JP7061502B2 - Polymerizable compositions, photosensitive compositions for black matrices and color filters - Google Patents

Description

The present invention relates to a polymerizable composition, a photosensitive composition for black matrix (BM), a cured product of the composition, a color filter using the cured product, and a method for producing the cured product.

Conventionally, a color filter has been widely used for the purpose of colorizing a liquid crystal display device or the like, and generally, red, green, and blue pixels are arranged in a mosaic pattern. As a method for producing this color filter, a dyeing method, a printing method, an inkjet method, an electrodeposition method, a colorant dispersion method and the like are known. In particular, a colorant dispersion method in which fine pixels are formed by photolithography using a colored polymerizable composition for a color filter in which a colorant is dispersed together with a photosensitive polymer and / or a photosensitive monomer is used to improve the flatness of the pixels. Due to its superiority, it has become the mainstream of color filter manufacturing methods.

The photosensitive composition for BM used for producing a color filter contains a pigment, a solvent, a dispersant, a photopolymerizable unsaturated compound, a polymerization initiator and the like. Since the photosensitive composition for BM can be polymerized and cured by irradiating it with ultraviolet rays or electron beams, it is useful for producing a black matrix (BM) constituting a color filter. BM removes excess solvent from a coating material obtained by applying a photosensitive material to a glass substrate or the like by drying, and then exposes the coating material with active energy rays via a photomask for forming pixels. It is formed by irradiating, curing (negative type) or increasing alkaline solubility (positive type), and then removing a portion to be dissolved with an alkaline solution or the like, and then applying post-baking, which is heating at 230 degrees or higher.
When a pigment is used in the above-mentioned photosensitive composition for BM, it is common to prepare a pigment dispersion liquid in which the pigment is dispersed in a resin or a dispersion medium in advance when preparing the photosensitive composition.

Patent Document 1 discloses reactive particles obtained by reacting particles with a hydrolyzable silane having a (meth) acryloyloxy group and an isocyanurate ring structure, and Patent Document 2 comprises blocked isocyanate silane. A photosensitive composition having excellent adhesion to a substrate containing a silane coupling agent is disclosed.

International Publication 2011/086958 Pamphlet International Publication 2013/187209 Pamphlet

In recent years, there has been a strong demand for high-definition display panels, reflecting the high quality of color image sensors and color LCD televisions. Therefore, a photosensitive composition for a highly adhesive BM, which has a high light-shielding property and can secure sufficient adhesiveness even in a BM having a low line width, has been studied. However, there is a problem that there is no photosensitive composition for BM that can obtain a cured product having high sensitivity, excellent storage stability, and a level of light-shielding property and high adhesiveness required for BM.

The problem to be solved by the present invention is that there has never been a photosensitive composition for BM that can obtain a cured product having high sensitivity, excellent storage stability, and a level of light-shielding property and high adhesiveness required for BM. That is to say.

An object of the present invention is a polymerizable composition and a photosensitive composition for BM, which can obtain a cured product having high sensitivity, excellent storage stability, and a level of light-shielding property and high adhesiveness required for BM, the polymerization thereof. It is an object of the present invention to provide a cured product obtained from a sex composition and a photosensitive composition for BM, a color filter containing the cured product, and a method for producing the cured product.

The present invention has achieved the above object by providing the following [1] to [10] after diligent studies.

[1] A blocked isocyanate silane compound (A), a polymerizable compound (B), and a polymerization initiator (C) having a structure obtained by reacting an isocyanate compound represented by the following general formula (I) with a blocking agent. A polymerizable composition containing.

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocycle.
Z ¹ represents a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocycle, and one or more of the methylene groups in the group represented by Z ¹ . -O-, -CO-, -COO-, -OCO-, -NR ^4- , -NR ⁴ CO-, -S-, -CS-, -SO _2- , under the condition that oxygen is not adjacent to each other. May be replaced with -SCO-, -COS-, -OCS- or CSO-
^R4 represents a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms.
a represents a number from 1 to 3, and when a ≧ 2, a plurality of R ^1s may be the same or different.
b represents a number from 0 to 2, and when b = 2, multiple R ^2s may be the same or different.
a + b = 3. )

[2] The polymerizable composition according to claim 1, wherein the blocked isocyanate silane compound (A) is a compound represented by the following general formula (II).

(In the formula, R ¹ , R ² , a, b and Z ¹ are the same as those in the above general formula (I).
R ³ represents a hydrogen atom or a methyl group.
X ¹ and X ³ each independently represent a direct bond or a hydrocarbon group having 1 to 20 carbon atoms.
X ² represents a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocycle.
One or more of the methylene groups in the groups represented by X ¹ , X ² and X ³ are -O-, -CO-, -COO-, -OCO-, under the condition that oxygen is not adjacent to each other. It may be replaced with -NR ^4- , -NR ⁴ CO-, -S-, -CS-, -SO _2- , -SCO-, -COS-, -OCS- or CSO-.
Y represents an oxygen atom, a sulfur atom, or -NR ^4- , and represents
^R4 represents a hydrogen atom and a hydrocarbon group having 1 to 20 carbon atoms.
c represents a number from 2 to 10 and represents
When c ≧ 2, multiple ^R3s may be the same or different.
d represents a number from 1 to 3 and represents
When d ≧ 2, R ¹ , R ² , X ³ and Z ¹ may be the same or different. )

（式中の＊は、一般式（ＩＩＩ）で表される基が、＊部分で、隣接する基と結合することを意味する。） [3] The polymerizable composition according to [1] or [2], wherein the blocked isocyanate silane compound (A) is a blocked isocyanate silane compound having a group represented by the following general formula (III).

(* In the formula means that the group represented by the general formula (III) is bonded to an adjacent group at the * part.)

[4] The polymerizable compound (B) is
Epoxy compounds represented by the following general formula (IV),
An unsaturated compound having a structure in which an epoxy compound represented by the following general formula (IV) and an unsaturated monobasic acid are esterified, or an epoxy compound represented by the following general formula (IV) and an unsaturated monobasic acid. The polymerizable composition according to any one of [1] to [3], which is an unsaturated compound having a structure in which polybasic acid anhydride is further esterified to an unsaturated compound having a structure in which and is esterified. thing.

(In the formula, M is a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -O-, -S-, -SO _2- , -SS-, -SO-, -CO-, -OCO-, or. Represents a substituent selected from the group consisting of the following formulas (a), (b), (c) and (d).
One or more hydrogen atoms in a hydrocarbon group having 1 to 20 carbon atoms represented by M may be replaced with a halogen atom.
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen atom, respectively.
The methylene group among the groups represented by R ¹¹ to R ¹⁸ may be replaced with —O— under the condition that oxygen is not adjacent to each other.
n represents a number from 0 to 10 and represents
When n is not 0, a plurality of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , and M, which are present in plurality, may be the same or different from each other. )

(In the formula, R ²¹ represents a hydrocarbon group having 1 to 20 carbon atoms.
R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ . , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ and R ⁵⁰ , respectively, independently have a hydrogen atom and 1 to 1 carbon atom. Represents 20 hydrocarbon groups, groups with 2 to 20 carbon atoms containing heterocycles, or halogen atoms.
R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ . , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ and one of the methylene groups in the group represented by R ⁵⁰ . One or more may be replaced with -O- or -S- under the condition that oxygen is not adjacent to each other.
R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁴ and R ²⁵ , R ²⁵ and R ²⁶ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁵ and R ³⁶ , R ³⁶ . And R ³⁷ , R ³⁷ and R ³⁸ , R ⁴³ and R ⁴⁴ , R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁷ and R ⁴⁸ , R ⁴⁸ and R ⁴⁹ and R ⁴⁹ and R ⁵⁰ are coupled and ringed. May form,
* In the formula means that the group represented by (a), (b), (c) and (d) is bonded to the adjacent group at the * portion. )

[5] The polymerizable composition according to any one of [1] to [4], wherein the polymerization initiator (C) is a compound having a group represented by the following general formula (V).

(In the formula, R ⁶¹ and R ⁶² each independently have a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocycle having 2 to 20 carbon atoms. Represents the group
One or more of the hydrogen atoms in the groups represented by R ⁶¹ and R ⁶² are halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group and vinyl group. , A vinyl ether group, a mercapto group, an isocyanate group or a group having 2 to 20 carbon atoms containing a heterocycle may be substituted.
One or more of the methylene groups in the groups represented by R ⁶¹ and R ⁶² are -O-, -CO-, -COO-, -OCO-, -NR ⁶³ under the condition that oxygen is not adjacent to each other. -, -NR ⁶³ CO-, -S-, -CS-, -SO _2- , -SCO-, -COS-, -OCS- or CSO-may be replaced.
R ⁶³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
m represents 0 or 1 and represents
* In the formula means that the group represented by the general formula (V) is bonded to an adjacent group at the * part. )

[6] The polymerizable composition according to any one of [1] to [5], which further contains a colorant (D).

[7] A photosensitive composition for a black matrix containing the polymerizable composition according to any one of [1] to [6].

[8] A method for producing a cured product, wherein the polymerizable composition according to any one of [1] to [6] or the photosensitive composition for black matrix according to [7] is cured by light or heat.

[9] The polymerizable composition according to any one of [1] to [6] or the cured product of the photosensitive composition for black matrix according to [7].

[10] A color filter containing the cured product according to [9].

According to the present invention, a polymerizable composition and a photosensitive composition for BM can be obtained, which can obtain a obtained cured product having excellent storage stability and the level of light-shielding property and high adhesiveness required for BM.

Hereinafter, the polymerizable composition of the present invention will be described in detail based on a preferred embodiment.

The polymerizable composition of the present invention is a blocked isocyanate silane compound (A) obtained by reacting an isocyanate compound represented by the above general formula (I) with a blocking agent (hereinafter, also referred to as a blocked isocyanate silane compound (A)). Description), a polymerizable compound (B) and a polymerization initiator (C). Hereinafter, each component will be described in order.

<Blocked isocyanate silane compound (A)>
The blocked isocyanate silane compound (A) is a compound having a structure obtained by reacting an isocyanate compound represented by the above general formula (I) with a blocking agent.

The radically polymerizable composition of the present invention contains a blocked isocyanate silane compound (A) having a structure obtained by reacting an isocyanate compound represented by the above general formula (I) with a blocking agent as an essential component. In the present invention, compounds having various structures can be used as a raw material for the blocked isocyanate silane compound (A) contained as an essential component in the polymerizable composition. Therefore, the structure of the "blocked isocyanate silane compound (A) having a structure obtained by reacting the isocyanate compound represented by the above general formula (I) with the blocking agent" is represented by the general formula (I). It varies greatly depending on the structure of the isocyanate compound and the blocking agent. Therefore, the structure of the "blocked isocyanate silane compound (A) having a structure obtained by reacting the isocyanate compound represented by the above general formula (I) with a blocking agent" is uniformly represented by a certain general formula. The current situation is that this cannot be done at all, and this is the common general knowledge of those skilled in the art. And since the characteristics of the substance, which are determined accordingly, cannot be easily understood unless the structure is specified, it cannot be expressed by the characteristics. Therefore, in the present invention, the blocked isocyanate silane compound (A) contained as an essential component in the polymerizable composition is obtained by reacting the isocyanate compound represented by the above general formula (I) with a blocking agent. It must be defined by the expression "blocked isocyanate silane compound (A) having a structure". That is, regarding the blocked isocyanate silane compound (A) used as an essential component in the present invention, there are circumstances in which it is impossible or approximately impractical to "directly specify the compound by its structure or characteristics at the time of filing". ..

Examples of the isocyanate compound represented by the general formula (I) include 3-isocyanatotrimethoxypropylsilane and 3-isocyanatotriethoxypropylsilane. Examples of commercially available isocyanate compounds represented by the general formula (I) include KBE-9007 (manufactured by Shinetsu Silicone Co., Ltd.) and A-Link35 (manufactured by Momentive Co., Ltd.).

In the present invention, the blocking agent can inactivate the isocyanate group by reacting with the isocyanate group or coordinating with the isocyanate group, dissociate by an external stimulus such as heat or light, and reactivate the isocyanate group. Means a compound. As the blocking agent, conventionally used agents can be used, for example, carboxylic acid esters such as dimethyl malonate and diethyl malonate; malonic acid, acetylacetone, and acetoacetic acid esters (methylacetate acetate, acetoacetic acid). Active methylene compounds such as ethyl); formamide oxime, acetamide oxime, acetoxime, diacetylmonooxime, benzophenone oxime, cyclohexanone oxime, methyl ethyl keto oxime (MEK oxime), methyl isobutyl keto oxime (MIBK oxime), dimethyl keto oxime, diethyl keto Oxime compounds such as oxime; aliphatic alcohols such as methanol, ethanol, propanol, butanol, 2-ethylhexanol, heptanol, hexanol, octanol, isononyl alcohol, stearyl alcohol; aromatic alcohols such as benzyl alcohol; isocyanuric acid EO-modified di Isocyanurate-modified alcohols such as acrylates and EO-modified diglycidyl ethers of isocyanuric acid; methyl glycol, ethyl glycol, ethyl diglycol, ethyl triglycol, butyl glycol, butyl diglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene. Glycol derivatives such as glycol monobutyl ether and propylene glycol monomethyl ether; phenols such as phenol, cresol, xylenol, ethylphenol, propylphenol, butylphenol, octylphenol, nonylphenol, nitrophenol, chlorophenol or their isomers; fluorene-modified bisalcohol Hydroxime-containing esters such as oxime lactate and amyl lactate; amine compounds such as dibutylamine, diisopropylamine, di-tert-butylamine, di-2-ethylhexylamine, dicyclohexylamine, benzylamine, diphenylamine, aniline and carbazole; ethyleneimine, Oxime compounds such as polyethyleneimine; alcohol amines such as monomethylethanolamine, diethylethanolamine, and triethylethanolamine; α-pyrrolidone, β-butyrolactam, β-propiolactam, γ-butyrolactam, δ-valerolactam, ε-caprolactam, etc. Oximes; guanidines such as 1,1,3,3-tetramethylguanidine; butyl mercaptan, f Mercaptans such as xyl mercaptan and dodecyl mercaptan; imidazoles such as imidazole and 2-ethylimidazole; acid amides such as acetanilide, acrylamide, acetate amide and dimer acid amide; Acid imides; urea compounds such as urea, thiourea and ethylene urea; benzotriazoles; pyrazoles such as 3,5-dimethylpyrazole and the like can be mentioned. One of these blocking agents can be reacted with the isocyanate compound represented by the general formula (I), or two or more thereof can be reacted with the isocyanate compound represented by the general formula (I). can.

Among the above-mentioned blocking agents, those having a dissociation temperature of 100 to 200 ° C. are preferable because they are stable at the time of prebaking and react at the time of post-baking. , Diacetylmonooxime, benzophenone oxime, cyclohexanone oxime, methyl ethyl keto oxime (MEK oxime), methyl isobutyl keto oxime (MIBK oxime), dimethyl keto oxime, diethyl keto oxime are preferable, and methyl ethyl keto oxime is most preferable.

Of the above blocking agents, fluorene-modified bis-alcohol and isocyanurate-modified alcohol are preferable because they improve the adhesion to the substrate.

The blocking reaction for obtaining the blocked isocyanate silane (A) can be carried out by a known reaction method. The amount of the blocking agent added to the isocyanate compound represented by the general formula (I) is usually 1 to 2 equivalents, preferably 1.05 to 1.5 equivalents, relative to 1 equivalent of the free isocyanate group. The reaction temperature of the blocking reaction is usually 50 to 150 ° C, preferably 60 to 120 ° C. The reaction time is preferably about 1 to 7 hours. Further, a catalyst or a solvent (aromatic hydrocarbon-based, ester-based, ether-based, ketone-based, or a mixed solvent of two or more of these) can be added to the reaction system.

Examples of the alkyl group having 1 to 8 carbon atoms represented by ^R1 in the general formula (I) include methyl, ethyl, propyl, iso-propyl, butyl, sec-butyl, tert-butyl, iso-butyl and amyl. , Iso-amyl, tert-amyl, hexyl, 2-hexyl, 3-hexyl, cyclohexyl, 1-methylcyclohexyl, heptyl, 2-heptyl, 3-heptyl, iso-heptyl, tert-heptyl, 1-octyl, iso- Examples include octyl, tert-octyl and the like.

In the above general formula (I), an isocyanate compound in which R ¹ is an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl and propyl is preferable from the viewpoint of easy availability of raw materials.
Further, in the above general formula (I), an isocyanate compound in which a is 3 and b is 0 is preferable from the viewpoint of adhesion.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ² and R ⁴ in the general formula (I) is not particularly limited, but is preferably an alkyl group having 1 to 20 carbon atoms. An alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, a cycloalkylalkyl group having 4 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms and 7 to 20 carbon atoms. Represents an arylalkyl group or the like. Since the obtained blocked isocyanate silane compound (A) has good sensitivity and adhesion to a substrate, it has an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and 3 to 10 carbon atoms. , A cycloalkylalkyl group having 4 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an arylalkyl group having 7 to 10 carbon atoms, and the like are preferable.

Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl and isooctyl. , 2-Ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, icosyl and the like. Examples of the alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, amyl, isoamyl, t-amyl, hexyl, heptyl, octyl and isooctyl. , 2-Ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl and the like.

Examples of the alkenyl group having 2 to 20 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2 -Heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl, 3-undecenyl, 4-dodecenyl, 3-cyclohexenyl, 2,5-cyclohexadienyl-1-methyl, and 4 , 8,12-Tetradecatorienylallyl and the like. Examples of the alkenyl group having 2 to 10 carbon atoms include vinyl, 2-propenyl, 3-butenyl, 2-butenyl, 4-pentenyl, 3-pentenyl, 2-hexenyl, 3-hexenyl, 5-hexenyl, 2 -Heptenyl, 3-heptenyl, 4-heptenyl, 3-octenyl, 3-nonenyl, 4-decenyl and the like can be mentioned.

The cycloalkyl group having 3 to 20 carbon atoms means a saturated monocyclic or saturated polycyclic alkyl group having 3 to 20 carbon atoms. Examples of the cycloalkyl group having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene, and bicyclo [1. 1.1] Pentanyl, tetradecahydroanthrasenyl and the like can be mentioned. Examples of the cycloalkyl group having 3 to 10 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, adamantyl, decahydronaphthyl, octahydropentalene and bicyclo [1. 1.1] Pentanyl and the like can be mentioned.

The cycloalkylalkyl group having 4 to 20 carbon atoms means a group having 4 to 20 carbon atoms in which the hydrogen atom of the alkyl group is substituted with the cycloalkyl group. Examples of the cycloalkylalkyl group having 4 to 20 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, cyclodecylmethyl, and 2-cyclo. Butylethyl, 2-cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 2-cyclononylethyl, 2-cyclodecylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3- Cyclohexylpropyl, 3-Cycloheptylpropyl, 3-Cyclooctylpropyl, 3-Cyclononylpropyl, 3-Cyclodecylpropyl, 4-Cyclobutylbutyl, 4-Cyclopentylbutyl, 4-Cyclohexylbutyl, 4-Cycloheptylbutyl, 4 -Cyclooctylbutyl, 4-cyclononylbutyl, 4-cyclodecylbutyl, 3-3-adamantylpropyl, decahydronaphthylpropyl and the like can be mentioned. Examples of the cycloalkylalkyl group having 4 to 10 carbon atoms include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, cyclononylmethyl, 2-cyclobutylethyl, and 2 -Cyclopentylethyl, 2-cyclohexylethyl, 2-cycloheptylethyl, 2-cyclooctylethyl, 3-cyclobutylpropyl, 3-cyclopentylpropyl, 3-cyclohexylpropyl, 3-cycloheptylpropyl, 4-cyclobutylbutyl, 4 -Cyclopentylbutyl, 4-cyclohexylbutyl and the like can be mentioned.

Examples of the aryl group having 6 to 20 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthryl, phenanthrenyl and the like, and the alkyl group, the alkenyl group, the carboxyl group, the halogen atom and the like. Examples thereof include 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl, 2,4,6-trimethylphenyl and the like, which have been substituted above, such as phenyl, biphenylyl, naphthyl and anthryl. Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl and naphthyl, and phenyl substituted with one or more of the above alkyl group, the above alkenyl group, the carboxyl group, the halogen atom and the like. , Biphenylyl, naphthyl, anthryl and the like, and specific examples thereof include 4-chlorophenyl, 4-carboxyphenyl, 4-vinylphenyl, 4-methylphenyl and 2,4,6-trimethylphenyl.

The arylalkyl group having 7 to 20 carbon atoms means a group having 7 to 20 carbon atoms in which the hydrogen atom of the alkyl group is replaced with an aryl group. For example, benzyl, α-methylbenzyl, α, α-dimethylbenzyl, phenylethyl, naphthylpropyl and the like can be mentioned. The arylalkyl group having 7 to 10 carbon atoms means a group having 7 to 10 carbon atoms in which the hydrogen atom of the alkyl group is replaced with an aryl group, and examples thereof include benzyl and α-methylbenzyl. Examples thereof include α, α-dimethylbenzyl and phenylethyl.

As used herein, the halogen atom means fluorine, chlorine, bromine or iodine.

The group having 2 to 20 carbon atoms containing the heterocycle represented by ^R2 in the above general formula (I) is not particularly limited, but for example, pyrrolyl, pyridyl, pyridylethyl, pyrimidyl, and the like. Pyridadil, piperazil, piperidil, pyranyl, pyranylethyl, pyrazolyl, triazil, triazilmethyl, pyrrolidyl, quinolyl, isocyanate, imidazolyl, benzoimidazolyl, triazolyl, furyl, furanyl, benzofuranyl, thienyl, thiophenyl, benzothiophenyl, thiadiazolyl, thiazolyl, benzothiazol. Oxazolidine, benzoxazolidine, isocyanazolidine, isooxazolyl, isocyanurate, indrill, morpholinyl, thiomorpholinyl, 2-pyrrolidinone-1-yl, 2-piperidone-1-yl, 2,4-dioxyimidazolidine-3- Examples thereof include yl and 2,4-dioxyoxazolidine-3-yl, and specific examples thereof include groups having the following structures including substituents and the like.

（上記式中、Ｒは、それぞれ独立に、水素原子又は炭素原子数１～６のアルキル基を表し、Ｚは直接結合又は炭素原子数１～６のアルキレン基を表し、＊は結合手を意味する。）

(In the above formula, R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, Z represents a direct bond or an alkylene group having 1 to 6 carbon atoms, and * means a bond. do.)

Examples of the alkyl group having 1 to 6 carbon atoms represented by R in the above formula include those having 1 to 6 carbon atoms among those exemplified as the above-mentioned alkyl group having 1 to 20 carbon atoms. can.

Examples of the alkylene group having 1 to 6 carbon atoms represented by Z in the above formula include methylene, ethylene, propylene, butylene, pentylene and hexylene.

As the hydrocarbon group having 1 to 20 carbon atoms represented by Z ¹ in the general formula (I), one hydrogen atom is removed from the hydrocarbon group having 1 to 20 carbon atoms represented by R ² above. The separated divalent groups can be mentioned.

The 2 to 20 carbon atoms containing the heterocycle represented by Z ¹ in the general formula (I) include hydrogen atoms from 2 to 20 carbon atoms containing the heterocycle represented by ^R2 . There is a divalent group in which one is eliminated.

The blocked isocyanate compound (A) represented by the general formula (II) is preferable because it increases the sensitivity of the polymerizable composition. Further, the blocked isocyanate compound (A) having a group represented by the general formula (III), particularly the blocked isocyanate in which X2 in the general formula ( ^II ) is a group represented by the general formula (III). The compound (A) is preferable because the obtained polymerizable composition has good adhesion to the substrate.

As the hydrocarbon group having 1 to 20 carbon atoms represented by X ¹ and X ³ in the general formula (II), the same hydrocarbon group having 1 to 20 carbon atoms represented by Z ¹ is used. Can be mentioned.

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by ^R4 in the general formula (II) include the same hydrocarbon groups having 1 to 20 carbon atoms represented by ^R2 .

As the hydrocarbon group having 1 to 20 carbon atoms represented by X2 in the general formula ( ^II ), hydrogen atoms are 3 to 13 from the hydrocarbon group having 1 to 20 carbon atoms represented by ^R2 . Examples thereof include groups of 3 to 13 valences that have been desorbed.

The 2 to 20 carbon atoms containing the heterocycle represented by X2 in the general formula (II) include hydrogen atoms from ² to 20 carbon atoms containing the heterocycle represented by ^R2 . There are 3 to 13 valent groups desorbed from 3 to 13.

The blocked isocyanate compound (A) having 2 or more a in the general formula (II) is preferable because it has good adhesion to the substrate, and the one having 3 a is particularly preferable.

The blocked isocyanate compound (A) having a c of 2 or more in the general formula (II) is preferable because the sensitivity of the polymerizable composition increases when it is added to the polymerizable composition.

In the polymerizable composition of the present invention, the content of the blocked isocyanate compound (A) is 0.1 to 5.0% by mass, particularly 0.1 to 1.0% by mass in the polymerizable composition of the present invention. Is preferable.

<Polymerizable compound (B)>
The polymerizable composition of the present invention contains the polymerizable compound (B).
As the polymerizable compound (B), a photocurable resin and / or a thermosetting resin can be used (however, the above-mentioned blocked isocyanate silane compound (A) is excluded).
Examples of the photocurable resin include a polymer of an acrylic acid ester; a product obtained by reacting an epoxy resin with an unsaturated monobasic acid; a reaction product of an epoxy resin and an unsaturated monobasic acid, and a polybasic acid anhydride. A polyimide resin having at least one structural unit having an imide molecular chain consisting of tetracarboxylic acid dianhydride and diamine and a carboxyl group side chain; a polybasic acid anhydride on the hydroxyl group of an epoxy vinyl ester resin. Examples thereof include an acid pendant type epoxy vinyl ester resin having a structure obtained by reacting with.
Examples of the thermosetting resin include phenol resin, urea resin, melamine resin, epoxy resin, unsaturated polyester resin, benzoguanamine derivative, isocyanate compound, blocked isocyanate compound, maleimide compound, benzoxazine compound, oxazoline compound, carbodiimide compound and cyclocarbonate compound. , Polyfunctional oxetane compounds, episulfide resins and the like.

Examples of the acrylic acid ester include (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) glycidyl acrylate, (meth) methyl acrylate, and (meth) butyl acrylate. (Meta) Isobutyl acrylate, (Meta)
-T-butyl acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, isononyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate , (Meta) methoxyethyl acrylate, (meth) dimethylaminomethyl acrylate, (meth) dimethylaminoethyl acrylate, (meth) aminopropyl acrylate, (meth) dimethylaminopropyl acrylate, ethoxy (meth) acrylate Ethyl, poly (ethoxy) ethyl (meth) acrylate, butoxyethoxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate, tetrahydrofuryl (meth) acrylate, (meth) acrylic acid Vinyl, allyl (meth) acrylate, benzyl (meth) acrylate, 4- (2-oxylanylmethoxy) butyl-2-propenate, 7-oxabicyclo [4.1.0] hepto-3-yl -2-Propenic acid ester, 7-oxabicyclo [4.1.0] hept-3-yl-2-propenic acid ester, 7-oxabicyclo [4.1.0] hept-3-ylmethyl-2-propene Acid ester, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,4-butanediol di (Meta) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylol ethanetri (meth) acrylate, trimethylol propanetri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) ) Acrylic, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, tricyclodecanedimethylol di (meth) acrylate, tri [(meth) acryloylethyl] isocyanurate, polyester (meth) acrylate oligomer, etc. Be done.

As the polymerizable compound (B), a commercially available product can also be used, for example, Kayarad DPHA, DPEA-12, PEG400DA, THE-330, RP-1040, NPGDA, PET30, R-684 (above, Nippon Kayaku Co., Ltd.). (Made); Aronix M-215, M-350 (above, manufactured by Toagosei); NK ester A-DPH, A-TMPT, A-DCP, A-HD-N, TMPT, DCP, NPG and HD-N (above) , Shin-Nakamura Chemical Industry Co., Ltd.); SPC-1000, SPC-3000 (all manufactured by Showa Denko); WR-301 (manufactured by ADEKA), V259ME (Nippon Kayaku Sumikin Chemical Co., Ltd.) and the like.

Examples of the epoxy resin include phenol and / or cresol novolac epoxy resin, polyphenylmethane type epoxy resin having a polyfunctional epoxy group, and an epoxy compound represented by the above general formula (IV).

In the present invention, the epoxy compound represented by the general formula (IV); the unsaturated compound having a structure obtained by esterifying the epoxy compound represented by the general formula (IV) and the unsaturated monobasic acid; and / Or an unsaturated compound having a structure in which an epoxy compound represented by the above general formula (IV) and an unsaturated monobasic acid are esterified, and an unsaturated compound having a structure in which a polybasic acid anhydride is further esterified. When the compound is used as the polymerizable compound (B), a cured product having high heat resistance can be obtained, which is preferable.

The hydrocarbon group having 1 to 20 carbon atoms represented by M in the general formula (IV) is the same as the hydrocarbon group having ¹ to 20 carbon atoms represented by Z1.

As the hydrocarbon group having 1 to 20 carbon atoms represented by R ¹¹ to R ¹⁸ and R ²¹ to R ⁵⁰ in the general formula (IV), the hydrocarbon having 1 to 20 carbon atoms represented by R ² is described above. The same group as the hydrogen group can be mentioned.

As the 2 to 20 carbon atoms containing the heterocycle represented by R ²² to R ⁵⁰ in the general formula (IV), the number of carbon atoms containing the hetero ring represented by R ² is 2 to 20. The same group as.

R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁴ and R ²⁵ , R ²⁵ and R ²⁶ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , in the above general formula (IV). R ³⁵ and R ³⁶ , R ³⁶ and R ³⁷ , R ³⁷ and R ³⁸ , R ⁴³ and R ⁴⁴ , R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁷ and R ⁴⁸ , R ⁴⁸ and R ⁴⁹ and R ⁴⁹ . Examples of the ring formed by the combination of R50 and ^R50 include 5 to 7 members such as cyclopentane, cyclohexane, cyclopentene, benzene, pyrrolidine, pyrrol, piperazine, morpholine, thiomorpholine, tetrahydropyridine, lactone ring and lactam ring. Examples thereof include a ring and a fused ring such as naphthalene and anthracene.

The unsaturated monobasic acid means an acid having an unsaturated bond in its structure and having one hydrogen atom per molecule that can be ionized into a hydrogen ion. Examples of unsaturated monobasic acids include acrylic acid, methacrylic acid, crotonic acid, lauric acid, sorbic acid, hydroxyethyl methacrylate malate, hydroxyethyl acrylate malate, hydroxypropyl methacrylate malate, hydroxypropyl acrylate malate, and di. Cyclopentadiene malate and the like can be mentioned.

The polybasic acid anhydride means a polybasic acid anhydride having a plurality of hydrogen atoms that can be ionized into hydrogen ions per molecule. Examples of polybasic acid anhydrides include biphenyltetracarboxylic dianhydride, tetrahydrophthalic anhydride, succinic anhydride, biphthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, 2,2'. -3,3'-Benzophenone tetracarboxylic acid anhydride, ethylene glycol bisamhydrotrimeritate, glycerol trisanhydrotrimeritate, hexahydroanhydride phthalic acid, methyltetrahydroanhydride phthalic acid, nagic acid anhydride, methylnagic acid anhydride , Trialkyltetrahydroanhydride, hexahydroanhydride, 5- (2,5-dioxotetrahydrofuryl) -3-methyl-3-cyclohexene-1,2-dicarboxylic acid anhydride, trialkyltetrahydroanhydride -Maleic anhydride adduct, dodecenyl anhydride succinic acid, methyl hymic anhydride and the like can be mentioned.

The reaction molar ratios of the epoxy resin, the unsaturated monobasic acid and the polybasic acid anhydride are preferably as follows.
That is, in an epoxy adduct having a structure in which 0.1 to 1.0 carboxyl groups of the unsaturated monobasic acid are added to one epoxy group of the epoxy resin, the hydroxyl group 1 of the epoxy adduct 1 is added. It is preferable that the ratio of the acid anhydride structure of the polybasic acid anhydride is 0.1 to 1.0 with respect to the number of pieces.
The reaction of the epoxy resin, the unsaturated monobasic acid and the polybasic acid anhydride can be carried out according to a conventional method.

In the present invention, a monofunctional epoxy compound or a polyfunctional epoxy compound can be used together with the photocurable resin and / or the thermosetting resin.

Examples of the monofunctional epoxy compound include glycidyl methacrylate, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, pentyl glycidyl ether, hexyl glycidyl ether, and heptyl. Glycyzyl ether, octyl glycidyl ether, nonyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, pentadecyl glycidyl ether, hexadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, Allyl glycidyl ether, propargyl glycidyl ether, p-methoxyethyl glycidyl ether, phenyl glycidyl ether, p-methoxy glycidyl ether, p-butylphenol glycidyl ether, cresyl glycidyl ether, 2-methyl cresyl glycidyl ether, 4-nonylphenyl glycidyl ether , Benzyl glycidyl ether, p-cumylphenyl glycidyl ether, trityl glycidyl ether, 2,3-epoxypropyl methacrylate, epoxidized soybean oil, epoxidized linseed oil, glycidyl butyrate, vinylcyclohexane monooxide, 1,2-epoxy- Examples thereof include 4-vinylcyclohexane, styrene oxide, pinene oxide, methylstyrene oxide, cyclohexene oxide, propylene oxide, 7-oxabicyclo [4.1.0] hept-3-yl-2-propenic acid ester and the like.

As the polyfunctional epoxy compound, it is preferable to use one or more compounds selected from the group consisting of bisphenol type epoxy compounds and glycidyl ethers, because a polymerizable composition having better properties can be obtained.
As the bisphenol type epoxy compound, a bisphenol type epoxy compound such as a hydrogenated bisphenol type epoxy compound can also be used.
Examples of the glycidyl ethers include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and 1,8-octanediol diglycidyl ether. 1,10-decanediol diglycidyl ether, 2,2-dimethyl-1,3-propanediol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, hexaethylene glycol diglycidyl Ether, 1,4-cyclohexanedimethanol diglycidyl ether, 1,1,1-tri (glycidyloxymethyl) propane, 1,1,1-tri (glycidyloxymethyl) ethane, 1,1,1-tri (glycidyl) Oxymethyl) methane, 1,1,1,1-tetra (glycidyloxymethyl) methane and the like can be used.
In addition, novolak type epoxy compounds such as phenol novolac type epoxy compound, biphenyl novolac type epoxy compound, cresol novolak type epoxy compound, bisphenol A novolak type epoxy compound, dicyclopentadiene novolac type epoxy compound; 3,4-epoxy-6-methyl. Alicyclic epoxy such as cyclohexylmethyl-3,4-epoxy-6-methylcyclohexanecarboxylate, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 1-epoxyethyl-3,4-epoxycyclohexane Compounds; glycidyl esters such as phthalic acid diglycidyl ester, tetrahydrophthalic acid diglycidyl ester, dimer acid glycidyl ester; glycidyl amines such as tetraglycidyl diaminodiphenylmethane, triglycidyl P-aminophenol, N, N-diglycidyl aniline; Heterocyclic epoxy compounds such as 1,3-diglycidyl-5,5-dimethylhydantoin and triglycidyl isocyanurate; dioxide compounds such as dicyclopentadienedioxide; naphthalene type epoxy compounds; triphenylmethane type epoxy compounds; dicyclopentadiene A type epoxy compound or the like can also be used.

When a photocurable resin is used as the polymerizable compound (B), it is preferable to use a (meth) acrylic acid ester polymer or an epoxy acrylate resin. When a thermosetting resin is used as the polymerizable compound (B), it is preferable to use a phenol novolac type epoxy resin.

In the polymerizable composition of the present invention, the content of the polymerizable compound (B) is preferably 5 to 90% by mass, particularly preferably 10 to 70% by mass in the polymerizable composition of the present invention.

<Polymer initiator (C)>
The polymerizable composition of the present invention contains a polymerization initiator (C).
Examples of the polymerization initiator (C) used in the polymerizable composition of the present invention include a radical polymerization initiator and a cationic polymerization initiator. As the radical polymerization initiator, a photoradical polymerization initiator that generates radicals by light irradiation or a thermal radical polymerization initiator that generates radicals by heating can be used, and conventionally known compounds can be used without particular limitation. It is possible. As the photoradical polymerization initiator, for example, a ketone compound such as an acetophenone compound, a benzyl compound, a benzophenone compound, a thioxanthone compound, an oxime ester compound and the like can be exemplified as preferable ones.

Examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 4'-isopropyl-2-hydroxy-2-methylpropiophenone, and 2-hydroxymethyl-2. -Methylpropiophenone, 2,2-dimethoxy-1,2-diphenylethane-1-one, p-dimethylaminoacetophenone, p-tershaributyldichloroacetophenone, p-tershaributyltrichloroacetophenone, p-azidobenzal Acetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanol-1, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -Butanone-1, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin-n-butyl ether, benzoin isobutyl ether, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2- Examples thereof include methyl-1-propane-1-one.

Examples of the benzyl compound include benzyl and the like.

Examples of the benzophenone compound include benzophenone, methyl o-benzoylbenzoate, Michler ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, 4-benzoyl-4'-methyldiphenylsulfide and the like. ..

Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-isopropylthioxanthone, 2,4-diethylthioxanthone and the like.

Examples of the oxime ester compound include compounds having a group represented by the above general formula (V). When a compound having a group represented by the above general formula (V) is used as the polymerization initiator (C), the sensitivity of the polymerizable composition is increased, which is preferable.

As the hydrocarbon group having 1 to 20 carbon atoms represented by R ⁶¹ to R ⁶³ in the general formula (V), the same group as the hydrocarbon group having 1 to 20 carbon atoms represented by R ² is used. Can be mentioned.

As the 2 to 20 carbon atoms containing the heterocycle represented by R ⁶¹ to R ⁶² in the general formula (V), the number of carbon atoms containing the hetero ring represented by R ² is 2 to 20. The same group as.

As the oxime ester compound, a compound represented by the following general formula (VI) is particularly suitable.
It is preferable from the viewpoint of sensitivity and heat resistance.

(In the formula, R ⁷¹ and R ⁷² each independently represent a hydrogen atom, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or 2 to 20 carbon atoms containing a heterocycle.
R ⁷³ and R ⁷⁴ are independently halogen atoms, nitro groups, cyano groups, hydroxyl groups, carboxyl groups, R ⁷⁵ , OR ⁷⁶ , SR ⁷⁷ , NR ⁷⁸ R ⁷⁹ , COR ⁸⁰ , SOR ⁸¹ , SO ₂ R ⁸² or Represents CONR ⁸³ R ⁸⁴
R ⁷⁵ to R ⁸⁴ independently represent hydrocarbon groups having 1 to 20 carbon atoms or 2 to 20 carbon atoms containing a heterocycle.
R ⁸³ and R ⁸⁴ may be coupled to each other to form a ring.
X ²¹ represents an oxygen atom, a sulfur atom, a selenium atom, CR ⁸⁵ R ⁸⁶ , CO, NR ⁸⁷ or PR ⁸⁸ .
X ²² represents a single bond or CO
R ⁸⁵ to R ⁸⁸ represent hydrocarbon groups having 1 to 20 carbon atoms.
One or more of the hydrogen atoms in the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms and 2 to 20 carbon atoms containing a heterocycle are halogen atoms, nitro groups, cyano groups, hydroxyl groups, and carboxyl groups. Alternatively, it may be substituted with a heterocyclic group, and one or more of the hydrocarbon groups having 1 to 20 carbon atoms and the methylene group having 2 to 20 carbon atoms containing the heterocycle are converted to -O-. May have been replaced,
R ⁷³ and R ⁷⁴ may independently form a ring together with an adjacent benzene ring.
j represents an integer from 0 to 4 and represents
k represents an integer from 0 to 5. )

As the hydrocarbon group having 1 to 20 carbon atoms represented by R ⁷¹ to R ⁷² and R ⁷⁵ to R ⁸⁸ in the general formula (VI), the hydrocarbon having 1 to 20 carbon atoms represented by R ² is described above. The same group as the hydrogen group can be mentioned.

The carbon having 2 to 20 carbon atoms containing the heterocycle represented by R ⁷¹ to R ⁷² and R ⁷⁵ to R ⁸⁴ in the general formula (VI) is the carbon containing the heterocycle represented by ^R2 . The same feeling as 2 to 20 atoms can be mentioned.

Examples of the ring formed by R ⁷³ and R ⁷⁴ together with the adjacent benzene ring include carbazole, fluorene, dibenzofuran, dibenzothiophene, phenotylazine, thioxanthone, xanthene, thioxanthene and dihydroacridine.

Preferred polymerization initiators include, for example, Compound No. 1 shown below. C1-No. Examples of the compound represented by the above general formula (VI) include C17, for example, the compound No. 1 shown below. C1 and No. C3 to No. C16 can be mentioned. However, the present invention is not limited by the following compounds.

Other radical polymerization initiators include phosphine oxide compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide and bis (cyclopentadienyl) -bis [2,6-difluoro-3- (pill-1). -Il)] Titanocene compounds such as titanium can be mentioned.

Examples of commercially available radical polymerization initiators include ADEKA PTOMER N-1414, N-1717, N-1919, ADEKA ARCLUS NCI-831, NCI-930 (all manufactured by ADEKA); IRGACURE184, IRGACURE369, IRGACURE651, IRGACURE907, IRGACURE. OXE 01, IRGACURE OXE 02, IRGACURE784 (above, manufactured by BASF); TR-PBG-304, TR-PBG-305, TR-PBG-309 and TR-PBG-314 (above, manufactured by Trony); and the like.

As the radical polymerization initiator, one type may be used alone or two or more types may be used in combination depending on the desired performance.

Examples of the thermal radical polymerization initiator include 2,2'-azobisisobutyronitrile, 2,2'-azobis (methylisobutyrate), 2,2'-azobis-2,4-dimethylvaleronitrile, 1, Azo-based initiators such as 1'-azobis (1-acetoxy-1-phenylethane); benzoyl peroxide, di-t-butylbenzoyl peroxide, t-butylperoxypivalate, di (4-t-butylcyclohexyl). ) Examples thereof include peroxide-based initiators such as peroxydicarbonate, persulfates such as ammonium persulfate, sodium persulfate, and potassium persulfate.

As the cationic polymerization initiator, any compound that can release a substance that initiates cationic polymerization by light irradiation or heating may be used, but an onium salt is preferably used.

Examples of the onium salt include salts of cations and anions represented by [M] ^{r +} [G] ^r− .
Here, the cation [M] ^{r +} is preferably onium, and its structure can be expressed by, for example, the following general formula, [(R ²⁹ ) _f Q] ^{r +} .

The R ²⁹ is an organic group having 1 to 60 carbon atoms and may contain any number of atoms other than carbon atoms. f is an integer of 1 to 5. The f R ^29s are independent of each other and may be the same or different. Further, at least one is preferably an organic group as described above having an aromatic ring. Q is an atom or atomic group selected from the group consisting of S, N, Se, Te, P, As, Sb, Bi, O, I, Br, Cl, F and N = N. Further, when the valence of Q in the cation [M] ^{r +} is q, it is necessary that the relationship r = f−q is established (however, N = N is treated as having a valence of 0).

Specific examples of the anion [G] ^r- include halide ions such as chloride ion, bromide ion, iodide ion, and fluoride ion; perchlorate ion, chlorate ion, and the like. Inorganic anions such as thiocyanate ion, hexafluorophosphate ion, hexafluoroantimonate ion, tetrafluoroborate ion; tetrakis (pentafluorophenyl) borate, tetra (3,5-difluoro-4-methoxyphenyl) borate , Tetrafluoroborate, tetraarylborate, tetrakis (pentafluorophenyl) borate and other borate anions; methanesulphonate ion, dodecylsulphonic acid ion, benzenesulphonic acid ion, toluenessulphonic acid ion, trifluoromethanesulphonic acid ion, naphthalene. Sulfonic acid ion, diphenylamine-4-sulfonic acid ion, 2-amino-4-methyl-5-chlorobenzene sulfonic acid ion, 2-amino-5-nitrobenzene sulfonic acid ion, phthalocyanine sulfonic acid ion, fluorosulfonic acid ion, trinitrobenzene Sulfonic acid anion, camphor sulfonic acid ion, nonafluorobutane sulfonic acid ion, hexadecafluorooctane sulfonic acid ion, sulfonic acid ion having a polymerizable substituent, JP-A-10-235999, JP-A-10-337959, JP-A-11. -102088, JP-A-2000-108510, JP-A-2000-168223, JP-A-2001-20969, JP-A-2001-322354, JP-A-2006-248180, JP-A-2006-297907, JP-A-8-253705, JP-A-2004. Organic sulfonic acid-based anions such as sulfonic acid ions described in JP-A-503379, JP-A-2005-336150, International Publication No. 2006/2806, etc .; octyl phosphate ion, dodecyl phosphate ion, octadecyl phosphate ion. , Phenylphosphate ion, Nonylphenylphosphate ion, Organic phosphate-based anions such as 2,2'-methylenebis (4,6-di-t-butylphenyl) phosphonate ion, Bistrifluoromethylsulfonylimide ion, Bis Perfluorobutane sulfonylimide ion, perfluoro-4-ethylcyclohexanesulfonic acid ion, tetrakis (pentafluorophenyl) borate ion, tris (fluoroalkylsulfonyl) carboanion and the like are bivalent. Examples thereof include benzenedisulfonic acid ion, naphthalene disulfonic acid ion and the like.

In the present invention, among such onium salts, it is particularly effective to use aromatic onium salts such as aryldiazonium salts, diallyliodonium salts and triarylsulfonium salts. From these, one of them can be used alone, or two or more of them can be mixed and used.

Other preferable ones are (η ^5-2,4 -cyclopentadiene-1-yl) [(1,2,3,4,5,6-η)-(1-methylethyl) benzene] -iron. -Iron-arene complex such as hexafluorophosphate, aluminum complex such as tris (acetylacetonato) aluminum, tris (ethylacetonatoacetato) aluminum, tris (salitylaldehidato) aluminum, and silanols such as triphenylsilanol. A mixture of the above can also be mentioned.

Among these, it is preferable to use an aromatic sulfonium salt from the viewpoint of practical use and photosensitivity.
As the aromatic sulfonium salt, commercially available ones can also be used, for example, WPAG-336, WPAG-376, WPAG-370, WPAG-469, WPAG-638 (manufactured by Wako Pure Chemical Industries, Ltd.), CPI-100P. , CPI-101A, CPI-200K, CPI-210S (manufactured by San-Apro), ADEKA OPTMER SP-506, ADEKA PTMER SP-066, ADEKA PTMER SP-130, ADEKA PTMER SP-140, ADEKA OPTMER SP. -082, ADEKA PTOMER SP-103, ADEKA PTOMER SP-601, ADEKA PTOMER SP-606, ADEKA PTOMER SP-701 (manufactured by ADEKA) and the like.

In the polymerizable composition of the present invention, the content of the polymerization initiator (C) is 0.1 to 30% by mass, particularly 0.5 to 10% by mass, based on the solid content of the polymerizable composition of the present invention. preferable. If the content of the polymerization initiator is less than 0.1% by mass, curing by exposure may be insufficient, and if it is more than 30% by mass, the initiator may precipitate in the resin composition.

Further, when the polymerizable composition of the present invention contains a photoradical polymerization initiator or a photocationic polymerization initiator as the polymerization initiator (C), it is used as a light source of active light used when curing the polymerizable composition. Can be used to emit light having a wavelength of 300 to 450 nm. Specifically, as the light source, for example, ultra-high pressure mercury, mercury vapor arc, carbon arc, xenon arc and the like can be used.

The polymerizable composition of the present invention may further contain a colorant (D).
Examples of the colorant (D) include pigments, dyes, natural pigments and the like.

Examples of the pigment include nitroso compounds; nitro compounds; azo compounds; diazo compounds; xanthene compounds; quinoline compounds; anthraquinone compounds; coumarin compounds; phthalocyanine compounds; isoindolinone compounds; isoindolin compounds; quinacridone compounds; antanthrone compounds; perinone. Compounds; Perylene compounds; Diketopyrrolopyrrole compounds; Thioindigo compounds; Dioxazine compounds; Triphenylmethane compounds; Kinophthalone compounds; Naphthalenetetracarboxylic acids; Azo dyes, cyanine dye metal complex compounds; Lake pigments; Furness method, channel method or thermal Carbon black obtained by the method, or carbon black such as acetylene black, ketjen black, or lamp black; the above carbon black adjusted or coated with an epoxy resin, the above carbon black is previously dispersed with a resin in a solvent, and 20 A compound adsorbed with a resin of up to 200 mg / g, an acidic or alkaline surface-treated carbon black, a compound having an average particle size of 8 nm or more and a DBP oil absorption of 90 ml / 100 g or less, CO in a volatile content at 950 ° C. And the total amount of oxygen calculated from CO ₂ is 9 mg or more per 100 m ² of the surface area of carbon black; graphite, graphitized carbon black, perylene black, lactam black, activated carbon, carbon fiber, carbon nanotube, carbon microcoil, carbon. Nanohorn, carbon aerogel, fullerene; black pigments such as aniline black, pigment black 7 and titanium black; chromium oxide green, miloli blue, cobalt green, cobalt blue, manganese, ferrocyanide, phosphate ultramarine, navy blue, ultramarine, Organic or inorganic pigments such as cerulean blue, pyridian, emerald green, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, synthetic iron black, amber, and extender pigment can be used. These pigments can be used alone or in combination of two or more.

As the above pigment, a commercially available pigment may be used, for example, Pigment Red 1, 2, 3, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48, 49, 88, 90, 97, 112, 119, 122, 123, 144, 149, 166, 168, 169, 170, 171, 177, 179, 180, 184, 185, 192, 200, 202, 209, 215, 216, 217, 220, 223, 224, 226, 227, 228, 240, 254; Pigment Orange 13, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 65, 71; Pigment Yellow 1, 3, 12, 13, 14, 16, 17, 20, 24, 55, 60, 73, 81, 83, 86, 93, 95, 97, 98, 100, 109, 110, 113, 114, 117, 120, 125, 126, 127, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 166, 168, 175, 180, 185; Pigment Green 7, 10, 36; Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 5, 15: 6, 22, 24, 56, 60, 61, 62, 64; Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 50 and the like can be mentioned.

Examples of the above dyes include azo dyes, anthraquinone dyes, indigoid dyes, triarylmethane dyes, xanthene dyes, alizarin dyes, aclysine dyes, stillben dyes, thiazole dyes, naphthol dyes, quinoline dyes, nitro dyes, indamine dyes, oxadin dyes, and phthalocyanine dyes. , Dyes such as cyanine dyes and the like, and these may be used in combination of a plurality.

In the polymerizable composition of the present invention, the content of the colorant (D) is preferably 0.01 to 10 parts by mass, more preferably 0.1 to 100 parts by mass with respect to 100 parts by mass of the polymerizable compound (B). 5 parts by mass.

<Filler>
The polymerizable composition of the present invention may contain a filler. As the filler, an inorganic filler or an organic filler can be used. As the inorganic filler, those usually blended in a sealing material such as a silicone resin composition and an epoxy resin composition can be used. For example, silicas such as fused silica, fused spherical silica, crystalline silica, colloidal silica, fumed silica, silica gel; metal oxides such as alumina, iron oxide and antimony trioxide; silicon nitride, aluminum nitride, boron nitride, carbonized. Ceramics such as silicon; Minerals such as mica and montmorillonite; Metal hydroxides such as aluminum hydroxide and magnesium hydroxide or those modified by organic modification treatment; Calcium carbonate, calcium silicate, magnesium carbonate, barium carbonate Metal carbonates such as or modified by organic modification treatment; pigments such as metal borate and carbon black; carbon fibers, graphite, whisker, kaolin, talc, glass fibers, glass beads, glass microspheres, etc. Examples thereof include silica glass, layered clay minerals, clay, silicon carbide, quartz, aluminum and zinc. Examples of the organic filler include acrylic beads, polymer fine particles, transparent resin beads, wood flour, pulp, cotton chips and the like.

Among the fillers, silicas, metal oxides and metal acid salts are preferable, and crystalline silica, talc, barium sulfate and titanium oxide are particularly preferable.

In the polymerizable composition of the present invention, the content of the filler is preferably 5 to 500 parts by mass, particularly 5 to 200 parts by mass with respect to 100 parts by mass of the polymerizable compound (B).

A solvent can be further added to the polymerizable composition of the present invention. As the solvent, usually, a solvent capable of dissolving or dispersing each of the above components ((polymerizable compound (B), polymerization initiator (C), etc.), etc.), for example, methyl ethyl ketone, methyl amyl ketone, diethyl, etc. Ketones such as ketones, acetone, methylisopropyl ketones, methylisobutylketones, cyclohexanones, 2-heptanones; ethyl ethers, dioxane, tetrahydrofurans, 1,2-dimethoxyethanes, 1,2-diethoxyethanes, dipropylene glycol dimethyl ethers and the like. Ether solvent; ester solvent such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, cyclohexyl acetate, ethyl lactate, dimethyl succinate, texanol; ethylene glycol monomethyl ether, ethylene glycol monoethyl Cellosolve-based solvents such as ether; alcohol-based solvents such as methanol, ethanol, iso- or n-propanol, iso-or n-butanol, amyl alcohol; ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol-1 -Ether ester solvents such as monomethyl ether-2-acetate, dipropylene glycol monomethyl ether acetate, 3-methoxybutyl ether acetate, ethoxyethyl ether propionate; BTX solvents such as benzene, toluene and xylene; hexane, heptane, octane , Cyclohexane and other aliphatic hydrocarbon solvents; Telepin oil, D-limonen, Pinen and other terpene-based hydrocarbon oils; Mineral Spirit, Swazole # 310 (Cosmo Matsuyama Petroleum Co., Ltd.), Solbesso # 100 (Exxon Chemical Co., Ltd.), etc. Paraffin-based solvent; Halogened aliphatic hydrocarbon-based solvent such as carbon tetrachloride, chloroform, trichloroethylene, methylene chloride, 1,2-dichloroethane; Halogenized aromatic hydrocarbon-based solvent such as chlorobenzene; Carbitol-based solvent; Aniline; Triethylamine; pyridine; acetic acid; acetonitrile; carbon disulfide; N, N-dimethylformamide; N, N-dimethylacetamide; N-methylpyrrolidone; dimethylsulfoxide; water, etc., and these solvents may be one or more. Can be used as a mixed solvent of.
Among these, ketones, ether ester solvents and the like, particularly propylene glycol-1-monomethyl ether-2-acetate, cyclohexanone and the like are preferable because they have good compatibility between the resist and the polymerization initiator in the photosensitive composition.

Further, in the polymerizable composition of the present invention, if necessary, a light / thermoacid generator; a thermosetting catalyst; a thermal polymerization inhibitor such as p-anisole, hydroquinone, pyrocatechol, t-butylcatechol, phenothiazine; Plasticizers; Adhesive promoters; Antifoaming agents; Leveling agents; Surface conditioners; Antioxidants; UV absorbers; Dispersants; Dispersing aids; Antiaggregating agents; Catalysts; Potential curing agents; Curing accelerators; Adhesion promotion Conventional additives such as agents; cross-linking agents; thickeners can be added.

In the polymerizable composition of the present invention, the amount of any component other than the blocked isocyanate silane compound (A), the polymerizable compound (B), the polymerization initiator (C), the colorant (D), the filler and the solvent is , Is appropriately selected according to the purpose of use, and is not particularly limited, but preferably, the total amount of the blocked isocyanate silane compound (A), the polymerizable compound (B), the polymerization initiator (C), the colorant and the filler is 100% by mass. The total amount is 50 parts by mass or less.

A dispersant that disperses the colorant can be added to the polymerizable composition of the present invention. The dispersant is not limited as long as it can disperse and stabilize a colorant or an inorganic compound, and a commercially available dispersant, for example, BYK series manufactured by Big Chemie, or the like can be used. In particular, a polymer dispersant made of polyester, polyether, or polyurethane having a basic functional group, an amine having a nitrogen atom as a basic functional group, and / or a quaternary salt thereof. Yes, those having an amine value of 1 to 100 mgKOH / g are preferably used.

Further, the polymerizable composition of the present invention can also improve the characteristics of the cured product by using another organic polymer. Examples of the organic polymer include polystyrene, polymethylmethacrylate, methylmethacrylate-ethylacrylate polymer, poly (meth) acrylic acid, styrene- (meth) acrylic acid polymer, and (meth) acrylic acid-methylmethacrylate polymer. , Ethylene-vinyl chloride polymer, ethylene-vinyl polymer, polyvinyl chloride resin, ABS resin, nylon 6, nylon 66, nylon 12, urethane resin, polycarbonate polyvinyl butyral, cellulose ester, polyacrylamide, saturated polyester, phenol resin, Examples thereof include phenoxy resin, polyamideimide resin, polyamic acid resin, and epoxy resin, and among these, polystyrene, (meth) acrylic acid-methylmethacrylate polymer, and epoxy resin are preferable. When another organic polymer is used, the amount used is preferably 10 to 100 parts by mass with respect to 100 parts by mass of the polymerizable compound (B).

The polymerizable composition of the present invention may further contain a chain transfer agent, a sensitizer, a surfactant, another silane coupling agent and the like.

As the chain transfer agent or sensitizer, a sulfur atom-containing compound is generally used. For example, thioglycolic acid, thioapple acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- (2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3-[N-( 2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3-mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mercaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, dodecyl (4-methylthio) phenyl ether, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol, 3-mercapto-2-butanol, mercaptophenol , 2-Mercaptoethylamine, 2-Mercaptoimidazole, 2-Mercaptobenzoimidazole, 2-Mercapto-3-pyridinol, 2-Mercaptobenzothiazole, Mercaptoacetic acid, Trimethylol propanthris (3-mercaptopropionate), Pentaerythritol tetrakis A mercapto compound such as (3-mercaptopropionate), a disulfide compound obtained by oxidizing the mercapto compound, iodoacetic acid, iodopropionic acid, 2-iodoethanol, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid. Iodized alkyl compounds such as, trimethylolpropanetris (3-mercaptoisobutyrate), butanediol bis (3-mercaptoisobutyrate), hexanedithiol, decandithiol, 1,4-dimethylmercaptobenzene, butanediol bisthio. Propionate, Butanediol bisthioglycolate, Ethyleneglycol bisthioglycolate, Trimethylol propanetristhioglycolate, Butanediol bisthiopropionate, Trimethylol propanetristhiopropionate, Trimethylol propanetristhioglycolate , Pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakisthioglycolate, trishydroxyethyl tristhiopropionate, diethylthioxanthone, diisopropylthioxanthone, the following compound No. Examples thereof include aliphatic polyfunctional thiol compounds such as C1, tris (2-hydroxyethyl) trimercaptopropionate, and isocyanurate, and Karenz MT BD1, PE1, and NR1 manufactured by Showa Denko KK.

Examples of the surfactant include fluorosurfactants such as perfluoroalkyl phosphates and perfluoroalkyl carboxylates; anionic surfactants such as higher fatty acid alkali salts, alkyl sulfonates and alkyl sulfates; higher amines. Cationic surfactants such as halides and quaternary ammonium salts; Nonionic surfactants such as polyethylene glycol alkyl ethers, polyethylene glycol fatty acid esters, sorbitan fatty acid esters, fatty acid monoglycerides; Amphoteric surfactants; Silicone surfactants Surfactants such as agents can be used, and these may be used in combination.

As the above-mentioned other silane coupling agent, for example, a silane coupling agent manufactured by Shin-Etsu Chemical Co., Ltd. can be used, among which isocyanate groups, methacryloyl groups or epoxy groups such as KBE-9007, KBM-502 and KBE-403 can be used. A silane coupling agent having the above is preferably used.

The polymerizable composition and cured product of the present invention are a curable paint, a varnish, a curable adhesive, a printed substrate, a display display device (color television, PC monitor, mobile information terminal, digital camera, or the like, and a color display liquid crystal display panel. Color filters, color filters for various display applications, color filters for CCD image sensors, touch panels, electric emission display devices, plasma display panels, black partition walls of organic EL), powder coatings, printing inks, printing plates, adhesives, Gel coats, photo resists for electronic engineering, electroplated resists, etching resists, solder resists, insulating films, black matrices, and resists for forming structures in the manufacturing process of LCDs, compositions for encapsulating electrical and electronic components. , Solder resist, magnetic recording material, micromechanical parts, waveguide, optical switch, plating mask, etching mask, color test system, glass fiber cable coating, screen printing stencil, for manufacturing three-dimensional objects by stereolithography. Materials, holographic recording materials, image recording materials, microelectronic circuits, decolorizing agents, decolorizing agents for image recording materials, decolorizing agents for image recording materials using microcapsules, printed wiring boards It can be used in various applications such as photoresist materials for UV and visible laser direct imaging systems, photoresist materials used for forming dielectric layers in sequential lamination of printed circuit boards, and protective films. The application is not particularly limited, but among the above applications, it can be particularly preferably used for a display display device.

When the polymerizable composition of the present invention is used as the black partition of the organic EL, it is possible to use an alkaline developable compound having a weight average molecular weight of 5000 or more because the pattern shape is verticalized, the developing adhesion is improved, and the heat resistance is improved. It is preferable, and more preferably, an alkali developable compound having a weight average molecular weight of 7,000 to 15,000 is used. Further, the alkali-developable compound is obtained by an esterification reaction between an epoxy-added compound having a structure in which an unsaturated monobasic acid is added to an epoxy compound represented by the above general formula (I) and a polybasic acid anhydride. It is particularly preferable that the unsaturated compound has such a structure.

A method for producing a cured product using the polymerizable composition of the present invention will be described in detail below.

The polymerizable composition of the present invention is a known means such as a spin coater, a roll coater, a bar coater, a die coater, a curtain coater, various types of printing, and dipping, soda glass, quartz glass, a semiconductor substrate, metal, paper, and plastic. It can be applied on a substrate such as. Further, once applied on a substrate such as a film, it can be transferred onto another substrate, and the coating method is not limited.
Further, a coating film of a polymerizable composition is formed on a substrate, the coating film is irradiated with active light through a mask having a predetermined pattern shape, and then the exposed film is a developer (particularly an alkaline developer). It is also possible to perform patterning by a step of developing the film in the above-mentioned manner and heating the film after the development.

When the polymerizable composition of the present invention contains a thermosetting resin as the polymerizable compound (B), the photocurable resin is heat-cured by heating to a temperature of, for example, about 140 to 180 ° C. The carboxyl group of the above reacts with a thermosetting resin such as an epoxy resin to form a cured coating film having excellent various properties. Even if it does not contain a thermosetting resin, the heat treatment improves the coating properties by thermally radically polymerizing the ethylenically unsaturated bonds of the photocurable components that remain unreacted during exposure. Therefore, heat treatment (thermosetting) may be performed depending on the purpose and application.

Further, as the light source of the energy ray used for curing the polymerizable composition of the present invention, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a medium pressure mercury lamp, a low pressure mercury lamp, a mercury steam arc lamp, a xenon arc lamp, etc. High electromagnetic energy, electron beam, X-ray, radiation, etc. with wavelengths of 2000 angstrom to 7000 angstrom obtained from carbon arc lamps, metal halide lamps, fluorescent lamps, tungsten lamps, excimer lamps, germicidal lamps, light emitting diodes, CRT light sources, etc. Although energy rays can be used, preferred examples thereof include ultrahigh pressure mercury lamps, mercury steam arc lamps, carbon arc lamps, xenon arc lamps and the like that emit light having a wavelength of 300 to 450 nm.

Furthermore, the laser direct drawing method, which forms an image directly from digital information of a computer or the like without using a mask by using a laser beam as an exposure light source, improves not only productivity but also resolution and position accuracy. As the laser light, light having a wavelength of 340 to 430 nm is preferably used, but an excimer laser, a nitrogen laser, an argon ion laser, a helium cadmium laser, a helium neon laser, and a krypton ion laser are used. , Various semiconductor lasers, YAG lasers and the like that emit light in the visible to infrared region are also used. When these lasers are used, a sensitizing dye that absorbs the visible to infrared region is added.

The polymerizable composition of the present invention is useful as a photosensitive composition for forming a dry film by applying and drying on a film.

The dry film has a structure in which a carrier film, a solder resist layer, and a peelable cover film used as needed are laminated in this order. The solder resist layer is a layer obtained by applying and drying an alkali-developable polymerizable composition on a carrier film or a cover film. A dry film can be obtained by forming a solder resist layer on a carrier film and then laminating a cover film on the cover film, or by forming a solder resist layer on a cover film and laminating this laminate on a carrier film.

As the carrier film, a thermoplastic film such as a polyester film having a thickness of 2 to 150 μm is used.
The solder resist layer is formed by uniformly applying the polymerizable composition to a carrier film or a cover film with a blade coater, a lip coater, a comma coater, a film coater or the like to a thickness of 5 to 100 μm, and drying the layer.
As the cover film, a polyethylene film, a polypropylene film or the like can be used, but one having a smaller adhesive force with the solder resist layer than the carrier film is preferable.

To make a solder resist film on a printed wiring board using a dry film, the cover film is peeled off, the solder resist layer and the circuit-formed base material are overlapped, and the circuit-formed base material is laminated using a laminator or the like. A solder resist layer is formed on the solder resist layer. A cured coating film can be formed by exposing, developing, and heat-curing the formed solder resist layer in the same manner as described above. The carrier film may be peeled off either before or after exposure.

Hereinafter, the present invention will be described in more detail with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to these Examples and the like.

[Production Example 1] Blocked isocyanate silane compound No. Synthesis of No. 1 In a four-necked flask, the following blocking agent No. After charging 0.1 mol of 1 and adjusting the temperature to 35 ° C., 0.1 mol of 3-isocyanatepropyltriethoxysilane was added dropwise while controlling the temperature so as not to rise above 40 ° C. Then, the mixture was stirred at an internal temperature of 40 ° C. for 1 hour. After confirming that the peak of the isocyanate group disappeared by IR, the following blocked isocyanate silane No. I got 1.

[Production Example 2] Blocked isocyanate silane No. No. 2 synthetic blocking agent No. Except for the fact that pentaerythritol triacrylate was used instead of 1, the same operation as in [Production Example 1] was carried out, and the blocked isocyanate silane No. I got 2.

[Production Example 3] Preparation of Polymerizable Compound B-1PGMEA Solution 184 g of 1,1-bis [4- (2,3-epoxypropyloxy) phenyl] indane, 58 g of acrylic acid, 2,6-di-tert-butyl 0.26 g of -p-cresol, 0.11 g of tetra-n-butylammonium bromide and 105 g of PGMEA were charged and stirred at 120 ° C. for 16 hours. The reaction mixture was cooled to room temperature, 160 g of PGMEA, 59 g of biphthalic anhydride and 0.24 g of tetra-n-butylammonium bromide were added, and the mixture was stirred at 120 ° C. for 4 hours. Further, 20 g of tetrahydrophthalic anhydride was added, and the mixture was stirred at 120 ° C. for 4 hours, 100 ° C. for 3 hours, 80 ° C. for 4 hours, 60 ° C. for 6 hours, and 40 ° C. for 11 hours, and then 128 g of PGMEA was added to obtain a PGMEA solution. The polymerizable compound B-1 was obtained (Mw = 5000, Mn = 2100, acid value (solid content equivalent) 92.7 mgKOH / g).

[Production Example 4] Production of Polymerizable Compound B-2PGMEA Solution 9,9-bis (4-glycidyloxyphenyl) fluorene 75.0 g, acrylic acid 23.8 g, 2,6-di-t-butyl-p-cresol 0.273 g, 0.585 g of tetrabutylammonium chloride, and 65.9 g of PGMEA were charged and stirred at 90 ° C. for 1 hour, 100 ° C. for 1 hour, 110 ° C. for 1 hour and 120 ° C. for 14 hours. After cooling to room temperature, 25.9 g of succinic anhydride, 0.427 g of tetrabutylammonium chloride, and 1.37 g of PGMEA were added, and the mixture was stirred at 100 ° C. for 5 hours. Further, add 30.0 g of 9,9-bis (4-glycidyloxyphenyl) fluorene, 0.269 g of 2,6-di-t-butyl-p-cresol, and 1.50 g of PGMEA at 90 ° C. for 90 minutes. After stirring at 120 ° C. for 4 hours, 122.2 g of PGMEA was added to obtain the desired polymerizable compound B-2 as a PGMEA solution (Mw = 4190, Mn = 2170, acid value (solid content equivalent) 52 mg · KOH). / G)

[Production Example 5] Carbon Black No. Production of No. 1 150 g of MA100 (carbon black manufactured by Mitsubishi Chemical Corporation) and 3000 ml of a peroxo disodium sulfate deionized aqueous solution (concentration 2.0 N) were mixed and stirred at 60 ° C. for 10 hours. After filtration, the obtained slurry was neutralized with sodium hydroxide, treated by diafiltration, and the obtained solid was dried at 75 ° C. overnight to obtain carbon black No. 1 as a black powder. I got 1.

[Production Example 6] Carbon Black Dispersion Liquid No. Production of carbon black No. 1 16 g of 1 and 3.6 g of the polymerizable compound B-1PGMEA solution, 2.4 g of DISPERBYK-161 (manufactured by BIC Chemie, dispersant) and 78 g of PGMEA were weighed and combined, and treated with a bead mill to disperse carbon black. Liquid No. I got 1.

[Examples 1 to 6 and Comparative Examples 1 to 4] Preparation of polymerizable composition Each component is mixed according to the formulation of [Table 1] and [Table 2] to form a polymerizable composition (Examples 1 to 6 and Comparative Example). 1 to 4) were obtained. The numerical values of the formulations in the table represent parts by mass. The reference numerals in the table represent the following components.
A-1: Blocked isocyanate silane compound No. 1
A-2: Blocked isocyanate silane compound No. 2
A-3: KBE-9007 (manufactured by Shinetsu Silicone Co., Ltd.)
A-4: KBM-5103 (manufactured by Shinetsu Silicone Co., Ltd.)
A-5: KBM-503 (manufactured by Shinetsu Silicone Co., Ltd.)
A-6: KBM-403 (manufactured by Shinetsu Silicone Co., Ltd.)
B-1: Polymerizable compound B-1PGMEA solution (solid content 45%)
B-2: Polymerizable compound B-2PGMEA solution (solid content 45%)
B-3: Kayarad DPHA (manufactured by Nippon Kayaku Co., Ltd.)
C-1: Compound No. C9
C-2: Compound No. C15
D-1: Carbon black dispersion liquid No. 1 (solid content 20% PGMEA dispersion)
E-1: PGMEA

The polymerizable compounds prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were evaluated as follows. The evaluation results are also shown in [Table 1] and [Table 2].

<Seal strength>
The above-mentioned polymerizable composition was spin-coated (500 rpm, 10 seconds) on a glass substrate, dried, and then prebaked at 100 ° C. for 100 seconds. After exposure using an ultra-high pressure mercury lamp as a light source, the glass substrate having a resin black matrix layer was obtained by baking at 230 ° C. for 30 minutes. Apply a thermosetting adhesive (seal agent: XN-21S manufactured by Mitsui Kagaku Co., Ltd.) to the glass substrate in an area of 6 mm x 3.5 mm so that the glass substrate with the resin black matrix layer and the black matrix layer serve as the adhesive surface. They were pasted together and the adhesive was cured. The pasted substrate was allowed to stand in a high-temperature and high-humidity device under the conditions of 120 ° C., 2 atm and 100% relative humidity for 5 hours. A three-point support bending test was carried out on this sample with Shimadzu EZ-Graph, and the adhesion strength was measured.

<Go board test>
The above-mentioned polymerizable composition was spin-coated (500 rpm, 10 seconds) on a glass substrate, dried, and then prebaked at 100 ° C. for 100 seconds. After exposure using an ultra-high pressure mercury lamp as a light source, the glass substrate having a resin black matrix layer was obtained by baking at 230 ° C. for 30 minutes. The obtained substrate with the resin black matrix layer was allowed to stand in a high-temperature and high-humidity device at 120 ° C., 2 atm, and a relative humidity of 100% for 5 hours. According to JIS K5600-5-6, 100 1 mm ² squares were prepared on the black layer with a cutter. A polyimide tape was attached on it, and the black layer was observed to have a peeling ratio. Those that did not come off at all were marked with ○, those that were partially peeled off were marked with △, and those that were completely peeled off were marked with ×.

<Storage stability>
The above polymerizable composition was filled in a screw tube bottle and allowed to stand at 40 ° C. for 3 days. The viscosity of the resist solution after standing was measured, and if the change in viscosity was within 5%, it was evaluated as ◯, and if the change in viscosity was 5% or more, it was evaluated as x.

<OD value>
The above-mentioned polymerizable composition was spin-coated (500 rpm, 10 seconds) on a substrate, dried, and then prebaked at 100 ° C. for 100 seconds. After exposure using an ultra-high pressure mercury lamp as a light source, a cured product was prepared by baking at 230 ° C. for 30 minutes. The OD value of the obtained membrane was measured using a Macbeth permeation densitometer, and the OD value was divided by the thickness after post-baking to calculate the OD value per 1 μm.
A cured product having an OD value of 3.5 or more per μm can be used as a black matrix, and a cured product having an OD value of 4.0 or more per thickness can be preferably used as a black matrix.

<Sensitivity>
(sensitivity)
Using a photomask with a mask opening of 6 μm, development was performed at intervals of 10 mJ / cm with an exposure amount of 10 mJ / cm ² to 100 mJ / cm ² , and the portion where the developed pattern became 6 μm or more was used as the sensitivity and exposed. A black matrix having an amount of 40 cJ / cm ² or less can be preferably used.

As is clear from [Table 1] and [Table 2], the polymerizable compositions of Examples 1 to 6 have excellent storage stability, high sensitivity, and a cured product obtained by using the polymerizable composition. Is clearly excellent in adhesiveness and adhesion to the substrate.
On the other hand, the polymerizable compositions or cured products of Comparative Examples 1 to 3 were not excellent in storage stability, sensitivity, adhesiveness to a substrate, and adhesion.
Therefore, it is clear that the polymerizable composition of the present invention is suitably used as a member of a display display device or the like.

Claims (8)

A polymerizable composition containing a blocked isocyanate silane compound (A) represented by the following general formula (II) , a polymerizable compound (B), and a radical polymerization initiator (C) .

(In the formula, R ¹ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
R ² represents a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms containing a heterocycle.
Z ¹ represents a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocycle, and one or more of the methylene groups in the group represented by Z ¹ . -O-, -CO-, -COO-, -OCO-, -NR 4-, -NR 4 CO-, -S-, -CS-, -SO 2-, under the condition that oxygen is ^{not adjacent} to each _other . May be replaced with -SCO-, -COS-, -OCS- or CSO-
R4 represents a hydrogen atom and a hydrocarbon group having ¹ to 20 carbon atoms.
a is a number from 1 to 3, and when a ≧ 2, a plurality of R 1s ^may be the same or different.
b represents a number from 0 to 2, and when b = 2, multiple R 2s ^may be the same or different.
a + b = 3,
R ³ represents a hydrogen atom or a methyl group.
X ¹ and X ³ each independently represent a direct bond or a hydrocarbon group having 1 to 20 carbon atoms.
X ² represents a hydrocarbon group having 1 to 20 carbon atoms or a group having 2 to 20 carbon atoms containing a heterocycle.
One or more of the methylene groups in the groups represented by X ¹ , X ² and X ³ are -O-, -CO-, -COO-, -OCO-, under the condition that oxygen is not adjacent to each other. It may be replaced with -NR ^4- , -NR ⁴ CO-, -S- , -CS-, -SO 2-, -SCO-, -COS-, -OCS- or CSO- _.
Y represents an oxygen atom, a sulfur atom, or -NR 4-, ^and represents
c represents a number from 2 to 10 and represents
When c ≧ 2, multiple R3s ^may be the same or different.
d represents a number from 1 to 3 and represents
When d ≧ 2, R ¹ , R ² , X ³ and Z ¹ may be the same or different. )
The polymerizable compound (B) is
An unsaturated compound having a structure obtained by esterifying an epoxy compound represented by the following general formula (IV) and an unsaturated monobasic acid, and an unsaturated compound having a structure obtained by further esterifying a polybasic acid anhydride. as well as
Trimethylolethanetri (meth) acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) A polymerizable composition which is an acrylic acid ester selected from acrylates, tri [(meth) acryloylethyl] isocyanurates and polyester (meth) acrylate oligomers .

(In the formula, M is a direct bond, a hydrocarbon group having 1 to 20 carbon atoms, -O-, -S-, -SO _2- , -SS-, -SO-, -CO-, -OCO-, or. Represents a substituent selected from the group consisting of the following formulas (a), (b), (c) and (d).
One or more hydrogen atoms in a hydrocarbon group having 1 to 20 carbon atoms represented by M may be replaced with a halogen atom.
R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ independently represent a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen atom, respectively.
The methylene group among the groups represented by R ¹¹ to R ¹⁸ may be replaced with —O— under the condition that oxygen is not adjacent to each other.
n represents a number from 0 to 10 and represents
When n is not 0, a plurality of R ¹¹ , R ¹² , R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , and M, which are present in plurality, may be the same or different from each other. )

(In the formula, R ²¹ represents a hydrocarbon group having 1 to 20 carbon atoms.
R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ . , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ and R ⁵⁰ , respectively, independently have a hydrogen atom and 1 to 1 carbon atom. Represents 20 hydrocarbon groups, groups with 2 to 20 carbon atoms containing heterocycles, or halogen atoms.
R ²² , R ²³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ , R ²⁹ , R ³⁰ , R ³¹ , R ³² , R ³³ , R ³⁴ , R ³⁵ , R ³⁶ , R ³⁷ , R ³⁸ . , R ³⁹ , R ⁴⁰ , R ⁴¹ , R ⁴² , R ⁴³ , R ⁴⁴ , R ⁴⁵ , R ⁴⁶ , R ⁴⁷ , R ⁴⁸ , R ⁴⁹ and one of the methylene groups in the group represented by R ⁵⁰ . One or more may be replaced with -O- or -S- under the condition that oxygen is not adjacent to each other.
R ²² and R ²³ , R ²³ and R ²⁴ , R ²⁴ and R ²⁵ , R ²⁵ and R ²⁶ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ , R ²⁹ and R ³⁰ , R ³⁵ and R ³⁶ , R ³⁶ . And R ³⁷ , R ³⁷ and R ³⁸ , R ⁴³ and R ⁴⁴ , R ⁴⁴ and R ⁴⁵ , R ⁴⁵ and R ⁴⁶ , R ⁴⁷ and R ⁴⁸ , R ⁴⁸ and R ⁴⁹ and R ⁴⁹ and R ⁵⁰ are coupled and ringed. May form,
* In the formula means that the group represented by (a), (b), (c) and (d) is bonded to the adjacent group at the * portion. ) The polymerizable composition according to claim 1 , wherein the blocked isocyanate silane compound (A) is a blocked isocyanate silane compound having a group represented by the following general formula (III).

(* In the formula means that the group represented by the general formula (III) is bonded to an adjacent group at the * part.) The polymerizable composition according to claim 1 or 2 , wherein the radical polymerization initiator (C) is a compound having a group represented by the following general formula (V).

(In the formula, R ⁶¹ and R ⁶² each independently have a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydrocarbon group having 1 to 20 carbon atoms, or a heterocycle having 2 to 20 carbon atoms. Represents the group
One or more of the hydrogen atoms in the groups represented by R ⁶¹ and R ⁶² are halogen atom, nitro group, cyano group, hydroxyl group, amino group, carboxyl group, methacryloyl group, acryloyl group, epoxy group and vinyl group. , A vinyl ether group, a mercapto group, an isocyanate group or a group having 2 to 20 carbon atoms containing a heterocycle may be substituted.
One or more of the methylene groups in the groups represented by R ⁶¹ and R ⁶² are -O-, -CO-, -COO-, -OCO-, -NR ⁶³ under the condition that oxygen is not adjacent to each other. -, -NR ⁶³ CO-, -S-, -CS-, -SO _2- , -SCO-, -COS-, -OCS- or CSO-may be replaced.
R ⁶³ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
m represents 0 or 1 and represents
* In the formula means that the group represented by the general formula (V) is bonded to an adjacent group at the * part. ) The polymerizable composition according to any one of claims 1 to 3 , further comprising a colorant (D). A photosensitive composition for a black matrix containing the polymerizable composition according to any one of claims 1 to 4 . A method for producing a cured product, wherein the polymerizable composition according to any one of claims 1 to 4 or the photosensitive composition for a black matrix according to claim 5 is cured by light or heat. The polymerizable composition according to any one of claims 1 to 4 , or the cured product of the photosensitive composition for a black matrix according to claim 5 . A color filter containing the cured product according to claim 7 .