaturated monomer having a linear or branched alkyl group having 1 to 4 carbon atoms. It can introduce | transduce by copolymerizing a body (m1). Moreover, a carboxyl group can be introduce | transduced by copolymerizing a carboxyl group-containing ethylenically unsaturated monomer (m2). Or, in the polybasic acid anhydride (H) with respect to a hydroxyl group in a resin copolymerized with a hydroxyl group-containing ethylenically unsaturated monomer or a hydroxyl group formed by a reaction between an epoxy group and a carboxyl group in the resin. It can introduce | transduce by making an acid anhydride group react. Further, the ethylenically unsaturated group can be introduced by the following three methods.

  The first is an epoxy group-containing ethylenically unsaturated monomer with respect to the carboxyl group in the carboxyl group-containing polymer (E) obtained by copolymerizing the carboxyl group-containing ethylenically unsaturated monomer (m2). There is a method of reacting an epoxy group in the body (F) (Reaction Formula 1). Second, the carboxyl group-containing ethylenically unsaturated monomer with respect to the epoxy group in the epoxy group-containing polymer (P) obtained by copolymerizing the epoxy group-containing ethylenically unsaturated monomer (m3). There is a method of reacting a carboxyl group in the body (Q) (Reaction Formula 2). The third is an isocyanate group in the isocyanate group-containing ethylenically unsaturated monomer with respect to the hydroxyl group in the hydroxyl group-containing polymer (E ′) obtained by copolymerizing the hydroxyl group-containing ethylenically unsaturated monomer. There is a method of reacting (Scheme 3).

(Reaction Formula 1)

[P ¹ is a polymer chain obtained by copolymerizing the ethylenically unsaturated monomer (M), and R ⁶ is a reaction residue of the epoxy group-containing ethylenically unsaturated monomer (F). ]

(Reaction Formula 2)

[P ² is a polymer chain obtained by copolymerizing the ethylenically unsaturated monomer (N), and R ⁷ is a reaction residue of the carboxyl group-containing ethylenically unsaturated monomer (Q). ]

(Reaction Formula 3)

[P ³ is a polymer chain obtained by copolymerizing an ethylenically unsaturated monomer (S), and R ⁸ is a reaction residue of an isocyanate group-containing ethylenically unsaturated monomer. ]

  As the method for introducing an ethylenically unsaturated group, it is preferable to use the first or second method (reaction formula 1 or 2) from the viewpoint of heat resistance and yellowing of the resin.

  The copolymer obtained by the first or second method (reaction formula 1 or 2) has a hydroxyl group [hydroxyl-containing polymers (G) and (K)], and the present invention further comprises The hydroxyl group in the polymer (G) or (K) can be reacted with the acid anhydride group in the polybasic acid anhydride (H) to generate a carboxyl group (Reaction Formula 4 or 5). Thereby, adjustment of an acid value can also be performed easily.

  (Reaction Formula 4)

[P ¹ is a polymer chain obtained by copolymerizing an ethylenically unsaturated monomer (M), R ⁶ is a reaction residue of an epoxy group-containing ethylenically unsaturated monomer (F), and R ⁸ is It is a reaction residue of a basic acid anhydride (H). ]

(Reaction Formula 5)

[P ² is a polymer chain obtained by copolymerizing an ethylenically unsaturated monomer (N), R ⁷ is a reaction residue of a carboxyl group-containing ethylenically unsaturated monomer (Q), and R ⁸ is It is a reaction residue of a basic acid anhydride (H). ]

  The ethylenically unsaturated group in the acrylic curable resin (A) thus obtained reacts with the polymerizable compound (C) having an ethylenically unsaturated group by light and heat, and the carboxyl group is heated. By reacting with the epoxy group in the epoxy compound (B), a cured product having a high crosslinking density and excellent in both heat resistance and heat yellowing resistance can be obtained.

  The acid value of the acrylic curable resin (A) is preferably 20 to 200 mgKOH / g, more preferably 40 to 100 mgKOH / g. If it is less than 20 mgKOH / g, the functional group (carboxyl group) that can react with the epoxy group in the epoxy resin may be reduced, and heat resistance and hardness may not be obtained satisfactorily. Viscosity is high and storage stability may deteriorate.

  As for the weight average molecular weight (Mw) of acrylic curable resin (A), 2000-25000 are preferable, More preferably, it is 4000-15000. When the weight average molecular weight (Mw) is less than 2,000, the heat resistance may be deteriorated, and when the weight average molecular weight (Mw) exceeds 25,000, the viscosity becomes high and coating may be difficult.

Next, the manufacturing method of acrylic curable resin (A) is demonstrated. The acrylic curable resin (A) includes an ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms and a carboxyl group-containing ethylenically unsaturated monomer (m2). To obtain a carboxyl group-containing polymer (E), and then reacting the epoxy group-containing ethylenically unsaturated monomer (F). (Scheme 1). Furthermore, the polybasic acid anhydride (H) can also be reacted with the polymer obtained by the reaction formula 1 [namely, the hydroxyl group-containing polymer (G)] (reaction formula 4).
Moreover, the ethylenically unsaturated containing the ethylenically unsaturated monomer (m1) which has a C1-C4 linear or branched alkyl group, and an epoxy-group-containing ethylenically unsaturated monomer (m3) After the monomer (N) is copolymerized to obtain the epoxy group-containing polymer (P), the carboxyl group-containing ethylenically unsaturated monomer (Q) is reacted (reaction formula 2), and further the reaction formula 2 can be obtained by reacting the polybasic acid anhydride (H) with the polymer obtained in Step 2 [namely, hydroxyl group-containing polymer (K)] (Reaction Formula 5).
Further, an ethylenically unsaturated monomer (S) containing an ethylenically unsaturated monomer (m1), an ethylenically unsaturated monomer (m2), and a hydroxyl group-containing ethylenically unsaturated monomer is copolymerized. After obtaining a hydroxyl group-containing polymer (E ′), it can be obtained by reacting an isocyanate group-containing ethylenically unsaturated monomer (Reaction Formula 3).

Examples of the ethylenically unsaturated monomer (M) include an ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms, and a carboxyl group-containing ethylenically unsaturated monomer. The body (m2) and other copolymerizable ethylenically unsaturated monomers used as required are included.
Further, as the ethylenically unsaturated monomer (N), an ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms, an epoxy group-containing ethylenically unsaturated monomer Monomer (m3) and other copolymerizable ethylenically unsaturated monomers used as needed are included.
Further, as the ethylenically unsaturated monomer (S), an ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms, a carboxyl group-containing ethylenically unsaturated monomer. A monomer (m2), a hydroxyl group-containing ethylenically unsaturated monomer, and other copolymerizable ethylenically unsaturated monomers used as necessary are included.

  Examples of the ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms include methyl (meth) acrylate, ethyl (meth) acrylate, and n-propyl (meth). Examples include acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, and t-butyl (meth) acrylate. Among these, methyl methacrylate is preferable from the viewpoint of transparency and heat resistance.

  The amount of the ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms may be selected from the ethylenically unsaturated monomer (M), (N) or (S ) 10 to 70% by weight is preferable in 100% by weight. Furthermore, 20 to 60% by weight is preferable. If it is less than 10% by weight, the transparency may be deteriorated. If it exceeds 70% by weight, the amount of carboxyl groups and ethylenically unsaturated groups to be introduced decreases, the crosslinking density of the resulting coating film decreases, and heat resistance and group Material adhesion may be reduced.

  Examples of the carboxyl group-containing ethylenically unsaturated monomer (m2) include (meth) acrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, α- (hydroxymethyl) acrylic acid, α- (hydroxymethyl). ) Methacrylic acid, p-vinylbenzoic acid, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) acryloyloxyethyl phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthalic acid, etc. It is done. Of these, (meth) acrylic acid is preferred from the viewpoint of reactivity.

  As a usage-amount of a carboxyl group-containing ethylenically unsaturated monomer (m2), 5 to 40 weight% is preferable in 100 weight% of ethylenically unsaturated monomers (M) or (S). If it is less than 5% by weight, the cured site with the epoxy compound (B) may be reduced and the substrate adhesion may be lowered, and if it exceeds 40% by weight, the solubility in a solvent may be deteriorated.

  Examples of the epoxy group-containing ethylenically unsaturated monomer (m3) include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, and 3,4-epoxybutyl (meth) ) Acrylate, 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, α-ethyl acrylate glycidyl, allyl glycidyl ether, crotonyl glycidyl ale, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate , N- (3,5-di Til-4-glycidyl) benzylacrylamide, o-vinylbenzylglycidyl ether, m-vinylbenzylglycidyl ether, p-vinylbenzylglycidyl ether, α-methyl-o-vinylbenzylglycidyl ether, α-methyl-m-vinylbenzylglycidyl Ether, α-methyl-p-vinylbenzylglycidyl ether, 2,3-diglycidyloxymethylstyrene, 2,4-diglycidyloxymethylstyrene, 2,5-diglycidyloxymethylstyrene, 2,6-diglycidyloxy Methylstyrene, 2,3,4-triglycidyloxymethylstyrene, 2,3,5-triglycidyloxymethylstyrene, 2,3,6-triglycidyloxymethylstyrene, 3,4,5-triglycidyloxymethylstyrene 2,4,6-triglycidyloxymethylstyrene and the like. 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.

  The amount of the epoxy group-containing ethylenically unsaturated monomer (m3) used is preferably 20 to 90% by weight in 100% by weight of the ethylenically unsaturated monomer (N). If it is less than 20% by weight, the amount of epoxy groups to be reacted with the carboxyl group-containing ethylenically unsaturated monomer (Q) is reduced and the amount of ethylenically unsaturated groups to be introduced is reduced. Sexuality may be insufficient. When it exceeds 90% by weight, the amount of the ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms is decreased, and transparency may be deteriorated.

Examples of the hydroxyl group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, ethyl-α- (hydroxymethyl) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate Hydroxyl group-containing (meth) acrylates such as monohydroxyethyl (meth) acrylate, phthalate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, p-hydroxyphenylethyl (meth) acrylate;
Hydroxyl group-containing (meth) acrylamides such as 2-hydroxyethylacrylamide and 2,3-dihydroxypropyl (meth) acrylamide;
Examples thereof include hydroxyl group-containing vinyl ethers such as 2-hydroxyethyl vinyl ether, diethylene glycol vinyl ether, and 4-hydroxybutyl vinyl ether.

  As the usage-amount of a hydroxyl-containing ethylenically unsaturated monomer, 20 to 90 weight% is preferable in 100 weight% of ethylenically unsaturated monomers (S). If it is less than 20% by weight, the amount of hydroxyl groups to be reacted with the isocyanate group-containing ethylenically unsaturated monomer is reduced, and the amount of ethylenically unsaturated groups to be introduced is reduced. There is a case. When it exceeds 90% by weight, the amount of the ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms is decreased, and transparency may be deteriorated.

  In the present invention, the ethylenically unsaturated monomer (M), (N) or (S) preferably contains an ethylenically unsaturated monomer (m4) represented by the following general formula (3). . By using the ethylenically unsaturated monomer (m4), the hydrophilicity can be easily controlled, and the solubility in an alkaline developer used for patterning the insulating film and the photospacer can be improved.

General formula (3)

[Wherein R ² represents a hydrogen atom or a methyl group, and R ³ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group, or an aromatic carbon group. A hydrogen group, and n ³ is an integer of 1 to 10. ]

  Examples of the ethylenically unsaturated monomer (m4) represented by the general formula (3) include methoxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolyethylene glycol (meta ) Alkoxy polyethylene glycol (meth) acrylates such as acrylate and ethoxypolyethylene glycol (meth) acrylate. In particular, methoxyethyl (meth) acrylate is most preferable from the viewpoint of heat resistance.

  The amount of the ethylenically unsaturated monomer (m4) shown in the general formula (3) is 5 to 100% by weight in the ethylenically unsaturated monomer (M), (N) or (S). 30% by weight is preferred. If it is less than 5% by weight, it is difficult to control the hydrophilicity, and the effect for improving the solubility in an alkali developer may be low. If it exceeds 30% by weight, the heat resistance may be deteriorated.

Other copolymerizable ethylenically unsaturated monomers that can be used for the ethylenically unsaturated monomers (M), (N) and (S) include, for example, 2-ethylhexyl (meth) acrylate, cyclohexyl (Meth) acrylate, 2,2,4-trimethylcyclohexyl (meth) acrylate, 4-t-butylcyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, isobornyl (meth) acrylate, adamantyl (meta ) Acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, tricyclo- (5,2,1,0,2.6) -decanyl (meth) acrylate, tricyclo- (5,2, 1,0,2.6) -decanyloxyethyl ( Data) aliphatic acrylates such as (meth) acrylates;
Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, rosin acrylate;
Oxetane (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (2-ethyl-2-methyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, 1,4-dioxaspiro [4,5] Cyclic ether-containing (meth) acrylates excluding epoxy groups such as (dec-2-yl) methyl (meth) acrylate;
Heterocyclic (meth) acrylates such as N- (meth) acryloyloxyethyl hexahydrophthalimide;
Alkoxypolypropylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate;
2-methacryloyloxy-γ-butyrolactone, 3-methacryloyloxy-γ-butyrolactone, 5-methacryloyloxy-2,6-norbornanecarbolactone, β-methacryloyloxy-β-methyl-δ-valerolactone, β-methacryloyloxy- Lactone skeleton-containing (meth) acrylates such as β-methyl-γ-butyrolactone and 2- (1-methacryloyloxy) ethyl-4-butanolide;
(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, 2-hydroxyethyl acrylamide, diacetone (meth) acrylamide, acryloylmorpholine;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;
Nitriles such as (meth) acrylonitrile;
Examples thereof include polymerizable oligomers such as one-end methacryloylated polymethyl methacrylate oligomer, one-end methacryloylated polystyrene oligomer, and one-end methacryloylated polyethylene glycol.

Furthermore, styrenes such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, vinyltoluene, indene;
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;
N-substituted maleimides such as N-methylmaleimide, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like can be mentioned.

  In particular, styrene and 2-methacryloyloxy-γ-butyrolactone are preferable in terms of adhesion, and tricyclo- (5,2,1,0,2.6) -decanyl (meth) acrylate is an epoxy compound having a monocyclo ring. , Epoxy compounds having a bicyclo ring, and epoxy compounds having a tricyclo ring are highly compatible with each other, and are more preferable in terms of transparency and adhesion.

  The polymerization of the ethylenically unsaturated monomer (M), (N) or (S) can be performed by a known method. That is, it can be carried out by optionally mixing an ethylenically unsaturated monomer with a polymerization initiator and heating. The polymerization temperature is 40 to 150 ° C, preferably 50 to 120 ° C.

  In the polymerization, 0.001 to 15 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the total of ethylenically unsaturated monomers. As the polymerization initiator, azo compounds and organic peroxides can be used. 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. 0.001 to 15 parts by weight of a chain transfer agent can be arbitrarily used for 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 (D) used for the photosensitive resin composition concerning this invention. For example, 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 and the like are particularly limited thereto. Is not to be done. These polymerization solvents may be used as a mixture of two or more.

  An ethylenically unsaturated monomer comprising an ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms and a carboxyl group-containing ethylenically unsaturated monomer (m2) As the epoxy group-containing ethylenically unsaturated monomer (F) that reacts with the carboxyl group in the carboxyl group-containing polymer (E) obtained by copolymerizing the body (M), the above-mentioned epoxy group-containing ethylenic monomer (F) is used. The thing similar to an unsaturated monomer (m3) can be used. Glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and (3,4-epoxycyclohexyl) methyl (meth) acrylate are desirable from the viewpoint of easy availability of industrial products.

  As the usage-amount of an epoxy-group-containing ethylenically unsaturated monomer (F), with respect to 1 mol of carboxyl groups in a carboxyl-group-containing polymer (E), an epoxy-group-containing ethylenically unsaturated monomer (F) It is preferable to react 0.1 to 0.9 mol of the epoxy group therein. More preferably, it is 0.2-0.7 mol. If the amount exceeds 0.9 mol, the amount of carboxyl groups in the acrylic curable resin (A) decreases, and the reaction with the epoxy compound (B) cannot be performed sufficiently, and the curing shrinkage is large and the substrate adhesion deteriorates. There is a case.

  The reaction temperature is 40 to 150 ° C, preferably 50 to 120 ° 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, gelation tends to occur during the addition reaction.

  An ethylenically unsaturated monomer comprising an ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms and an epoxy group-containing ethylenically unsaturated monomer (m3) Examples of the carboxyl group-containing ethylenically unsaturated monomer (Q) that reacts with the epoxy group of the epoxy group-containing polymer (P) obtained by copolymerizing the product (N) include the above-mentioned carboxyl group-containing ethylenically unsaturated monomers. The thing similar to a saturated monomer (m2) can be used. Of these, (meth) acrylic acid is preferred from the viewpoint of reactivity.

  The amount of the carboxyl group-containing ethylenically unsaturated monomer (Q) used is that the carboxyl group-containing ethylenically unsaturated monomer (Q) with respect to 1 mol of the epoxy group in the epoxy group-containing polymer (P). It is preferable to react 0.2 to 1 mol of the carboxyl group therein. More preferably, it is 0.3-1 mol. If it is less than 0.2 mol, the concentration of the ethylenically unsaturated group may be low, and heat resistance and the like may be insufficient. Further, gelation may occur when the remaining epoxy group is reacted with the polybasic acid anhydride (H). If it exceeds 1 mol, the carboxyl group-containing ethylenically unsaturated monomer (Q) may remain.

  The reaction temperature is 40 to 150 ° C, preferably 50 to 120 ° 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, gelation tends to occur during the addition reaction.

  Ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms, carboxyl group-containing ethylenically unsaturated monomer (m2), and hydroxyl group-containing ethylenically unsaturated monomer As an isocyanate group-containing ethylenically unsaturated monomer to be reacted with a hydroxyl group in a hydroxyl group-containing polymer (E ′) obtained by copolymerizing an ethylenically unsaturated monomer (S) containing, for example, Examples include 2-methacryloyloxyethyl isocyanate, 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethoxyethyl isocyanate, 1,1-bis (acryloylmethyl) ethyl isocyanate.

  With respect to the amount of the isocyanate group-containing ethylenically unsaturated monomer used, the isocyanate group in the isocyanate group-containing ethylenically unsaturated monomer is added to 0.1 mol of the hydroxyl group in the hydroxyl group-containing polymer (E ′). It is preferable to make it react 1-0.9 mol. More preferably, it is 0.2-0.7 mol. When it exceeds 0.9 mol, the curing shrinkage is large and the substrate adhesion may be deteriorated.

  The reaction temperature is preferably 40 to 120 ° C. More preferably, it is 50-100 degreeC. 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, gelation tends to occur during the addition reaction.

  Further, a hydroxyl group-containing polymer (G) or an epoxy group-containing polymer (P) obtained by reacting an epoxy group-containing ethylenically unsaturated monomer (F) with a carboxyl group-containing polymer (E). As a polybasic acid anhydride (H) to be reacted with a hydroxyl group in a hydroxyl group-containing polymer (K) obtained by reacting a carboxyl group-containing ethylenically unsaturated monomer (Q) with For example, maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride 3,3 ′, 4,4′-biphenylsulfonetetracarboxylic anhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane anhydride, 9 Polybasic acid anhydrides such as 9- bis (3,4-carboxyphenyl) fluorene anhydride. From the viewpoint of solvent solubility, tetrahydrophthalic anhydride and hexahydrophthalic anhydride are particularly preferred.

  The amount of the polybasic acid anhydride (H) used is such that the acid anhydride group in the polybasic acid anhydride (H) is 0. 1 mol with respect to 1 mol of the hydroxyl group in the hydroxyl group-containing polymer (G) or (K). It is preferable to carry out the reaction between 05 and 0.95 mol. More preferably, it is 0.2-0.7 mol. If it is less than 0.05 mol, the effect of improving adhesion may not be sufficiently obtained, and further, alkali developability, which is one of the purposes for introducing a carboxyl group, may not be sufficiently obtained.

  The reaction temperature is 40 to 150 ° C, preferably 50 to 120 ° 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, gelation tends to occur during the addition reaction.

  In the case of the above addition reaction between the carboxyl group and the epoxy group (Reaction Formula 1 and Reaction Formula 2) and the addition reaction between the hydroxyl group and the acid anhydride group (Reaction Formula 4 and Reaction Formula 5), as necessary A known catalyst can be used. Examples of the catalyst include triethylamine, tributylamine, dimethylbenzylamine, 1,8-diazabicyclo [5,4,0] undec-7-ene, 1,5-diazabicyclo [4,3,0] non-5-ene. , Tertiary amines such as 1,4-diazabicyclo [2,2,2] octane, and phosphine compounds such as triphenylphosphine. The amount of the catalyst used is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 5 parts by weight, and 0.1 to 2 parts by weight based on 100 parts by weight of the total solid content in the reaction system. Most preferred.

  A known catalyst can be used in the addition reaction (reaction formula 3) between the hydroxyl group and the isocyanate group. Examples thereof include tertiary amine compounds and organometallic compounds. Examples of the tertiary amine compound include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- And diazabicyclo- [4.3.0] -5-nonene.

  Examples of organometallic compounds include tin compounds and non-tin compounds. Examples of the tin-based compound include dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate, dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, Examples include tributyltin acetate, triethyltin ethoxide, tributyltin ethoxide, dioctyltin oxide, tributyltin chloride, tributyltin trichloroacetate, tin 2-ethylhexanoate and the like. Examples of non-tin compounds include titanium compounds such as dibutyltitanium dichloride, tetrabutyltitanate, butoxytitanium trichloride, and lead compounds such as lead oleate, lead 2-ethylhexanoate, lead benzoate, and lead naphthenate. Iron, such as iron 2-ethylhexanoate and iron acetylacetonate, cobalt-based such as cobalt benzoate, cobalt 2-ethylhexanoate, zinc-based such as zinc naphthenate and zinc 2-ethylhexanoate, naphthene Examples thereof include zirconium acid. These can be used alone or in combination.

  Furthermore, at the time of the addition reaction, a gas having a polymerization inhibiting 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.

  Next, at least one epoxy compound (B) selected from the group consisting of an epoxy compound having a monocyclo ring, an epoxy compound having a bicyclo ring, and an epoxy compound having a tricyclo ring [hereinafter sometimes referred to as an epoxy compound (B). is there. ] Will be described. Generally, it is possible to improve chemical resistance, heat resistance and substrate adhesion by adding an epoxy compound. Furthermore, in this invention, the film | membrane and pattern which are excellent in transparency and hardness can be obtained by using an epoxy compound (B).

  The epoxy compound (B) is cured by reacting with an epoxy group in the compound and a carboxyl group in the acrylic curable resin (A). The amount of the epoxy compound (B) used is adjusted by the ratio between the number of moles of carboxyl groups in the acrylic curable resin (A) and the number of moles of epoxy groups in the epoxy compound (B). The molar ratio of the number of moles of carboxyl groups (a) in the acrylic curable resin (A) to the number of moles (b) of epoxy groups in the epoxy compound (B) is (a) / (b) = 0. 0.5 to 2 is preferable, and 0.75 to 1.5 is more preferable. When (a) / (b) is less than 0.5, the amount of epoxy resin increases, and the shape deterioration or alkali developability at the time of pattern formation may deteriorate. From (a) / (b) = 2 If it is large, the carboxyl group remains in the protective film, so that the heat resistance may be deteriorated due to a decrease in insulating properties or poor curing.

  Examples of the epoxy compound having a monocyclo ring include hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ester, cyclohexanediol diglycidyl ether, cyclohexanedidiglycidyl ester, vinylcyclohexene dioxide, tetraglycidylbisaminomethylcyclohexane, 3,4-epoxycyclohexenylmethyl-3 ′, 4′-epoxycyclohexenecarboxylate, 1,2: 8,9 diepoxy limonene, lactone-modified epoxidized butanetetracarboxylic acid tetrakis- (3-cyclohexenylmethyl), 2 , 2-Bis (hydroxymethyl) -1-butanol, 1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct, 3,4-epoxycyclohexylmethyl (meth) ) Acrylate, 2- (3,4-epoxy) cyclohexyl-5,1-spiro (3,4-epoxy) cyclohexyl-m-dioxane, and the like. EP-4080S, 4085S [above, ( ADEKA Co., Ltd.], CY-175, 177, 179, Araldite CY-182, 192, 184 [above, manufactured by Ciba Specialty Chemicals], ERL-4234, 4299, 4221, 4206 [above. U. C. C company], Shodyne 509 [Showa Denko Co., Ltd.], Epicron 200, 400 [above, DIC Corporation], Epicoat 871, 872 [above, Japan Epoxy Resin Co., Ltd.], ED -5661, 5562 [above, manufactured by Celanese Coating Co., Ltd.], Celoxide 2021, 2021A, 2021P, 2080, 3000, Epolide CT300, 400, EHPE3150, EHPE3150CE [above, Daicel Chemical Industries, Ltd. Manufactured]. It is not limited to this as long as it is an epoxy compound having a monocyclo ring such as cyclohexane.

  Examples of the epoxy compound having a bicyclo ring include norbornenediol diglycidyl ether and isobornyldiol diglycidyl ether.

  Examples of the epoxy compound having a tricyclo ring include tricyclodecanyl diglycidyl ether, glycidyl etherified product of dicyclopentadiene and a phenol novolak polymer, and the product is EP-4088S [manufactured by ADEKA Co., Ltd.] ], XD-1000, XD-1000-L, XD-1000-2L [manufactured by Nippon Kayaku Co., Ltd.], EPICLON HP-7200, HP-7200L, HP-7200H, HP-7200HH [above, DIC ( Etc.].

  Among these, an epoxy compound represented by the following general formula (1) [glycidyl etherified product of dicyclopentadiene and phenol novolac polymer, as products, XD-1000, XD-1000-L, XD-1000-2L [or more] Nippon Kayaku Co., Ltd.], EPICLON HP-7200, HP-7200L, HP-7200H, HP-7200HH [above, DIC Corporation]] is preferably used.

  General formula (1)

Wherein, n ¹ is an integer of 0. ]

  In addition, as an epoxy compound represented by the following general formula (2) [1,2-epoxy-4- (2-oxiranyl) cyclohexane adduct of 2,2-bis (hydroxymethyl) -1-butanol, It is preferable to use EHPE3150 [manufactured by Daicel Chemical Industries, Ltd.].

General formula (2)

[Wherein, R ¹ is a hydrogen atom or a methyl group, and n ² is an integer of 1-20. ]

  By using the epoxy compounds represented by the above general formulas (1) and (2), it is possible to obtain a coating film that ensures the transparency of the film and the pattern and has both heat resistance and insulation properties.

  These epoxy compounds (B) may use only 1 type, or may use 2 or more types together. Further, as the epoxy compound (B), a low molecular weight epoxy compound having a molecular weight (formula weight) of 150 to 1000 is used in combination with the epoxy compound represented by the general formula (1) or the general formula (2). More preferred. By using a low molecular weight epoxy compound, it is possible to adjust the developing speed and improve the crosslinking density of the thermosetting film, thereby improving the heat resistance and adjusting the adhesion of the substrate.

Next, the polymerizable compound (C) having an ethylenically unsaturated group will be described. The polymerizable compound (C) having an ethylenically unsaturated group is composed of an ethylenically unsaturated monomer and, if necessary, a resin having an ethylenically unsaturated group. However, the “acrylic curable resin (A) having an ethylenically unsaturated group” in the present invention is not included in the “polymerizable compound (C) having an ethylenically unsaturated group”.
The polymerizable compound (C) having an ethylenically unsaturated group is not particularly limited as long as it is a known compound. For example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) ) Acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate and polybasic acid anhydride 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipenta Reaction products of erythritol penta (meth) acrylate and polybasic acid anhydrides, various acrylic esters such as tricyclodecanyl (meth) acrylate, ester acrylate, melamine (meth) acrylate, epoxy (meth) acrylate, urethane acrylate And methacrylic acid esters and others, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol Examples include rutrivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like, and these can be used alone or in admixture of two or more.

  Here, the polymerizable compound (C) having an ethylenically unsaturated group is usually photocured by adding ultraviolet rays or an electron beam [adding a photopolymerization initiator (I) as necessary], In the present invention, heat curing may be performed by heat [adding a thermal polymerization initiator (J) if necessary].

  The amount of the polymerizable compound (C) having an ethylenically unsaturated group is preferably 10 to 60% by weight, more preferably 15 to 50% by weight, particularly preferably 100% by weight of the solid content of the photosensitive composition. Is 20-40% by weight. If it is less than 10% by weight, the photocuring reactivity may be poor and polymerization may not proceed, and if it exceeds 60% by weight, the substrate adhesion due to curing shrinkage may be reduced.

  Next, the solvent (D) will be described in detail. The amount of the solvent (D) used is preferably an amount that makes the solid content concentration of the photosensitive composition 5 to 50% by weight. By setting the solid content concentration of the photosensitive composition in such a range, it is possible to provide an insulating film and a photospacer having a more uniform thickness and high smoothness. That is, when the solid content concentration exceeds 50% by weight, the leveling property of the insulating film and the photospacer and the transparency of the obtained insulating film and photospacer may be lowered, while the solid content concentration is 5%. This is because if the amount is less than% by weight, a film and a pattern having a predetermined thickness may not be obtained.

  Therefore, the solid content concentration is more preferably in the range of 10 to 40% by weight from the viewpoint of a better balance between the leveling property of the photosensitive composition and the chemical resistance of the resulting film and pattern. .

  Here, the solvent (D) for adjusting the solid content of the photosensitive composition is not particularly limited as long as it does not react with other components (inactive) constituting the photosensitive composition. Preferably, the same organic solvent that can be used in the synthesis of the acrylic curable resin (A) described above can be used. Specifically, a single type of ketone solvent or an ester solvent is preferably used alone or in combination of two or more types.

  Among them, it is more preferable to use a solvent represented by the following general formula (4).

General formula (4)

[Wherein, R ⁴ is an alkyl group having 1 to 3 carbon atoms, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]

  By using the solvent represented by the general formula (4), it is possible to prevent the occurrence of various unevenness in any of the spin coating method and the slit coating method, and it has an epoxy compound having a monocyclo ring and a bicyclo ring. Since the compatibility with at least one epoxy compound (B) selected from the group consisting of an epoxy compound and an epoxy compound having a tricyclo ring is good, the flatness of the film and the pattern can be improved.

  Examples of the solvent represented by the general formula (4) include cyclohexyl esters of alkyl acids, such as cyclohexyl acetate, cyclohexyl propionate, cyclohexyl butyrate, cyclohexyl isobutyrate, 2-methylcyclohexyl acetate, and 2-ethylcyclohexyl acetate. , Acetate-2-propylcyclohexyl, acetate-2-isopropylcyclohexyl, acetate-4-methylcyclohexyl, acetate-4-ethylcyclohexyl, acetate-4-propylcyclohexyl, acetate-4-isopropylcyclohexyl, propionate-2-methylcyclohexyl , Propionate-2-ethylcyclohexyl, propionate-2-propylcyclohexyl, propionate-2-isopropylcyclohexyl, propionate-4-methylcyclohexyl, pro 4-ethylcyclohexyl onion, 4-propylcyclohexyl propionate, 4-isopropylcyclohexyl propionate, 2-methylcyclohexyl butyrate, 2-ethylcyclohexyl butyrate, 2-propylcyclohexyl butyrate, 2-isopropyl butyrate Examples include cyclohexyl, 4-methylcyclohexyl butyrate, 4-ethylcyclohexyl butyrate, 4-propylcyclohexyl butyrate, and 4-isopropylcyclohexyl butyrate.

  Among them, it is preferable to use cyclohexyl acetate (alias: cyclohexyl acetate) or 2-methylcyclohexyl acetate (alias: 2-methylhexyl acetate).

  The content of the solvent represented by the general formula (4) is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, and still more preferably 35 to 100% by weight in the total 100% by weight of the solvent (D). The range is 65% by weight. If it is less than 20% by weight, good coatability may not be obtained. Moreover, when it exceeds 80 weight%, solvent selectivity may fall.

  Next, the photopolymerization initiator (I) will be described. The photosensitive composition of the present invention preferably contains a photopolymerization initiator (I). The photopolymerization initiator (I) is not particularly limited as long as it is a known one, and examples thereof include metallocene compounds including titanocene compounds described in JP-A Nos. 59-152396 and 61-151197. Hexaarylbiimidazole derivatives, halomethyl-s-triazine derivatives, N-aryl-α-amino acids such as N-phenylglycine, N-aryl-α-amino acid salts, N-aryl described in JP-A-10-39503 -Radical activators such as -α-amino acid esters, α-aminoalkylphenone compounds, oxime ester initiators described in JP-A 2000-80068, JP-A 2006-36750, and the like. .

Specific examples of the photopolymerization initiator (I) that can be used in the present invention include 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 Halomethylated triazine derivatives such as 1,6-bis (trichloromethyl) -s-triazine;
2-trichloromethyl-5- (2′-benzofuryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- [β- (2′-benzofuryl) vinyl] -1,3,4-oxa Diazole, 2-trichloromethyl-5-[[beta]-[2 '-(6 "-benzofuryl) vinyl]]-1,3,4-oxadiazole, 2-trichloromethyl-5 monofuryl-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.

  The amount of the photopolymerization initiator (I) used is preferably from 0.01 to 10% by weight, more preferably from 0.05 to 7% by weight, particularly preferably from 100% by weight of the total solid content of the photosensitive composition. 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.

  Next, the thermal polymerization initiator (J) will be described. The thermal polymerization initiator (J) is not particularly limited as long as it is a known one, but a compound having a 10-hour half-life temperature in the range of 100 ° C to 250 ° C is preferable. More preferably, a compound in the range of 110 ° C to 180 ° C is more preferable. When the 10-hour half-life temperature is less than 100 ° C., the storage stability may be deteriorated, and when it exceeds 250 ° C., radicals are not efficiently generated at the time of thermal curing, and curing may not proceed.

Examples of the thermal polymerization initiator (J) having a 10-hour half-life temperature of 100 ° C. or higher and lower than 250 ° C. include the following compounds. t-butyl peroxyacetate (half-life temperature 102 ° C.), 2,2-di- (t-butylperoxy) butane (half-life temperature 103 ° C.), t-butyl peroxybenzoate (half-life temperature 104 ° C.), n-butyl 4,4-di- (t-butylperoxy) valerate (half-life temperature 105 ° C.), di- (2-t-butylperoxyisopropyl) benzene (half-life temperature 119 ° C.), dicumyl peroxide (Half-life temperature 116 ° C), di-t-hexyl peroxide (half-life temperature 116 ° C), 2,5, -dimethyl-2,5-di (t-butylperoxy) hexane (half-life temperature 118 ° C) ), T-butylcumyl peroxide (half-life temperature 120 ° C.), di-t-butyl peroxide (half-life temperature 124 ° C.), diisopropylbenzene hydroperoxide (Half-life temperature 145 ° C.), 1,1,3,3-tetramethylbutyl hydroperoxide (half-life temperature 153 ° C.), cumene hydroperoxide (half-life temperature 158 ° C.), t-butyl hydroperoxide Peroxide polymerization initiators such as (half-life temperature of 167 ° C.), t-butyltrimethylsilyl peroxide (half-life temperature of 176 ° C.);
1-[(1-cyano-1-methylethyl) azo] formamide (half-life temperature 104 ° C.), 2,2′-azobis (N-butyl-2-methylpropionamide) (half-life temperature 110 ° C.), 2 , 2′-azobis (N-cyclohexyl-2-methylpropionamide) (half-life temperature 111 ° C.), 2,2′-azobis (2,4,4-trimethylpentane) (half-life temperature 110 ° C.), etc. Polymerization initiators;
In addition, 2,3-dimethyl-2,3-diphenylbutane (half-life temperature 210 ° C.) and the like can be mentioned.

  The amount of the thermal polymerization initiator (J) used is preferably from 0.01 to 10% by weight, more preferably from 0.05 to 7% by weight, particularly preferably from 100% by weight of the total solid content of the photosensitive composition. 0.1 to 5% by weight. When the amount is less than 0.01% by weight, the thermosetting reactivity is poor and the polymerization may not proceed. When the amount exceeds 10% by weight, the heat resistance of the film and pattern obtained from the photosensitive composition is reduced due to a decrease in the molecular weight. Deterioration may occur.

  The following additives can be used in the photosensitive 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.

  In the photosensitive composition of the present invention, the thickness of the formed color filter protective film, interlayer insulating film, photospacer, etc. is preferably 0.005 to 30 μm, and 0.01 to 20 μm. More preferably, the thickness is 0.1 to 10 μm. 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.

  In addition, the method for applying the photosensitive 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. It can also be applied by printing methods such as screen printing, offset printing, and gravure printing.

  Further, the drying method after applying the photosensitive 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 10 to 10 hours, and more preferably a temperature of 100 to 250 ° C. and a heat curing condition of 0.5 to 5.0 hours.

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 the thermosetting performed after photocuring, the carboxylic acid in the acrylic curable resin (A) can be changed depending on the kind of each component used in the photosensitive composition, the addition amount (blending amount), and the like. The temperature at which the epoxy group in the epoxy compound (B) undergoes a crosslinking reaction is preferred, and the temperature is preferably in the range of 50 to 300 ° C., and is preferably heat-cured under the conditions of 0.1 to 10 hours, more preferably The heat curing conditions are in the range of 100 to 250 ° C for 0.5 to 5.0 hours, more preferably in the range of 150 to 250 ° C for 0.5 to 2 hours.

  By using the photosensitive composition of the present invention, a coating film excellent in heat resistance, transparency, substrate adhesion, and insulation is obtained as an interlayer insulating film and a photospacer for liquid crystal panels and touch panels, particularly touch panels. be able to. 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 photosensitive 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, various coatings, UV inks, photosensitive lithographic printing plates and the like. it can.

  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”.

[Production Example 1]
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 100 parts of methoxypropyl acetate, heated to 90 ° C., and the inside of the reaction vessel was purged with nitrogen. , 21 parts of methacrylic acid, 17 parts of styrene and 13 parts of dimethyl 2,2′-azobis (2-methylpropionate) were added dropwise over 2 hours, and then the same temperature for 3 hours. And stirring was continued to obtain a carboxyl group-containing polymer. Subsequently, dry air was introduced into the reaction vessel, charged with 20 parts of glycidyl methacrylate, 20 parts of methoxypropyl acetate, 1 part of dimethylbenzylamine, and 0.1 part of methoquinone, and then stirred at the same temperature for 10 hours. A system curable resin was obtained. Here, the reaction rate of glycidyl methacrylate was 99% as determined from the change in the acid value of the polymer before and after the reaction. After cooling to room temperature, an acrylic curable resin solution P-1 having a solid content of 30% was obtained by dilution with methoxypropyl acetate.

[Production Examples 2, 3, 5, 13, 14, 16, 17, 19, 20]
The composition shown in Table 1 was synthesized in the same manner as in Production Example 1, and the acrylic curable resin solution P-2, P-3, P-5, P-13, P-14, P-16 having a solid content of 30%. , P-17, P-19 and P-20 were obtained. In Production Example 13 (P-13), Production Example 16 (P-16), Production Example 17 (P-17), and Production Example 20 (P-20), modification to give an ethylenically unsaturated group was performed. Not.

[Production Example 4]
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 100 parts of methoxypropyl acetate, heated to 90 ° C., and the inside of the reaction vessel was purged with nitrogen. , 6 parts of methacrylic acid, 25 parts of 2-methacryloyloxy-γ-butyrolactone, 26 parts of 2-hydroxyethyl methacrylate and 4 parts of dimethyl 2,2′-azobis (2-methylpropionate) were previously mixed uniformly. Was added dropwise over 2 hours, followed by stirring at the same temperature for 3 hours to obtain a carboxyl group-containing polymer. Subsequently, the temperature of the reaction vessel is cooled to 70 ° C., and dry air is further introduced into the reaction vessel. 25 parts of 2-methacryloyloxyethyl isocyanate, 25 parts of methoxypropyl acetate, 0.1 part of dibutyltin dilaurate, 0.1 part of methoquinone .1 part was charged, and then stirring was continued at the same temperature for 10 hours to obtain an acrylic curable resin. Here, it was confirmed by the IR spectrum that the reaction between the hydroxyl group and the isocyanate group was completed. After cooling to room temperature, it was diluted with methoxypropyl acetate to obtain an acrylic curable resin solution P-4 having a solid content of 30%.

[Production Examples 9, 15, 18]
The compositions shown in Table 1 were synthesized in the same manner as in Production Example 4 to obtain acrylic curable resin solutions P-9, P-15, and P-18 having a solid content of 30%. In Production Example 15, the polymer obtained as an intermediate does not contain a carboxyl group.

[Production Example 6]
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 100 parts of methoxypropyl acetate, heated to 90 ° C., and the inside of the reaction vessel was purged with nitrogen. 30 parts of ethyl acrylate, 37 parts of acrylic acid, 8 parts of PME-400, 5 parts of tricyclo- (5,2,1,0,2.6) -decanyl (meth) acrylate and dimethyl 2,2′-azobis ( A mixed liquid in which 9 parts of 2-methylpropionate) were uniformly mixed in advance was dropped over 2 hours, and then stirred at the same temperature for 3 hours to obtain a carboxyl group-containing polymer. Subsequently, dry air was introduced into the reaction vessel, charged with 58 parts of glycidyl methacrylate, 77 parts of methoxypropyl acetate, 1 part of dimethylbenzylamine and 0.1 part of methoquinone, and then continued stirring at the same temperature for 10 hours. A containing polymer was obtained. Here, the reaction rate of glycidyl methacrylate was 99% as determined from the change in the acid value of the polymer before and after the reaction. Further, 19 parts of tetrahydrophthalic anhydride was charged, and stirring was continued at the same temperature for 10 hours to obtain an acrylic curable resin. Here, it was confirmed by the IR spectrum that the reaction between the hydroxyl group and the acid anhydride was completed. After cooling to room temperature, it was diluted with methoxypropyl acetate to obtain an acrylic curable resin solution P-6 having a solid content of 30%.

[Production Examples 7 and 8]
The compositions shown in Table 1 were synthesized in the same manner as in Production Example 6 to obtain acrylic curable resin solutions P-7 and P-8 having a solid content of 30%.

[Production Example 10]
A reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 100 parts of methoxypropyl acetate, heated to 90 ° C., the inside of the reaction vessel was purged with nitrogen, and then 30 parts of methyl methacrylate from the dropping tank. 30 parts of ethyl acrylate, 23 parts of glycidyl methacrylate, 7 parts of tricyclo- (5,2,1,0,2.6) -decanyl methacrylate, 10 parts of 2-methacryloyloxy-γ-butyrolactone and dimethyl 2,2 ′ -A mixed solution in which 7 parts of azobis (2-methylpropionate) was uniformly mixed in advance was added dropwise over 2 hours, followed by stirring at the same temperature for 3 hours to obtain an epoxy group-containing polymer. Subsequently, dry air was introduced into the reaction vessel, charged with 12 parts of acrylic acid, 28 parts of methoxypropyl acetate, 1 part of dimethylbenzylamine and 0.1 part of methoquinone, and then stirred at the same temperature for 10 hours. A containing polymer was obtained. Here, the reaction rate of acrylic acid was 99% as determined from the change in the epoxy value of the polymer before and after the reaction. Furthermore, 16 parts of succinic anhydride was charged, and then stirring was continued at the same temperature for 10 hours to obtain an acrylic curable resin. Here, it was confirmed by the IR spectrum that the reaction between the hydroxyl group and the acid anhydride was completed. After cooling to room temperature, it was diluted with methoxypropyl acetate to obtain an acrylic curable resin solution P-10 having a solid content of 30%.

[Production Examples 11 and 12]
The compositions shown in Table 1 were synthesized in the same manner as in Production Example 10 to obtain acrylic curable resin solutions P-11 and P-12 having a solid content of 30%.

MMA: methyl methacrylate EA: ethyl acrylate n-BMA: n-butyl methacrylate GMA: glycidyl methacrylate M-100: 3,4-epoxycyclohexylmethyl methacrylate (manufactured by Daicel Chemical Industries)
VBGE: p-vinylbenzyl glycidyl ether 2MTA: 2-methoxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
PME-400: Methoxypolyethylene glycol monomethacrylate (manufactured by NOF Corporation)
FA513M: Tricyclo- (5,2,1,0,2.6) -decanyl (meth) acrylate (manufactured by Hitachi Chemical Co., Ltd.)
GBLMA: 2-methacryloyloxy-γ-butyrolactone (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
HEMA: 2-hydroxyethyl methacrylate HMA: hexyl methacrylate CHMA: cyclohexyl methacrylate LMA: lauryl methacrylate BzMA: benzyl methacrylate AMA: allyl methacrylate V-601: dimethyl 2,2'-azobis (2-methylpropionate) (Wako Pure Chemical) Manufactured by Kogyo Corporation)
V-65: 2,2′-azobis (2,4-dimethylvaleronitrile) (manufactured by Wako Pure Chemical Industries, Ltd.)
AIBN: N, N-azobisisobutyronitrile PGMAc: methoxypropyl acetate (manufactured by Daicel Chemical Industries)
HPE: ethyl 3-hydroxypropionate 4HBAGE: 4-hydroxybutyl acrylate glycidyl ether (manufactured by Nippon Kasei Co., Ltd.)
MOI: 2-methacryloyloxyethyl isocyanate (made by Showa Denko KK)
AOI: 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK)
THPA: Tetrahydrophthalic anhydride SA: Succinic anhydride DMBA: Dimethylbenzylamine DBTDL: Dibutyltin dilaurate TEBAC: Triethylbenzylammonium chloride IPA: Isopropyl alcohol

[Examples 1 to 16, Comparative Examples 1 to 12]
In the blending compositions shown in Table 2 and Table 3, the mixture was stirred and mixed so as to be uniform, then filtered through a 1 μm filter, and photosensitive resin compositions S-1 to S-16 and H-1 to H- 12 was obtained.

XD-1000: epoxy compound containing dicyclopentadiene skeleton (manufactured by Nippon Kayaku Co., Ltd.) epoxy equivalent 250
EHPE3150: 1,2-epoxy-4- (2-oxiranyl) cyclosoxane adduct of 2,2-bis (hydroxymethyl) -1-butanol (manufactured by Daicel Chemical Industries), epoxy equivalent 179
Celoxide 2021P: 3,4-epoxycyclohexenylmethyl-3′4′-epoxycyclohexenecarboxylate (manufactured by Daicel Chemical Industries) Epoxy equivalent 145
EP-4088S: tricyclodecanyl diglycidyl ether (manufactured by ADEKA) epoxy equivalent 170
DPHA: dipentaerythritol hexaacrylate TMPTA: trimethylolpropane triacrylate Irg907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one (manufactured by Ciba Japan; product name IRGACURE907) )
Irg184: 1-hydroxy-cyclohexyl phenyl ketone (manufactured by Ciba Japan; product name IRGACURE184)
OXE02: Ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (O-acetyloxime) (manufactured by Ciba Japan; product name IRGACURE OXE02)
VAm-111: 2,2′-azobis (N-cyclohexyl-2-methylpropionamide) (manufactured by Wako Pure Chemical Industries, Ltd.)
KBM403: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.)
PGMAc: Methoxypropyl acetate (manufactured by Daicel Chemical Industries)
CHXA: cyclohexyl acetate (manufactured by Daicel Chemical Industries)
Irg369: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (manufactured by Ciba Japan; product name IRGACURE 369)
α-AAF: α-aminoacetophenone MIBK-ST: Silica sol 30% by mass methyl isobutyl ketone dispersion (manufactured by Nissan Chemical Co., Ltd.)
YH434L: glycidyl aminated product of bisphenol F (tetrafunctional epoxy, manufactured by Tohto Kasei Co., Ltd., epoxy equivalent 130)
NC7000L: Naphthalene skeleton-containing epoxy compound (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent 230)
EX411: Pentaerythritol tetraglycidyl ether (tetrafunctional epoxy, manufactured by Nagase ChemteX Corporation, epoxy equivalent 229)
V-05: Carbodilite V-05 (carbodiimide curing agent, Nisshinbo Co., Ltd., carbodiimide equivalent 262)
TMA: trimellitic anhydride 2E4MI: 2-ethyl-4-methylimidazole HPE: ethyl 3-hydroxypropionate EGE: ethylene glycol monoethyl ether

  About the photosensitive composition obtained by the Example and the comparative example, a sample board | substrate is produced with the following method, and developability, transparency, hardness, insulation, base-material adhesiveness, flatness, and storage stability are evaluated. did.

<Preparation of sample substrate for evaluation>
(Preparation of ink)
ε-type copper phthalocyanine pigment (CI Pigment Blue 15: 6) 10.0 parts (“Heliogen Blue L-6700F” manufactured by BASF), phthalocyanine pigment derivative [following formula (5)] 1.0 part, acrylic Resin solution (methyl methacrylate / n-butyl methacrylate / benzyl methacrylate / methacrylic acid = 30/30/30/10 (weight ratio), Mw 30,000, methoxypropyl acetate solution having a solid content of 50%) 40.0 parts, methoxypropyl A mixture of 48.0 parts of acetate was uniformly stirred and mixed, and then dispersed with a sand mill for 5 hours using glass beads having a diameter of 1 mm, and then filtered with a 5 μm filter to prepare a copper phthalocyanine dispersion.

Formula (5)

[Cu-pc represents a copper phthalocyanine residue. ]

  Subsequently, 45.0 parts of the copper phthalocyanine dispersion, 15.0 parts of the acrylic resin solution, 5.6 parts of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), photopolymerization initiator (Ciba Geigy) “Irgacure 907” manufactured by 2.0), 0.2 parts of a sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.), and 32.2 parts of methoxypropyl acetate were stirred and mixed uniformly. It filtered with a 1 micrometer filter and obtained the blue coloring composition (ink B).

  Instead of the ε-type copper phthalon-cyanine pigment, 8.33 parts of diketopyrrolopyrrole pigment (CI Pigment Red 254) (“Irgafour Red B-CF” manufactured by Ciba Geigy Co.), anthraquinone pigment (C.I. Pigment Red 177) 1.33 parts (Ciba Geigy "chromoftal red A2B"), anthraquinone pigment (CI Pigment Yellow 199) 0.34 parts (Ciba Geigy "chromoftal yellow GT-") AD ”) in the same manner as the blue colored composition (ink B) except that 1.0 part of the compound represented by the following formula (6) was used instead of the phthalocyanine pigment derivative. Ink R) was obtained.

Formula (6)

(Preparation of adhesion test substrate)
Ink B was applied on a 10 cm × 10 cm square glass substrate using a spin coater, and then dried in an oven at 80 ° C. for 5 minutes to form a coating film having a thickness of 1.5 μm. The substrate was cooled to room temperature, and then exposed through a photomask using a high-pressure mercury lamp at an exposure amount of 100 mJ / cm ² . Thereafter, the substrate is immersed in a developer composed of 5% by weight sodium carbonate aqueous solution at 25 ° C. for 1 minute, developed, washed with pure water and air-dried, and further baked in an oven at 240 ° C. for 40 minutes. went. The adhesion test substrate thus prepared was designated as substrate B. A substrate for adhesion test prepared using ink R in the same manner was used as substrate R.
(Production of sample substrate)
The photosensitive composition S-1 was applied on a 10 cm × 10 cm square glass substrate, the substrate B, and the substrate R using a spin coater, and then dried in an oven at 80 ° C. for 5 minutes to obtain a film thickness of 2. A 0 μm coating film was formed. The substrate was cooled to room temperature, and then exposed through a photomask using a high-pressure mercury lamp at an exposure amount of 100 mJ / cm ² . Thereafter, the substrate is immersed in a developer composed of 5% by weight sodium carbonate aqueous solution at 25 ° C. for 1 minute, developed, washed with pure water and air-dried, and further baked in an oven at 240 ° C. for 40 minutes. By performing, the sample substrate U-1 was produced.

  Sample substrates U-2 to U-28 were prepared in the same manner as the sample substrate U-1, except that the photosensitive resin compositions S-2 to S-16 and H-1 to H-12 were used.

<Evaluation of coating film>
(Developability evaluation)
The photosensitive composition was applied on a 10 cm × 10 cm square glass substrate using a spin coater, and then dried in an oven at 80 ° C. for 5 minutes to form a coating film having a thickness of 2.0 μm. The substrate was cooled to room temperature, and then exposed through a photomask using a high-pressure mercury lamp at an exposure amount of 100 mJ / cm ² . Thereafter, the substrate was immersed in a developer composed of a 5% by weight aqueous sodium carbonate solution at 25 ° C. for 30 seconds and 1 minute, washed with pure water, and air-dried. The remaining degree of the development residue at this time was observed. When the development residue was not observed when immersed in the developer for 30 seconds, when the development residue was not observed when immersed in the developer for 1 minute, Δ was observed even when immersed in the developer for 1 minute. Time was marked with x. ○ and Δ are practical levels.

(Transparency evaluation)
The transmittance of the sample substrates U-1 to U-28 (glass substrate) was measured with a spectrophotometer (“U-3310” manufactured by Hitachi, Ltd.). Considering practical required physical properties, a case where the transmittance at a wavelength of 400 nm was 95% or more was judged as ○, and a case where it was smaller than 95% was judged as ×.

(Hardness evaluation)
In accordance with JIS K5600, using a pencil hardness tester ("Clemens-type scratch hardness tester" manufactured by Tester Sangyo Co., Ltd.), the hardness of the pencil core is changed variously, and the sample substrates U1 to U-28 are loaded at a load of 500 g. The coating on the (glass substrate) was tested 5 times. The hardness of the core when scratches were not scratched or scratched only once out of 5 times was defined as the pencil hardness of the coating film. Considering practical required physical properties, it was determined that a pencil hardness of 2H or higher was good.

(Insulation evaluation)
About the sample board | substrates U-1 to U-28 (glass board | substrate), the volume resistance value was measured with the digital ultrahigh resistance / microammeter R8340A (Daiichi Kagaku company make, probe URS, applied voltage 5V). In consideration of practical required physical properties of the interlayer insulating film, those having a surface resistance in the range of 1 × 10 ^{12 to} 3 × 10 ¹⁶ Ω / □ are insulative. It was.

(Base material adhesion evaluation)
Based on JIS K5400, 100 cross-cut test of 1 mm square was implemented about the coating film on sample board | substrate U-1-U-28 (glass substrate), and the peeling state was observed with the cellophane tape. The adhesion number in 100 pieces (the number of grids remaining without being peeled) was counted to evaluate the glass adhesion. In consideration of practical required physical properties, 90 or more was judged as ◯, 80 to 89 as Δ, and 79 or less as x. ○ and Δ are practical levels.

  Further, the adhesion of the sample substrates U-1 to U-28 (substrate B and substrate R) was evaluated in the same manner as the coating film on the glass substrate. However, here, the peeled state at the interface between the coating film made of ink B or ink R and the coating film made of the photosensitive composition was observed.

(Flatness evaluation)
For the sample substrates U-1 to U-28 (glass substrates), using a surface shape measuring device “Dektak150” (manufactured by ULVAC, Inc.), the measurement length is 1,000 μm, the measurement range is 1,000 μm square, and the number of measurement points is n = 5. The average roughness was measured. When this value is less than 40 nm, the flatness is indicated by ◯, when it is in the range of 40 to 100 nm, Δ is indicated, and when it exceeds 100 nm, it is indicated by ×. ○ and Δ are practical levels.

(Storage stability)
In order to evaluate the storage stability, the initial viscosity and time-lapse viscosity of the photosensitive compositions S-1 to S-16 and H-1 to H-12 were measured with a B-type viscometer (25 ° C., rotation speed 100 rpm). . The initial viscosity was measured after the photosensitive compositions S1 to S16 and H-1 to H-12 were prepared and allowed to stand at room temperature for 1 day. The viscosity with time was measured after leaving at 50 ° C. for 1 week. When the value of (aging viscosity−initial viscosity) is within ± 10% with respect to the initial viscosity, the storage stability was evaluated as “◯”, and when out of the range of ± 10%, it was evaluated as “X”.

The evaluation results are shown in Table 4 and Table 5.

  As shown in Table 4, the photosensitive resin compositions of Examples 1 to 16 were good in all of developability, transparency, hardness, insulation, substrate adhesion, flatness, and storage stability. On the other hand, the photosensitive compositions of Comparative Examples 1 to 12 shown in Table 5 are poor in developability, transparency, hardness, insulation, substrate adhesion, flatness, and storage stability. There was nothing that was all good.

[Example 17]
(Production of sample substrate)
The photosensitive composition S-14 produced in Example 14 was applied on a 10 cm × 10 cm square glass substrate, substrate B, and substrate R using a spin coater, and then dried in an oven at 80 ° C. for 5 minutes. Thus, a coating film having a thickness of 2.0 μm was formed. Further, a sample substrate U-29 was produced by baking in an oven at 240 ° C. for 40 minutes.

[Example 18 and Comparative Example 13]
Sample substrates U-30 and U-31 were produced in the same manner as in Example 17 except that the photosensitive composition S-15 produced in Example 15 and H-4 produced in Comparative Example 4 were used.

  Transparency, hardness, insulation, adhesion, and flatness were evaluated by the above methods, and the results are shown in Table 6.

  As shown in Table 6, the photosensitive compositions of Examples 17 and 18 had good transparency, hardness, insulation and adhesion, and also had good flatness, whereas Comparative Example 13 This photosensitive composition had poor hardness, adhesion, and flatness.

Claims (17)

An acrylic curable resin (A) having a linear or branched alkyl group having 1 to 4 carbon atoms, a carboxyl group, and an ethylenically unsaturated group;
At least one epoxy compound (B) selected from the group consisting of an epoxy compound having a monocyclo ring, an epoxy compound having a bicyclo ring, and an epoxy compound having a tricyclo ring,
A polymerizable compound (C) having an ethylenically unsaturated group, and
A photosensitive composition comprising a solvent (D). The photosensitive composition according to claim 1, wherein the epoxy compound (B) is a compound represented by the following general formula (1).
General formula (1)

Wherein, n ¹ is an integer of 0. ] The photosensitive composition according to claim 1, wherein the epoxy compound (B) is a compound represented by the following general formula (2).
General formula (2)

[Wherein, R ¹ is a hydrogen atom or a methyl group, and n ² is an integer of 1-20. ]   The molar ratio of the number of moles of carboxyl groups (a) in the acrylic curable resin (A) to the number of moles (b) of epoxy groups in the epoxy compound (B) is (a) / (b) = 0. The photosensitive composition according to claim 1, which is 0.5-2. The acrylic curable resin (A) comprises an ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms and a carboxyl group-containing ethylenically unsaturated monomer (m2). ) And an ethylenically unsaturated monomer (M) to obtain a carboxyl group-containing polymer (E),
The photosensitive composition in any one of Claims 1-4 formed by making the epoxy group in an epoxy-group-containing ethylenically unsaturated monomer (F) react with the carboxyl group in this polymer (E). The acrylic curable resin (A) comprises an ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms and a carboxyl group-containing ethylenically unsaturated monomer (m2). ) And an ethylenically unsaturated monomer (M) to obtain a carboxyl group-containing polymer (E),
After reacting the epoxy group in the epoxy group-containing ethylenically unsaturated monomer (F) with the carboxyl group in the polymer (E) to obtain a hydroxyl group-containing polymer (G),
The photosensitive composition in any one of Claims 1-4 formed by making the acid anhydride group in a polybasic acid anhydride (H) react with the hydroxyl group in this polymer (G). The acrylic curable resin (A) is an ethylenically unsaturated monomer (m1) having a linear or branched alkyl group having 1 to 4 carbon atoms and an epoxy group-containing ethylenically unsaturated monomer (m3). ) To obtain an epoxy group-containing polymer (P) by copolymerizing an ethylenically unsaturated monomer (N) containing
After reacting the carboxyl group in the carboxyl group-containing ethylenically unsaturated monomer (Q) with the epoxy group in the polymer (P) to obtain a hydroxyl group-containing polymer (K),
The photosensitive composition in any one of Claims 1-4 formed by making the acid anhydride group in a polybasic acid anhydride (H) react with the hydroxyl group in this polymer (K). The ethylenically unsaturated monomer (M) or the ethylenically unsaturated monomer (N) contains an ethylenically unsaturated monomer (m4) represented by the following general formula (3). The photosensitive composition in any one.
General formula (3)

[Wherein R ² represents a hydrogen atom or a methyl group, and R ³ represents a hydrogen atom, a linear or branched alkyl group having 1 to 8 carbon atoms, an alicyclic hydrocarbon group, or an aromatic carbon group. A hydrogen group, and n ³ is an integer of 1 to 10. ]   The photosensitive composition according to any one of claims 1 to 8, wherein the acrylic curable resin (A) has an acid value of 20 to 200 mgKOH / g.   The photosensitive composition according to any one of claims 1 to 9, wherein the acrylic curable resin (A) has a weight average molecular weight of 2000 to 25000. The photosensitive composition in any one of Claims 1-10 in which a solvent (D) contains the solvent represented by following General formula (4).
General formula (4)

[Wherein, R ⁴ is an alkyl group having 1 to 3 carbon atoms, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. ]   The photosensitive composition in any one of Claims 1-11 containing a photoinitiator (I).   The photosensitive composition in any one of Claims 1-12 containing a thermal-polymerization initiator (J).   The coating agent for color filter protective films containing the photosensitive composition in any one of Claims 1-13.   The color filter protective film formed from the coating agent for color filter protective films of Claim 14.   The interlayer insulation film for touchscreens formed using the photosensitive composition in any one of Claims 1-13.   The photospacer for touchscreens formed using the photosensitive composition in any one of Claims 1-13.