JP2009265372A - Polymerizable composition, light-shielding color filter, and solid-state image sensor - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymerizable composition having high curing sensitivity, with which a high-precision light-shielding film pattern can be formed while decrease in the light-shielding performance in a peripheral portion is suppressed and generation of residual matter in an unexposed portion is suppressed, and to provide a light-shielding color filter having a colored region formed by using the polymerizable composition, and to provide a solid-state image sensor having the light-shielding color filter. <P>SOLUTION: The polymerizable composition contains (A) a titanium black dispersion containing titanium black and an alkali-soluble resin having at least one unsaturated double bond, (B) a polymerizable compound, and (C) a photopolymerization initiator. The light-shielding color filter has a colored region formed by using the polymerizable composition. The solid-state image sensor has the light-shielding color filter. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polymerizable composition, a light-shielding color filter, and a solid-state imaging device.

A color filter used in a liquid crystal display device includes a light shielding film called a black matrix for the purpose of shielding light between colored pixels and improving contrast. A solid-state image sensor is also provided with a light-shielding color filter for the purpose of preventing noise and improving image quality.
As a composition for forming a black matrix for a liquid crystal display device or a light-shielding color filter for a solid-state imaging device, a photosensitive composition containing a black color material such as carbon black or titanium black is known ( For example, see Patent Documents 1 to 5).
Japanese Patent Laid-Open No. 10-246955 JP-A-9-54431 Japanese Patent Laid-Open No. 10-46042 JP 2006-36750 A JP 2007-115921 A

The black matrix for liquid crystal display devices is mainly required to have a light shielding property in the visible region, whereas the light shielding color filter needs to have a light shielding property in the infrared region in addition to the light shielding property in the visible region. .
While the black matrix for liquid crystal display devices is required to be miniaturized, the light-shielding color filter for solid-state image sensors (especially, the surface opposite to the light-receiving element forming surface of the support (hereinafter referred to as “back surface”). The light-shielding color filter for shielding light) is required to uniformly shield light over a larger area than the black matrix for liquid crystal display devices.

However, when a light-shielding color filter having a large area is formed using the above-described conventional photosensitive composition as a light-shielding color filter for a solid-state imaging device, a region where the film thickness is thinner in the periphery of the light-shielding color filter than in the central portion ( Step) may occur, and the light shielding ability around the light shielding color filter may be lowered.
Further, when the content of the black color material is increased in order to obtain a high light-shielding property, there is a problem that a residue tends to be generated in the periphery of the light-shielding color filter and the sensitivity is also lowered. Furthermore, when the amount of photoinitiator is increased in order to improve sensitivity, there is a problem that storage stability is lowered.

This invention is made | formed in view of the above, and makes it a subject to achieve the following objectives.
That is, an object of the present invention is to provide a polymerizable composition capable of forming a high-definition light-shielding film pattern in which a decrease in light-shielding ability in the peripheral portion is suppressed, curing sensitivity is high, and residues in unexposed portions are suppressed. And
In addition, the present invention provides a light-shielding color filter that suppresses a decrease in light-shielding ability at the peripheral portion and has high sensitivity, and a solid-state imaging device including a light-shielding color filter that suppresses a decrease in light-shielding ability at the peripheral portion The purpose is to provide.

Specific means for solving the above-described problems are as follows.
<1> A titanium black dispersion containing (A) an alkali-soluble resin having at least one unsaturated double bond and titanium black, (B) a polymerizable compound, and (C) a photopolymerization initiator. It is a polymerizable composition.
<2> The polymerizable composition as described in <1> above, wherein the (C) photopolymerization initiator is an oxime compound.

<3> The polymerizable composition as described in <1> or <2> above, wherein the content of titanium black with respect to the total solid content of the polymerizable composition is 40% by mass or more and 80% by mass or less. It is.
<4> The polymerizable composition as described in any one of <1> to <3> above, which is used for forming a light-shielding color filter.

<5> A light-shielding color filter having a colored region formed on the support using the polymerizable composition according to <4>.
<6> A solid-state imaging device including the light-shielding color filter according to <5>.

In the present invention, the “light-shielding color filter” refers to a light-shielding pattern obtained by exposing and developing a polymerizable composition containing at least a titanium black dispersion, a polymerizable compound, and a photopolymerization initiator. The color of the “light-shielding color filter” in the present invention may be an achromatic color such as black or gray, or a black or gray color mixed with a chromatic color.
The “light-shielding color filter” is obtained by exposing and developing a polymerizable composition containing at least a titanium black dispersion, a polymerizable compound, and a photopolymerization initiator. In other words.

According to the present invention, it is possible to provide a polymerizable composition having high sensitivity, a residue in an unexposed portion being suppressed, and good storage stability.
Furthermore, according to the present invention, there is provided a polymerizable composition capable of forming a high-definition light-shielding film pattern in which a decrease in light-shielding ability in a peripheral portion is suppressed, a curing sensitivity is high, and a residue in an unexposed portion is suppressed. Can do.
The present invention also provides a light-shielding color filter in which a decrease in light-shielding ability in the peripheral portion is suppressed, and a solid-state imaging device including a light-shielding color filter in which a decrease in light-shielding ability in the peripheral portion is suppressed. can do.

The present invention is described in detail below.
The polymerizable composition of the present invention includes (A) a titanium black dispersion containing an alkali-soluble resin having at least one unsaturated double bond and titanium black, (B) a polymerizable compound, and (C) light. It is a polymerizable composition containing a polymerization initiator. Hereinafter, each component contained in the polymerizable composition will be described.

<Polymerizable composition>
[(A) Titanium black dispersion]
(A) Titanium black dispersion is a composition comprising an alkali-soluble resin having at least one unsaturated double bond and titanium black as a coloring material, wherein titanium black is dispersed in an appropriate liquid. It is a dispersion formed.
The dispersibility and dispersion stability of titanium black are improved when the polymerizable composition contains titanium black as a previously prepared titanium black dispersion.
Hereinafter, first, titanium black will be described.

-Titanium black-
The titanium black of the present invention is black particles having titanium atoms. Preferred are low-order titanium oxide and titanium oxynitride. The surface of titanium black particles can be modified as necessary for the purpose of improving dispersibility and suppressing aggregation. It can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide, zirconium oxide, and can also be treated with a water repellent material as disclosed in JP-A-2007-302836. .

  Titanium black is produced by heating a mixture of titanium dioxide and metal titanium in a reducing atmosphere (Japanese Patent Laid-Open No. 49-5432), ultrafine dioxide obtained by high-temperature hydrolysis of titanium tetrachloride. A method of reducing titanium in a reducing atmosphere containing hydrogen (Japanese Patent Laid-Open No. 57-205322), a method of reducing titanium dioxide or titanium hydroxide at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 60-65069, Japanese Patent Laid-Open No. Sho 61-201610), a method in which a vanadium compound is attached to titanium dioxide or titanium hydroxide and reduced at a high temperature in the presence of ammonia (Japanese Patent Laid-Open No. 61-201610), etc. is not.

  The particle size of the titanium black particles is not particularly limited, but from the viewpoint of dispersibility and colorability, the average particle size is preferably 3 nm or more and 2000 nm or less, more preferably the average particle size is 10 nm or more and 500 nm or less. Preferably, the average particle diameter is 10 nm or more and 100 nm or less.

The specific surface area of titanium black is not particularly limited. However, since the water repellency after surface treatment of such titanium black with a water repellent becomes a predetermined performance, the value measured by the BET method is usually 5 m ² / g or more and about 150 m ² / g or less, and particularly preferably about 20 m ² / g or more and 100 m ² / g or less.

  Examples of commercially available titanium black include, for example, Titanium Black 10S, 12S, 13R, 13M, 13M-C, 13R, 13R-N, Ako Kasei Co., Ltd., Tilac D manufactured by Mitsubishi Materials Corporation. However, the present invention is not limited to these.

The content of the titanium black dispersion added to the polymerizable composition of the present invention is adjusted so that the content in terms of solid content of titanium black in the polymerizable composition is 30% by mass to 94% by mass. The The content of titanium black in the polymerizable composition is more preferably in the range of 40% by mass to 92% by mass, and still more preferably in the range of 40% by mass to 80% by mass.
By setting it as the said range, sclerosis | hardenability of polymeric composition becomes favorable and can form a uniform film | membrane. Further, since titanium black is contained at a high concentration, sufficient light shielding properties can be obtained, and a polymerizable composition containing the titanium black dispersion can be suitably used for forming a light shielding color filter.

-Alkali-soluble resin having at least one unsaturated double bond-
The titanium black dispersion in the polymerizable composition of the present invention contains an alkali-soluble resin having at least one unsaturated double bond (hereinafter also referred to as “specific alkali-soluble resin”) together with the titanium black. . That is, in the titanium black dispersion, the alkali-soluble resin functions as a titanium black dispersion resin. When the titanium black dispersion of the polymerizable composition in the present invention contains a specific alkali-soluble resin that functions as a titanium black dispersion resin together with the above titanium black, the polymer dispersant itself essential for the dispersion of titanium black can be obtained. Since it has both alkali solubility and curability, as a result, both the curability of the polymerizable composition, particularly the exposed portion and the unexposed portion, are improved.

The specific alkali-soluble resin used in the present invention has an acid group for making the resin alkali-soluble and at least one unsaturated divalent resin in order to improve various properties such as non-image area removability in the structure. Has a double bond. As a structure containing the unsaturated double bond, as a preferred specific embodiment, one having at least one selected from groups represented by the following partial structure (a) to partial structure (c) in the side chain is preferable. Can be mentioned. This resin, which is soluble in an alkaline aqueous solution and used as a binder resin for a negative image recording material, is at least one selected from groups represented by partial structures (a) to (c) in the side chain. If you have. Of course, you may have multiple types of such groups, and you may have all of these simultaneously.
Hereinafter, the side chains represented by the partial structure (a) to the partial structure (c) will be described in detail.

In the partial structure (a) to the partial structure (c), R ^{4 to} R ⁶ , R ^{10 to} R ¹² , and R ^{16 to} R ²⁰ each independently represent a monovalent substituent. X and Z each independently represent an oxygen atom, a sulfur atom, or —N (R ²² ) —, and R ²² represents a hydrogen atom or a monovalent organic group. Y represents an oxygen atom, a sulfur atom, a phenylene group which may have a substituent, or —N (R ²³ ) —, and R ²³ represents a hydrogen atom or a monovalent organic group.

In the partial structure (a), R ^{4 to} R ⁶ each independently represents a monovalent substituent, and R ⁴ is preferably a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom and a methyl group are preferable in terms of high radical reactivity. R ⁵ and R ⁶ are each independently a hydrogen atom, a halogen atom, an amino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, an alkyl group which may have a substituent, or a substituent. An aryl group that may have a group, an alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylamino group that may have a substituent, and a substituent An arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, and the like. Among them, a hydrogen atom, a carboxyl in view of high radical reactivity. A group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable.

X represents an oxygen atom, a sulfur atom, or —N (R ²² ) —, and R ²² represents a hydrogen atom or a monovalent organic group. Here, examples of R ²² include an alkyl group which may have a substituent, and among them, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable in terms of high radical reactivity.

  Here, examples of the substituent that can be introduced include an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an aryloxy group, a halogen atom, an amino group, an alkylamino group, an arylamino group, a carboxyl group, an alkoxycarbonyl group, A sulfo group, a nitro group, a cyano group, an amide group, an alkylsulfonyl group, an arylsulfonyl group and the like can be mentioned.

In the partial structure (b), R ¹⁰ preferably includes a hydrogen atom or an alkyl group which may have a substituent. Among them, a hydrogen atom or a methyl group is preferable in view of high radical reactivity. Is preferred. R ¹¹ and R ¹² are each independently a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, a carboxyl group, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl group that may have a substituent. An aryl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylamino group which may have a substituent, a substituent An arylamino group that may have a substituent, an alkylsulfonyl group that may have a substituent, an arylsulfonyl group that may have a substituent, and the like. Among them, in terms of high radical reactivity, a hydrogen atom A carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent are preferable.

Here, examples of the substituent that can be introduced include the same groups as those exemplified in the description of the partial structure (a). Y represents an oxygen atom, a sulfur atom, a phenylene group which may have a substituent, or —N (R ²³ ) —. Examples of R ²³ include an alkyl group which may have a substituent, and among them, a hydrogen atom, a methyl group, an ethyl group, and an isopropyl group are preferable in terms of high radical reactivity.

In the partial structure (c), R ^{16 to} R ²⁰ each independently represents a monovalent substituent, and R ^{16 to} R ²⁰ are preferably a hydrogen atom, a halogen atom, an amino group, a dialkylamino group, Carboxyl group, alkoxycarbonyl group, sulfo group, nitro group, cyano group, alkyl group which may have a substituent, aryl group which may have a substituent, alkoxy group which may have a substituent, substituted An aryloxy group which may have a group, an alkylamino group which may have a substituent, an arylamino group which may have a substituent, an alkylsulfonyl group which may have a substituent, a substituent An arylsulfonyl group which may have a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, an aryl which may have a substituent. Le group.

Examples of the substituent that can be introduced include the same groups as those exemplified in the description of the partial structure (a). Z represents an oxygen atom, a sulfur atom, or —N (R ²² ) —. R ²² has the same meaning as ^{R 22} in the partial structure (a), and preferred examples are also the same.

  Further, the specific alkali-soluble resin used in the titanium black dispersion contained in the polymerizable composition of the present invention improves various properties such as alkali solubility of the resin itself, that is, non-image area removability, in the structure. In order to have an acid group. The specific alkali-soluble resin preferably contains a radically polymerizable compound having an acid group as a copolymer component.

  Examples of the acid group include carboxylic acid, sulfonic acid, phosphoric acid group, phenolic hydroxyl group, and the like, and particularly preferred is a carboxylic acid group. One or more of these can be used, and the content of these copolymerization components used is preferably 5 mol% or more and 50 mol% or less, and particularly preferably suppresses image strength damage due to alkali water development. From this viewpoint, it is 10 mol% or more and 40 mol% or less.

  Furthermore, the specific alkali-soluble resin used in the titanium black dispersion contained in the polymerizable composition according to the present invention is not limited to the above-described specific unless the effects of the present invention are impaired for the purpose of improving various performances such as image strength. In addition to a copolymer component having a functional group (structural unit) and a structural unit having an acid group (alkali-soluble group), it can further interact with other structural units having various functions, such as titanium black. A structural unit having a functional group, a functional group having affinity with the dispersion medium used in the dispersion, and the like can be included as a copolymerization component.

  Examples of the copolymerizable component copolymerizable with the specific alkali-soluble resin according to the present invention include radical polymerizable compounds selected from acrylic acid esters, methacrylic acid esters, styrenes, acrylonitriles, methacrylonitriles, and the like. Can be mentioned.

  Specifically, for example, acrylic acid esters such as alkyl acrylate (the alkyl group preferably has 1 to 20 carbon atoms) (specifically, for example, benzyl acrylate, 4-biphenyl acrylate, butyl Acrylate, sec-butyl acrylate, t-butyl acrylate, 4-t-butylphenyl acrylate, 4-chlorophenyl acrylate, pentachlorophenyl acrylate, 4-cyanobenzyl acrylate, cyanomethyl acrylate, cyclohexyl acrylate, 2-ethoxyethyl acrylate, ethyl acrylate 2-ethylhexyl acrylate, heptyl acrylate, hexyl acrylate, isobornyl acrylate, isopropyl acrylate, methyl acrylate, 3,5-dimethyl Adamantyl acrylate, 2-naphthyl acrylate, neopentyl acrylate, octyl acrylate, phenethyl acrylate, phenyl acrylate, propyl acrylate, tolyl acrylate, amyl acrylate, tetrahydrofurfuryl acrylate, 2-hydroxyethyl acrylate, 3-hydroxypropyl acrylate, 2-hydroxy Propyl acrylate, 4-hydroxybutyl acrylate, 5-hydroxypentyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate, etc.)

Methacrylic acid esters (eg, benzyl methacrylate, 4-biphenyl methacrylate, butyl methacrylate, sec-butyl methacrylate, t-butyl methacrylate, 4- t-butylphenyl methacrylate, 4-chlorophenyl methacrylate, pentachlorophenyl methacrylate, 4-cyanophenyl methacrylate, cyanomethyl methacrylate, cyclohexyl methacrylate, 2-ethoxyethyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, heptyl methacrylate, hexyl methacrylate, isoboro Nyl methacrylate, isopropyl methacrylate, methyl methacrylate, 3,5- Methyl adamantyl methacrylate, 2-naphthyl methacrylate, neopentyl methacrylate, octyl methacrylate, phenethyl methacrylate, phenyl methacrylate, propyl methacrylate, tolyl methacrylate, amyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxyethyl methacrylate, 3-hydroxypropyl methacrylate, 2- Hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, propargyl methacrylate, etc.

Styrenes such as styrene and alkyl styrene (for example, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, diethyl styrene, isopropyl styrene, butyl styrene, hexyl styrene, cyclohexyl styrene, decyl styrene, benzyl styrene, chloromethyl styrene, Trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, etc.), alkoxy styrene (eg methoxy styrene, 4-methoxy-3-methyl styrene, dimethoxy styrene, etc.), halogen styrene (eg chloro styrene, dichloro styrene, trichloro styrene, Tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluoro Ren, 2-bromo-4-trifluoromethyl styrene, 4-fluoro-3-trifluoromethyl styrene etc.), acrylonitrile, methacrylonitrile, and the like.

  Among these radically polymerizable compounds, methacrylic acid esters, acrylamides, methacrylamides, and styrenes are preferably used, and benzyl methacrylate, t-butyl methacrylate, 4-t-butylphenyl methacrylate, pentachlorophenyl methacrylate, 4-cyanophenyl methacrylate, cyclohexyl methacrylate, ethyl methacrylate, 2-ethylhexyl methacrylate, isobornyl methacrylate, isopropyl methacrylate, methyl methacrylate, 3,5-dimethyladamantyl methacrylate, 2- Naphthyl methacrylate, neopentyl methacrylate, phenyl methacrylate, tetrahydrofurfuryl methacrylate, 2-hydroxyethyl Methacrylate, 3-hydroxypropyl methacrylate, 2-hydroxypropyl methacrylate, allyl methacrylate,

Acrylamide, N-methylacrylamide, N-isopropylacrylamide, morpholylacrylamide, piperidylacrylamide, Nt-butylacrylamide, N-cyclohexylacrylamide, N-phenylacrylamide, N-naphthylacrylamide, N-hydroxymethylacrylamide, N- Hydroxyethylacrylamide, N-allylacrylamide, 4-hydroxyphenylacrylamide, 2-hydroxyphenylacrylamide, N, N-dimethylacrylamide, N, N-diisopropylacrylamide, N, N-di-t-butylacrylamide, N, N- Dicyclohexylacrylamide, N, N-phenylacrylamide, N, N-dihydroxyethylacrylamide, N, N-diallylacryl Bromide,

Methacrylamide, N-methylmethacrylamide, N-isopropylmethacrylamide, morpholylmethacrylamide, piperidylmethacrylamide, Nt-butylmethacrylamide, N-cyclohexylmethacrylamide, N-phenylmethacrylamide, N-naphthylmethacrylamide N-hydroxymethylmethacrylamide, N-hydroxyethylmethacrylamide, N-allylmethacrylamide, 4-hydroxyphenylmethacrylamide, 2-hydroxyphenylmethacrylamide, N, N-dimethylmethacrylamide, N, N-diisopropylmethacrylamide N, N-di-t-butylmethacrylamide, N, N-dicyclohexylmethacrylamide, N, N-phenylmethacrylamide, N, N-dihydroxyethylmethacrylate Acrylamide, N, N-diallyl methacrylamide,

Styrene, methyl styrene, dimethyl styrene, trimethyl styrene, isopropyl styrene, butyl styrene, cyclohexyl styrene, chloromethyl styrene, trifluoromethyl styrene, ethoxymethyl styrene, acetoxymethyl styrene, methoxy styrene, 4-methoxy-3-methyl styrene , Chlorostyrene, dichlorostyrene, trichlorostyrene, tetrachlorostyrene, pentachlorostyrene, bromostyrene, dibromostyrene, iodostyrene, fluorostyrene, trifluorostyrene, 2-bromo-4-trifluoromethylstyrene, 4- Fluoro-3-trifluoromethylstyrene.

  These may be used alone or in combination of two or more. The content of these copolymerization components in the specific alkali-soluble resin is preferably 0 mol% or more and 90 mol% or less, particularly preferably 0 mol. % Or more and 60 mol% or less. When the content is in the above range, sufficient pattern formation can be obtained.

  Examples of the solvent used for synthesizing such a polymer compound include ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, propanol, butanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxy. Examples include ethyl acetate, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, toluene, ethyl acetate, methyl lactate, and ethyl lactate. It is done. These solvents may be used alone or in combination of two or more.

  Specific examples of such specific alkali-soluble resin include the following Exemplified Compound 1 to Exemplified Compound 31.

  The specific alkali-soluble resin is at least one structural unit selected from the group consisting of structural units represented by the following general formulas (1) to (3) in terms of polymerizability and alkali developability, and the following general It is preferable that it is resin which has a structural unit represented by Formula (4).

In the general formulas (1) to (3), A ¹ , A ² , and A ³ each independently represent an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and R ²¹ represents a substituent. It represents an alkyl group that may have. G ¹ , G ² , and G ³ each independently represent a divalent organic group. X and Z each independently represent an oxygen atom, a sulfur atom, or —N (R ²² ) —, and R ²² represents an alkyl group which may have a substituent. Y represents an oxygen atom, a sulfur atom, a phenylene group which may have a substituent, or —N (R ²³ ) —, and R ²³ represents an alkyl group which may have a substituent. R ^{1 to} R ²⁰ each independently represents a monovalent substituent.

In the general formula (1), R ^{1 to} R ³ each independently represents a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may further have a substituent. Among them, R ¹ and R ² are preferably hydrogen atoms, and R ³ is preferably a hydrogen atom or a methyl group.
R ^{4 to} R ⁶ in the general formula (1) each independently represent a monovalent substituent, and examples of R ⁴ include a hydrogen atom or an alkyl group which may further have a substituent. . Of these, a hydrogen atom, a methyl group, and an ethyl group are preferable. R ⁵ and R ⁶ in the general formula (1) are each independently a hydrogen atom, a halogen atom, an alkoxycarbonyl group, a sulfo group, a nitro group, a cyano group, or an alkyl group which may further have a substituent. An aryl group which may further have a substituent, an alkoxy group which may further have a substituent, an aryloxy group which may further have a substituent, and an alkylsulfonyl group which may further have a substituent And an arylsulfonyl group which may further have a substituent, among others, a hydrogen atom, an alkoxycarbonyl group, an alkyl group which may further have a substituent, and an aryl group which may further have a substituent Is preferred.
Here, examples of the substituent that may have include a methoxycarbonyl group, an ethoxycarbonyl group, an isopropyloxycarbonyl group, a methyl group, an ethyl group, and a phenyl group.

In the general formula (1), A ¹ represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and X represents an oxygen atom, a sulfur atom, or —N (R ²² ) —. Here, examples of R ²¹ and R ²² include an alkyl group which may have a substituent.
G ¹ in the general formula (1) represents a divalent organic group, and an alkylene group which may have a substituent is preferable. More preferably, an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, or a substituent having 6 to 20 carbon atoms. An aromatic group that may have a substituent, among others, a linear or branched alkylene group having 1 to 10 carbon atoms that may have a substituent, and a substituent having 3 to 10 carbon atoms. A cycloalkylene group which may be substituted, and an aromatic group which may have a substituent having 6 to 12 carbon atoms are preferred in terms of performance such as strength and developability.

Here, preferable examples of the substituent in G ¹ include a substituent other than a hydroxyl group and a substituent having a hetero atom to which a hydrogen atom other than the hydroxyl group is bonded (for example, an amino group, a thiol group, a carboxy group, or the like). be able to.

In the structural unit represented by the general formula (1) in the present invention, A ¹ is an oxygen atom, a sulfur atom or —N (R ²¹ ) —, and X is an oxygen atom, a sulfur atom or —N (R ²² ). -G ¹ is an alkylene group which may have a substituent, R ¹ and R ² are hydrogen atoms, R ³ is a hydrogen atom or a methyl group, and R ⁴ is hydrogen It is preferably an atom or an alkyl group, and R ⁵ and R ⁶ are each independently a hydrogen atom, an alkoxycarbonyl group, an alkyl group, or an aryl group, and R ²¹ and R ²² are preferably an alkyl group.

In the general formula (2), R ^{7 to} R ⁹ each independently represents a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may further have a substituent. Among them, R ⁷ , R ⁸ is preferably a hydrogen atom, and R ⁹ is preferably a hydrogen atom or a methyl group.
R ^{10 to} R ¹² in the general formula (2) each independently represent a monovalent substituent, and specific examples of the substituent include a hydrogen atom, a halogen atom, a dialkylamino group, and alkoxycarbonyl. A group, a sulfo group, a nitro group, a cyano group, an alkyl group which may further have a substituent, an aryl group which may further have a substituent, an alkoxy group which may further have a substituent, and a substituent. Further examples include an aryloxy group which may further have, an alkylsulfonyl group which may further have a substituent, an arylsulfonyl group which may further have a substituent, and the like. Among them, a hydrogen atom, an alkoxycarbonyl group, a substituent An alkyl group which may further have a group and an aryl group which may further have a substituent are preferred.
Here, as a substituent which may be included, those exemplified in the general formula (1) are similarly exemplified.

A ² in the general formula (2) represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, where R ²¹ is a hydrogen atom or an alkyl group which may have a substituent. Etc.
G ² in the general formula (2) represents a divalent organic group, but is preferably an alkylene group which may have a substituent. Preferably, an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, or a substituent having 6 to 20 carbon atoms. An aromatic group that may be included is mentioned, among others, a linear or branched alkylene group having 1 to 10 carbon atoms that may have a substituent, and a substituent having 3 to 10 carbon atoms An cycloalkylene group which may be substituted and an aromatic group which may have a substituent having 6 to 12 carbon atoms are preferred in terms of performance such as strength and developability.
Here, preferable examples of the substituent in G ² include a substituent other than a hydroxyl group and a substituent having a hetero atom to which a hydrogen atom other than the hydroxyl group is bonded (for example, an amino group, a thiol group, and a carboxy group). be able to.
When G ² in the general formula (2) has a substituent having a hetero atom to which a hydrogen atom other than a hydroxyl group is bonded, the storage stability is lowered by using an onium salt compound as an initiator described later. There is.
Y in the general formula (2) represents an oxygen atom, a sulfur atom, -N (R ²³ )-or a phenylene group which may have a substituent. Here, examples of R ²³ include a hydrogen atom and an alkyl group which may have a substituent.

In the structural unit represented by the general formula (2) in the present invention, R ¹⁰ is a hydrogen atom or an alkyl group, and R ¹¹ and R ¹² are each independently a hydrogen atom, an alkoxycarbonyl group, an alkyl group, or an aryl group. R ⁷ and R ⁸ are hydrogen atoms, R ⁹ is a hydrogen atom or a methyl group, A ² is an oxygen atom, a sulfur atom or —N (R ²¹ ) —, and G ² May have a straight chain or branched alkylene group having 1 to 10 carbon atoms, a cycloalkylene group that may have a substituent having 3 to 10 carbon atoms, or a group having 6 to 12 carbon atoms. An aromatic group which may have a substituent, wherein Y is an oxygen atom, a sulfur atom, —N (R ²³ ) — or a phenylene group which may have a substituent, and R ²¹ , R ²³ May optionally have a hydrogen atom or a substituent It is preferable that.

In the general formula (3), R ^{13 to} R ¹⁵ each independently represents a monovalent substituent, and examples thereof include a hydrogen atom and an alkyl group which may further have a substituent. Among them, R ¹³ , ^{R 14} is preferably a hydrogen ^{atom, R 15} is a hydrogen atom or a methyl group.
R ^{16 to} R ²⁰ in the general formula (3) each independently represent a monovalent substituent, and R ^{16 to} R ²⁰ are, for example, a hydrogen atom, a halogen atom, a dialkylamino group, an alkoxycarbonyl group, a sulfo group. Group, nitro group, cyano group, alkyl group which may further have a substituent, aryl group which may further have a substituent, alkoxy group which may further have a substituent, and further having a substituent An aryloxy group that may further have a substituent, an arylsulfonyl group that may further have a substituent, and the like. Among them, a hydrogen atom, an alkoxycarbonyl group, and a substituent may be further included. The alkyl group which may have and the aryl group which may further have a substituent are preferable. Examples of the substituent that can be introduced include those listed in the general formula (1).
A ³ in the general formula (3) represents an oxygen atom, a sulfur atom, or —N (R ²¹ ) —, and Z represents an oxygen atom, a sulfur atom, or —N (R ²² ) —. Examples of R ²¹ and R ²² include the same as those in general formula (1).

G ³ in the general formula (3) represents a divalent organic group, and an alkylene group which may have a substituent is preferable. Preferably, an alkylene group which may have a substituent having 1 to 20 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 20 carbon atoms, or a substituent having 6 to 20 carbon atoms. An aromatic group that may be included is mentioned, among others, a linear or branched alkylene group having 1 to 10 carbon atoms that may have a substituent, and a substituent having 3 to 10 carbon atoms An cycloalkylene group which may be substituted and an aromatic group which may have a substituent having 6 to 12 carbon atoms are preferred in terms of performance such as strength and developability.
Here, preferable examples of the substituent in G ³ include a substituent other than a hydroxyl group and a substituent having a hetero atom to which a hydrogen atom other than the hydroxyl group is bonded (for example, an amino group, a thiol group, and a carboxy group). be able to.

In the structural unit represented by the general formula (3) in the present invention, R ¹³ and R ¹⁴ are hydrogen atoms, R ¹⁵ is a hydrogen atom or a methyl group, R ^{16 to} R ²⁰ are hydrogen atoms, alkoxy A carbonyl group, an optionally substituted alkyl group, or an optionally substituted aryl group, wherein A ³ is an oxygen atom, a sulfur atom or —N (R ²¹ ) —, and Z is An oxygen atom, a sulfur atom, or —N (R ²² ) —, wherein R ²¹ and R ²² are the same as those in formula (1), and G ³ may have a substituent. A linear or branched alkylene group having 1 to 10 carbon atoms, a cycloalkylene group which may have a substituent having 3 to 10 carbon atoms, or an aromatic group which may have a substituent having 6 to 12 carbon atoms It is preferably a group.

The specific alkali-soluble resin in the present invention contains at least one structural unit selected from the structural units represented by the general formulas (1) to (3) in order to suppress thermal sag in post-baking. It is preferable to contain at least 1.5 times the content of the structural unit represented by From the viewpoint of curability, at least one structural unit selected from the structural units represented by the general formulas (1) to (3) is selected from 2. of the content of the structure represented by the general formula (4). It is more preferably 0 or more times, and most preferably 3.0 or more times.
Further, from the viewpoint of improving curability and reducing development residue, at least one structural unit selected from the structural units represented by the general formulas (1) to (3) is contained in an amount of 35 mol% or more and 95 or more. The compound is preferably contained in a range of less than mol%. More preferably, it is 37 mol% or more and less than 90 mol%. More preferably, it is the range of 40 mol% or more and less than 85 mol%. Among these, from the viewpoint of curability, a resin containing 40 mol% or more and less than 85 mol% of the structural unit represented by the general formula (1) is most preferable.

  Synthesis of a polymer compound having at least one structural unit selected from the structural units represented by the general formulas (1) to (3) is described in paragraphs [0027] to [0027] of JP-A No. 2003-262958. 0057] can be carried out based on the synthesis method described in [0057]. Among them, the synthesis method 1) in the same publication is preferable.

  The specific alkali-soluble resin is preferably a resin obtained by the following synthesis method (1) or synthesis method (2).

Synthesis method (1)
A polymer is synthesized using a compound represented by the following general formula (5) as one of the copolymerization components, and a base is allowed to act to extract protons and desorb L, and is represented by the general formula (1). A method for obtaining a desired polymer compound having a structure.

In the general formula (5), L represents an anionic leaving group, preferably a halogen atom, an alkyl or arylsulfonyloxy group or the like. ^{R 3 ~R 6, A 1,} G 1, and for X are as defined as in the general formula (1).
As the base used for causing the elimination reaction, either an inorganic compound or an organic compound may be used. Details and preferred embodiments of this method are described in paragraphs [0028] to [0033] of JP-A No. 2003-262958.

  Preferred inorganic compound bases include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like, and organic compound bases include sodium methoxide, sodium ethoxide, potassium t- Examples thereof include metal alkoxides such as butoxide, organic amine compounds such as triethylamine, pyridine and diisopropylethylamine.

Synthesis method (2)
For a polymer synthesized using a compound represented by the following general formula (6) as a copolymerization component, an elimination reaction is caused in a specific functional group by base treatment, X ¹ is removed, and a radical reactive group is removed. How to get.

In General Formula (6), A ⁴ represents an oxygen atom, a sulfur atom, or —N (R ²⁷ ) —, A ⁵ represents an oxygen atom, a sulfur atom, or —NR ²⁸ —, and R ²⁴ , R ²⁵ , R ²⁶ , R ²⁹ , R ³⁰ and R ³¹ each independently represent hydrogen or a monovalent organic group, X ¹ represents a group to be removed by elimination reaction, and G ⁴ represents an organic linking group. n represents an integer of 1 to 10.

In the present invention, A ⁴ is preferably an oxygen atom. R ²⁴ is preferably a methyl group, R ²⁵ , R ²⁶ , R ²⁹ and R ³⁰ are preferably a hydrogen atom, and R ³¹ is preferably a methyl group or a hydrogen atom. Further, X ¹ is preferably a bromine atom, and G ⁴ is preferably an ethylene group.

  Details and preferred embodiments of the above method are described in detail in JP-A No. 2003-335814.

  Examples of the resin obtained by the synthesis method (2) include the polymer compounds described in JP-A No. 2003-335814, specifically, for example, (i) a polyvinyl polymer compound, and (ii) a polyurethane polymer compound. (Iii) polyurea polymer compound, (iv) poly (urethane-urea) polymer compound, (v) polyester polymer compound, (vi) polyamide polymer compound, (vii) acetal-modified polyvinyl alcohol compound Preferred examples thereof include the following polymer compounds and specific compounds obtained from the respective descriptions.

  Specific examples of the compound represented by the general formula (5) include the following compounds (M-1) to (M-12), but the present invention is not limited thereto.

  Examples of the compound represented by the general formula (6) include the following compounds (i-1) to (i-50), but the present invention is not limited thereto.

  The specific alkali-soluble resin in the present invention preferably contains a structural unit represented by the following general formula (4).

In the general formula (4), R ^A is hydrogen or an alkyl group having 1 to 6 carbon atoms, and R ^B is a divalent linking group.
R ^A is preferably a hydrogen atom or a methyl group.
Wherein ^{R B} is may be a divalent linking group, for example optionally substituted alkylene group having 1 to 12 carbon atoms, ^-U-R C -V- (however, U and V are each independently Represents a direct bond or an alkylene group having 1 to 3 carbon atoms, and R ^C represents an optionally substituted cyclohexyl ring, benzene ring or naphthalene ring), or —R ^D —X—R ^E — (provided that R ^D and R ^E each independently represents an optionally substituted alkylene group having 1 to 10 carbon atoms, an optionally substituted benzene ring or naphthalene ring, and X represents an ester bond, an amide bond, a urethane bond, an ether bond, a thioether bond, a carbonate bond, a urea bond or an imide bond) and the like, it is preferable among them R ^B is a divalent linking group having 1 to 6 carbon atoms.

  Among the specific alkali-soluble resins in the present invention, at least one structural unit selected from the group consisting of structural units represented by the general formulas (1) to (3) and the general formula (4). Specific examples of the resin having a structural unit include exemplified compounds 101 to 121 shown in the following table.

  The acid value of the specific alkali-soluble resin is preferably 5.0 mgKOH / g or more and 110 mgKOH / g or less, more preferably 5.5 mgKOH / g or more and 75 mgKOH / g or less, still more preferably 6.0 mgKOH / g or more and 70 mgKOH. / G or less is preferable. If the acid value is 110 mgKOH / g or less, pattern peeling during development can be suppressed, and if it is 5.0 mgKOH / g or more, alkali developability is good.

  In the present invention, the acid value of the specific alkali-soluble resin can be calculated, for example, from the average content of acid groups in the resin molecule. Moreover, the resin which has a desired acid value can be obtained by changing content of the monomer unit containing the acid group which comprises specific alkali-soluble resin.

The mass average molecular weight of the specific alkali-soluble resin in the present invention is preferably 10,000 or more and 300,000 or less, and preferably 15,000 or more and 200,000 or less, from the viewpoint of pattern peeling inhibition during development and developability. Is more preferably 20,000 or more and 100,000 or less, and particularly preferably 25,000 or more and 50,000 or less.
In addition, the mass average molecular weight of specific alkali-soluble resin can be measured by GPC, for example.

  The content of the specific alkali-soluble resin relative to the total solid content of the polymerizable composition of the present invention is preferably 2% by mass or more and 60% by mass or less in terms of polymerizability and alkali developability. From the viewpoint of coexistence of suppression, 4% by mass to 50% by mass is more preferable, and 6% by mass to 40% by mass is more preferable.

-Dispersant-
The titanium black dispersion contained in the polymerizable composition of the present invention contains a dispersant (hereinafter sometimes referred to as “pigment dispersant”) for the purpose of adjusting the dispersibility of titanium black. Is preferred.
Examples of pigment dispersants that can be used in the present invention include polymer dispersants [for example, polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth) acrylates. , (Meth) acrylic copolymers, naphthalenesulfonic acid formalin condensates], polyoxyethylene alkyl phosphate esters, polyoxyethylene alkyl amines, alkanol amines, pigment derivatives, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer from the structure thereof.

The polymer dispersant is adsorbed on the surface of titanium black and a pigment described later that is used in combination, if desired, and acts to prevent re-aggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures.
On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  Specific examples of the pigment dispersant that can be used in the present invention include “Disperbyk-101 (polyamidoamine phosphate), 107 (carboxylic acid ester), 110 (copolymer containing an acid group), 130 (polyamide) manufactured by BYK Chemie. ), 161, 162, 163, 164, 165, 166, 170 (polymer copolymer) ”,“ BYK-P104, P105 (high molecular weight unsaturated polycarboxylic acid) ”,“ EFKA 4047, 4050, 4010, manufactured by EFKA, 4165 (polyurethane series), EFKA4330, 4340 (block copolymer), 4400, 4402 (modified polyacrylate), 5010 (polyesteramide), 5765 (high molecular weight polycarboxylate), 6220 (fatty acid polyester), 6745 (phthalocyanine) Derivatives), 6750 (azo) "Adisper PB821, PB822" manufactured by Ajinomoto Fan Techno Co., "Floren TG-710 (urethane oligomer)" manufactured by Kyoeisha Chemical Co., "Polyflow No. 50E, No. 300 (acrylic copolymer)", “Disparon KS-860, 873SN, 874, # 2150 (aliphatic polycarboxylic acid), # 7004 (polyetherester), DA-703-50, DA-705, DA-725” manufactured by Enomoto Kasei Co., Ltd., Kao “Demol RN, N (Naphthalenesulfonic acid formalin polycondensate), MS, C, SN-B (aromatic sulfonic acid formalin polycondensate)”, “Homogenol L-18 (polymer polycarboxylic acid)”, “ Emulgen 920, 930, 935, 985 (polyoxyethylene nonylphenyl ether) ”,“ acetamine 86 (stearylamine acetate) ", Lubrizol" Solsperse 5000 (phthalocyanine derivative), 22000 (azo pigment derivative), 13240 (polyesteramine), 3000, 17000, 27000 (polymer having a functional part at the end), 24000, 28000, 32000, 38500 (graft type polymer) ”,“ Nikkor T106 (polyoxyethylene sorbitan monooleate), MYS-IEX (polyoxyethylene monostearate) ”manufactured by Nikko Chemicals, and the like.

  These dispersants may be used alone or in combination of two or more. In the present invention, it is particularly preferable to use a pigment derivative and a polymer dispersant in combination from the viewpoint of suppressing the viscosity change of the dispersion over time.

In addition, the (A) titanium black dispersion of the present invention includes a composite oxide such as Cu, Fe, Mn, V, Ni, cobalt oxide, iron oxide, carbon black, for the purpose of adjusting dispersibility, colorability, and the like. You may contain black pigments, such as aniline black, manganese oxide, and graphite, 1 type or in combination of 2 or more types. In this case, the content ratio of titanium black in the total pigment is preferably 50% by mass or more, more preferably 55% by mass or more, and further preferably 60% by mass or more.
In addition, the (A) titanium black dispersion of the present invention has an existing pigment such as red, blue, green, yellow, cyan, magenta, violet, orange, or the like, for the purpose of controlling the light-shielding property at a desired wavelength. It is also possible to add known colorants such as dyes.

  In the present invention, the content of the combined pigment is preferably in the range of 2 parts by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the total pigment of titanium black and other pigments used in combination as desired. More preferably, the combined pigment is 2 parts by mass or more and 30 parts by mass or less, and further preferably the combined pigment is 2 parts by mass or more and 10 parts by mass or less.

In the preparation of the titanium black dispersion according to the present invention, the polymer component contained in the titanium black dispersion is 5 parts by mass or more and 200 parts by mass or less, more preferably 10 parts by mass or more and 100 parts by mass with respect to 100 parts by mass of titanium black. It is preferable to add below.
If the polymer component is 5 parts by mass or more, the surface property of the black color material can be kept better, and if the polymer component is 200 parts by mass or less, the inherently required black color such as light-shielding property and colorability The characteristics of the material can be further improved.
Further, specifically, when a polymer dispersant is used, the amount of use thereof ranges from 5 parts by mass to 100 parts by mass with respect to 100 parts by mass of pigment (total pigment including titanium black). The range of 10 to 80 parts by mass is more preferable.
In the case of using a pigment derivative, the amount used is preferably in the range of 1 part by mass to 30 parts by mass with respect to 100 parts by mass of the pigment, and in the range of 3 parts by mass to 20 parts by mass. More preferably, it is in the range of 5 parts by mass or more and 15 parts by mass or less.

[(B) Polymerizable compound]
The polymerizable composition of the present invention contains (B) a polymerizable compound.
The polymerizable compound that can be used in the polymerizable composition of the present invention is an addition polymerizable compound having at least one ethylenically unsaturated double bond, and has at least one terminal ethylenically unsaturated bond, preferably 2 It is selected from compounds having at least one. Such a compound group is widely known in the industrial field, and can be used without any particular limitation in the present invention.
These have chemical forms such as monomers, prepolymers, i.e. dimers, trimers and oligomers, or mixtures thereof and copolymers thereof. Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), and esters and amides thereof. In this case, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used. In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and monofunctional or polyfunctional A dehydration condensation reaction product with a functional carboxylic acid is also preferably used. Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable. As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

  Specific examples of the monomer of an ester of an aliphatic polyhydric alcohol compound and an unsaturated carboxylic acid include acrylic acid esters such as ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, and tetramethylene glycol. Diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate , Tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate , Pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomer, isocyanuric acid There are EO-modified triacrylate and the like.

  Methacrylic acid esters include tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethacrylate, Hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- (3-methacryloxy- 2-hydroxypro ) Phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane.

Itaconic acid esters include ethylene glycol diitaconate, propylene glycol diitaconate, 1,3-butanediol diitaconate, 1,4-butanediol diitaconate, tetramethylene glycol diitaconate, pentaerythritol diitaconate And sorbitol tetritaconate.
Examples of crotonic acid esters include ethylene glycol dicrotonate, tetramethylene glycol dicrotonate, pentaerythritol dicrotonate, and sorbitol tetradicrotonate. Examples of isocrotonic acid esters include ethylene glycol diisocrotonate, pentaerythritol diisocrotonate, and sorbitol tetraisocrotonate.
Examples of maleic acid esters include ethylene glycol dimaleate, triethylene glycol dimaleate, pentaerythritol dimaleate, and sorbitol tetramaleate.

  Examples of other esters include aliphatic alcohol esters described in JP-B-51-47334 and JP-A-57-196231, JP-A-59-5240, and JP-A-59-5241. And those having an aromatic skeleton described in JP-A-2-226149 and those containing an amino group described in JP-A-1-165613. Furthermore, the ester monomers described above can also be used as a mixture.

Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like.
Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B No. 54-21726.

  Further, urethane-based addition polymerizable compounds produced by using an addition reaction of isocyanate and hydroxyl group are also suitable. Specific examples thereof include, for example, one molecule described in JP-B-48-41708. A vinyl urethane containing two or more polymerizable vinyl groups in one molecule obtained by adding a vinyl monomer containing a hydroxyl group represented by the following general formula (A) to a polyisocyanate compound having two or more isocyanate groups. Compounds and the like.

^{_{CH 2 = C (R 4)}} COOCH 2 CH (R 5) OH (A)
(However, in general formula (A), R ⁴ and R ⁵ each represent H or CH _3. )

  Also, urethane acrylates such as those described in JP-A-51-37193, JP-B-2-32293, JP-B-2-16765, JP-B-58-49860, JP-B-56- Urethane compounds having an ethylene oxide skeleton described in Japanese Patent No. 17654, Japanese Patent Publication No. 62-39417, and Japanese Patent Publication No. 62-39418 are also suitable. Furthermore, by using polymerizable compounds having an amino structure or a sulfide structure in the molecule described in JP-A-63-277653, JP-A-63-260909, and JP-A-1-105238. Can obtain a photopolymerizable composition having an excellent photosensitive speed.

  Other examples include polyester acrylates, epoxy resins and (meth) acrylic acid as described in JP-A-48-64183, JP-B-49-43191, JP-B-52-30490, and JP-A-52-30490. Mention may be made of polyfunctional acrylates and methacrylates such as reacted epoxy acrylates. Also, specific unsaturated compounds described in JP-B-46-43946, JP-B-1-40337, JP-B-1-40336, vinylphosphonic acid compounds described in JP-A-2-25493, and the like Can be mentioned. In some cases, a structure containing a perfluoroalkyl group described in JP-A-61-22048 is preferably used. Furthermore, the Japan Adhesion Association magazine vol. 20, no. 7, pages 300 to 308 (1984), which are introduced as photocurable monomers and oligomers, can also be used.

About these polymeric compounds, the details of usage methods, such as the structure, single use, combined use, and addition amount, can be arbitrarily set according to the final performance design of polymeric composition. For example, it is selected from the following viewpoints.
From the viewpoint of sensitivity, a structure having a large unsaturated group content per molecule is preferable, and in many cases, a bifunctional or higher functionality is preferable. Further, in order to increase the strength of the cured film, those having three or more functionalities are preferable, and further, different functional numbers and different polymerizable groups (for example, acrylic acid ester, methacrylic acid ester, styrene compound, vinyl ether compound). A method of adjusting both sensitivity and intensity by using a combination of these materials is also effective.
In addition, selection and use of polymerizable compounds for compatibility and dispersibility with other components (for example, photopolymerization initiators, colorants (pigments, dyes), etc.) contained in the polymerizable composition Is an important factor. For example, compatibility may be improved by the use of a low-purity compound or a combination of two or more. In addition, a specific structure may be selected for the purpose of improving adhesion to a hard surface such as a support.

  In the total solid content of the polymerizable composition, the content of the polymerizable compound (B) is preferably 5% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 85% by mass or less, and 20 More preferably, it is at least 80% by mass.

[(C) Photopolymerization initiator]
The polymerizable composition of the present invention contains (C) a photopolymerization initiator.
The photopolymerization initiator in the present invention is a compound that is decomposed by light and initiates and accelerates polymerization of the polymerizable compound (B), and preferably has absorption in a wavelength region of 300 nm to 500 nm. Moreover, a photoinitiator can be used individually or in combination of 2 or more types.

  Examples of the photopolymerization initiator include organic halogenated compounds, oxydiazole compounds, carbonyl compounds, ketal compounds, benzoin compounds, acridine compounds, organic peroxide compounds, azo compounds, coumarin compounds, azide compounds, metallocene compounds, hexaaryls. Examples include rubiimidazole compounds, organic boric acid compounds, disulfonic acid compounds, oxime ester compounds, onium salt compounds, and acylphosphine (oxide) compounds.

  Specific examples of the organic halogenated compounds include Wakabayashi et al., “Bull Chem. Soc Japan” 42, 2924 (1969), US Pat. No. 3,905,815, Japanese Examined Patent Publication No. 46-4605, Japanese Unexamined Patent Publication No. 48-36281, Japanese Unexamined Patent Publication No. 55-3070, Japanese Unexamined Patent Publication No. 60-239736, Japanese Unexamined Patent Publication No. 61-169835, Japanese Unexamined Patent Publication No. 61-169837, Japanese Unexamined Patent Publication No. 62-58241. JP, 62-21401, JP 63-70243, 63-298339, M.M. P. Hutt “Journal of Heterocyclic Chemistry” 1 (No 3), (1970) ”, and the oxazole compound and s-triazine compound substituted with a trihalomethyl group.

  As the s-triazine compound, more preferably, an s-triazine derivative in which at least one mono-, di-, or trihalogen-substituted methyl group is bonded to the s-triazine ring, specifically, for example, 2,4,6- Tris (monochloromethyl) -s-triazine, 2,4,6-tris (dichloromethyl) -s-triazine, 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6- Bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β-trichloroethyl) -4,6-bis (trichloro Methyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (3,4-epoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4,6-bis (trichloromethyl)- s-triazine, 2- [1- (p-methoxyphenyl) -2,4-butadienyl] -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -S-triazine, 2- (p-methoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (pi-propyloxystyryl) -4,6-bis (trichloromethyl)- s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-natoxynaphthyl) -4,6-bis (trichloromethyl) s-triazine, 2-phenylthio-4,6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4,6-bis (trichloromethyl) -s-triazine, 2,4,6-tris (dibromomethyl) ) -S-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-methoxy-4,6- Bis (tribromomethyl) -s-triazine and the like can be mentioned.

  Examples of the oxydiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2- Examples include trichloromethyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, and the like. .

  Examples of the carbonyl compound include benzophenone, Michler ketone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone and other benzophenone derivatives, 2,2-dimethoxy-2 -Phenylacetophenone, 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenylketone, α-hydroxy-2-methylphenylpropanone, 1-hydroxy-1-methylethyl- (p-isopropylphenyl) ketone, 1-hydroxy -1- (p-dodecylphenyl) ketone, 2-methyl- (4 ′-(methylthio) phenyl) -2-morpholino-1-propanone, 1,1,1-trichloromethyl- (p-butylphenyl) , Acetophenone derivatives such as 2-benzyl-2-dimethylamino-4-morpholinobutyrophenone, thioxanthone, 2-ethylthioxanthone, 2-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone Thioxanthone derivatives such as 2,4-diisopropylthioxanthone, and benzoic acid ester derivatives such as ethyl p-dimethylaminobenzoate and ethyl p-diethylaminobenzoate.

  Examples of the ketal compound include benzyl methyl ketal and benzyl-β-methoxyethyl ethyl acetal.

  Examples of the benzoin compound include mbenzoin isopropyl ether, benzoin isobutyl ether, benzoin methyl ether, methyl o-benzoylbenzoate, and the like.

  Examples of the acridine compound include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the organic peroxide compound include trimethylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis (tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-butylperoxide). Oxy) cyclohexane, 2,2-bis (tert-butylperoxy) butane, tert-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroper Oxide, 1,1,3,3-tetramethylbutyl hydroperoxide, tert-butylcumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) hexane, 2 , -Oxanoyl peroxide, succinic peroxide, benzoyl peroxide, 2,4-dichlorobenzoyl peroxide, diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate, di-2-ethoxyethyl peroxydicarbonate , Dimethoxyisopropyl peroxycarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, tert-butyl peroxyacetate, tert-butyl peroxypivalate, tert-butyl peroxyneodecanoate, tert- Butyl peroxyoctanoate, tert-butyl peroxylaurate, tersyl carbonate, 3,3 ′, 4,4′-tetra- (t-butylperoxycarbonyl) benzophenone, 3,3 ′, 4 '-Tetra- (t-hexylperoxycarbonyl) benzophenone, 3,3', 4,4'-tetra- (p-isopropylcumylperoxycarbonyl) benzophenone, carbonyldi (t-butylperoxydihydrogen diphthalate) , Carbonyldi (t-hexylperoxydihydrogen diphthalate) and the like.

  Examples of the azo compound include azo compounds described in JP-A-8-108621.

  Examples of the coumarin compound include 3-methyl-5-amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl). ) Amino) -3-phenylcoumarin, 3-butyl-5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, and the like.

  Examples of the azide compound include organic azide compounds described in U.S. Pat. No. 2,848,328, U.S. Pat. No. 2,852,379 and U.S. Pat. No. 2,940,553, 2,6-bis (4-azidobenzylidene) -4-ethyl. And cyclohexanone (BAC-E).

  Examples of the metallocene compound include JP-A-59-152396, JP-A-61-151197, JP-A-63-41484, JP-A-2-249, JP-A-2-4705, Various titanocene compounds described in JP-A-5-83588, such as di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di -Cyclopentadienyl-Ti-bis-2,4-di-fluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di- Cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentaful Lophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4,6-trifluoropheny -1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4 , 5,6-pentafluorophen-1-yl, iron-arene complexes described in JP-A-1-304453 and JP-A-1-152109, and the like.

As the biimidazole compound, for example, a hexaarylbiimidazole compound (rophine dimer compound) is preferable.
Examples of the hexaarylbiimidazole compound include lophine dimers described in JP-B-45-37377 and JP-B-44-86516, JP-B-6-29285, U.S. Pat. No. 3,479,185, and the like. Various compounds described in each specification such as 4,311,783 and 4,622,286, specifically, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-bromophenyl)) 4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o, p-dichlorophenyl) ) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetra (m-methoxyphenyl) vididazole, 2, 2'-bis (o , O′-dichlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-nitrophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-methylphenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole, 2,2′-bis (o-trifluorophenyl) -4,4 ′, 5,5 Examples include '-tetraphenylbiimidazole.

  Examples of the organic borate compound include JP-A-62-143044, JP-A-62-1050242, JP-A-9-188585, JP-A-9-188686, JP-A-9-188710, JP-A-2000. -131837, Japanese Patent Application Laid-Open No. 2002-107916, Japanese Patent No. 2764769, Japanese Patent Application No. 2000-310808, etc., and Kunz, Martin “Rad Tech '98. Proceeding April 19-22, 1998, Chicago”. Organoboron salts described in JP-A-6-157623, JP-A-6-175564, JP-A-6-175561, JP-A-6-175554 In Japanese Patent Laid-Open No. 6-175553 Organoboron iodonium complexes, organoboron phosphonium complexes described in JP-A-9-188710, JP-A-6-348011, JP-A-7-128785, JP-A-7-140589, JP-A-7- Specific examples include organoboron transition metal coordination complexes such as those described in Japanese Patent No. 306527 and Japanese Patent Laid-Open No. 7-292014.

  Examples of the disulfone compound include compounds described in JP-A No. 61-166544 and Japanese Patent Application No. 2001-132318.

  Examples of oxime ester compounds include J.M. C. S. Perkin II (1979) 1653-1660), J. MoI. C. S. Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, JP-A 2000-66385, compounds described in JP-A 2000-80068, JP-T 2004-534797 Compounds and the like.

  The oxime compound as the photopolymerization initiator is more preferably a compound represented by the following formula (3) from the viewpoints of sensitivity, temporal stability, and coloring during post-heating.

  In formula (3), R and X each independently represent a monovalent substituent, A represents a divalent organic group, and Ar represents an aryl group. n is an integer of 1-5.

The monovalent substituent represented by R is preferably a monovalent nonmetallic atomic group shown below.
Examples of the monovalent nonmetallic atomic group represented by R include an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkenyl group which may have a substituent, and a substituent. An alkynyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, and a substituent An arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, an alkoxycarbonyl group which may have a substituent, an aryloxycarbonyl group which may have a substituent, and a substituent. Good phosphinoyl group, heterocyclic group which may have a substituent, alkylthiocarbonyl group which may have a substituent, arylthiocarbonyl group which may have a substituent, dialkyl which may have a substituent Aminocal Group, optionally dialkylaminothiocarbonyl group, or the like may have a substituent.

  As the alkyl group which may have a substituent, an alkyl group having 1 to 30 carbon atoms is preferable, for example, methyl group, ethyl group, propyl group, butyl group, hexyl group, octyl group, decyl group, dodecyl group, Okudadecyl group, isopropyl group, isobutyl group, sec-butyl group, t-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl group 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group, 4-methylphenacyl group, 2-methylphenacyl group , 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, 3-nitro Enashiru group, and the like.

  As the aryl group which may have a substituent, an aryl group having 6 to 30 carbon atoms is preferable, and a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, a 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o- , M-, and p-cumenyl group, mesityl group, pentarenyl group, binaphthalenyl group, turnaphthalenyl group, quarternaphthalenyl group, heptaenyl group, biphenylenyl group, indacenyl group, fluoranthenyl group, acenaphthylenyl group, aceanthrylenyl group, Phenalenyl, fluorenyl, anthryl, bianthracenyl, teranthraceni Group, quarter anthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexa Examples thereof include a phenyl group, a hexacenyl group, a rubicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group.

  The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, for example, methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, hexyl. Examples thereof include a sulfinyl group, a cyclohexylsulfinyl group, an octylsulfinyl group, a 2-ethylhexylsulfinyl group, a decanoylsulfinyl group, a dodecanoylsulfinyl group, an octadecanoylsulfinyl group, a cyanomethylsulfinyl group, and a methoxymethylsulfinyl group.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, for example, phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group. 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenyl Sulfinyl group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexyl. Sulfonyl group, cyclohexylsulfonyl group, octylsulfonyl group, 2-ethylhexylsulfonyl group, decanoylsulfonyl group, dodecanoylsulfonyl group, octadecanoylsulfonyl group, cyanomethylsulfonyl group, methoxymethylsulfonyl group, perfluoroalkylsulfonyl group, etc. Can be mentioned.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, and a 2-chlorophenylsulfonyl group. 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylamino Enirusuruhoniru group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 or more and 20 or less carbon atoms. For example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1- Naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxy Benzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxy A benzoyl group etc. are mentioned.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, Examples include octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, trifluoromethyloxycarbonyl group, and the like.

  The aryloxycarbonyl group which may have a substituent includes a phenoxycarbonyl group, a 1-naphthyloxycarbonyl group, a 2-naphthyloxycarbonyl group, a 4-methylsulfanylphenyloxycarbonyl group, and a 4-phenylsulfanylphenyloxycarbonyl group. 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3 -Chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl group, 3-nitrophenyloxycarbonyl group, 4-fur B phenyloxycarbonyl group, 4-cyanophenyl oxycarbonyl group, and 4-methoxyphenyloxycarbonyl group.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms in total, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphino group. Yl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Examples of the alkylthiocarbonyl group which may have a substituent include, for example, a methylthiocarbonyl group, a propylthiocarbonyl group, a butylthiocarbonyl group, a hexylthiocarbonyl group, an octylthiocarbonyl group, a decylthiocarbonyl group, an octadecylthiocarbonyl group, A trifluoromethylthiocarbonyl group etc. are mentioned.

  Examples of the arylthiocarbonyl group which may have a substituent include 1-naphthylthiocarbonyl group, 2-naphthylthiocarbonyl group, 4-methylsulfanylphenylthiocarbonyl group, 4-phenylsulfanylphenylthiocarbonyl group, 4-dimethyl. Aminophenylthiocarbonyl group, 4-diethylaminophenylthiocarbonyl group, 2-chlorophenylthiocarbonyl group, 2-methylphenylthiocarbonyl group, 2-methoxyphenylthiocarbonyl group, 2-butoxyphenylthiocarbonyl group, 3-chlorophenylthiocarbonyl group Group, 3-trifluoromethylphenylthiocarbonyl group, 3-cyanophenylthiocarbonyl group, 3-nitrophenylthiocarbonyl group, 4-fluorophenylthiocarbonyl group, 4-cyanophenylthiocarbonyl group Boniru group, 4-methoxyphenyl thiocarbonyl group.

  Examples of the dialkylaminocarbonyl group that may have a substituent include a dimethylaminocarbonyl group, a dimethylaminocarbonyl group, a dipropylaminocarbonyl group, and a dibutylaminocarbonyl group.

  Examples of the dialkylaminothiocarbonyl group which may have a substituent include a dimethylaminothiocarbonyl group, a dipropylaminothiocarbonyl group, and a dibutylaminothiocarbonyl group.

  Among them, from the viewpoint of increasing sensitivity, R is more preferably an acyl group, and specifically, an acetyl group, an ethyloyl group, a propioyl group, a benzoyl group, and a toluyl group are preferable.

Examples of the divalent organic group represented by A may include an alkylene having 1 to 12 carbon atoms which may have a substituent, cyclohexylene which may have a substituent, and a substituent. Alkynylene is mentioned.
Examples of the substituent that can be introduced into these groups include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group, p- Aryloxy groups such as tolyloxy group, alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy groups such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group Group, acyl group such as methacryloyl group, methoxalyl group, methylsulfanyl group, alkylsulfanyl group such as tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, Alkylamino groups such as hexylamino group, dimethylamino groups, diethylamino groups, morpholino groups, dialkylamino groups such as piperidino groups, phenylamino groups, arylamino groups such as p-tolylamino groups, methyl groups, ethyl groups, tert- In addition to alkyl groups such as butyl group and dodecyl group, phenyl groups, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group and the like, hydroxy group, carboxy group, formyl group, mercapto Group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group Group, triphenylphenacylphos Niumiru group, and the like.
Among them, A is an alkylene substituted with an unsubstituted alkylene group or an alkyl group (for example, a methyl group, an ethyl group, a tert-butyl group, or a dodecyl group) from the viewpoint of increasing sensitivity and suppressing coloration due to heating. Group, alkylene group substituted with alkenyl group (for example, vinyl group, allyl group), aryl group (for example, phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, styryl group) An alkylene group substituted with

The aryl group represented by Ar is preferably an aryl group having 6 to 30 carbon atoms, and may have a substituent.
Specifically, phenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 9-anthryl group, 9-phenanthryl group, 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o-, m-, and p-cumenyl group, mesityl group, pentalenyl group, binaphthalenyl group, Turnaphthalenyl group, Quarter naphthalenyl group, Heptaenyl group, Biphenylenyl group, Indacenyl group, Fluoranthenyl group, Acenaphthylenyl group, Aceantrirenyl group, Phenalenyl group, Fluorenyl group, Anthryl group, Bianthracenyl group, Teranthracenyl group, Quarter Anthracenyl group, anthraquinolyl group, phenanthri Group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, hexaphenyl group, hexacenyl group, rubicenyl group, coronenyl group, A trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyrantrenyl group, an obalenyl group, and the like can be given. Of these, a substituted or unsubstituted phenyl group is preferable from the viewpoint of increasing sensitivity and suppressing coloring due to heating.

  When the phenyl group has a substituent, examples of the substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group. Group, aryloxy group such as phenoxy group, p-tolyloxy group, methylthioxy group, ethylthioxy group, alkylthioxy group such as tert-butylthioxy group, arylthiooxy group such as phenylthioxy group, p-tolyloxy group, methoxycarbonyl Groups, butoxycarbonyl groups, alkoxycarbonyl groups such as phenoxycarbonyl groups, acyloxy groups such as acetoxy groups, propionyloxy groups, benzoyloxy groups, acetyl groups, benzoyl groups, isobutyryl groups, acryloyl groups, methacryloyl groups, methoxalyl groups, etc. Group, Alkylsulfanyl groups such as tilsulfanyl group, tert-butylsulfanyl group, arylsulfanyl groups such as phenylsulfanyl group, p-tolylsulfanyl group, alkylamino groups such as methylamino group, cyclohexylamino group, dimethylamino group, diethylamino group, Dialkylamino groups such as morpholino group and piperidino group, arylamino groups such as phenylamino group and p-tolylamino group, alkyl groups such as ethyl group, tert-butyl group and dodecyl group, hydroxy group, carboxy group, formyl group, mercapto Group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, di Chill sulfo Niu mill group, triphenyl phenacyl phosphonium Niu mill group, and the like.

  In the general formula (3), it is preferable in terms of sensitivity that the structure of “SAr” formed by Ar and adjacent S is the following structure.

  Examples of the monovalent substituent represented by X include an alkyl group that may have a substituent, an aryl group that may have a substituent, an alkenyl group that may have a substituent, and a substituent. An alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy group which may have a substituent, and a substituent. Good arylthioxy group, acyloxy group which may have a substituent, alkylsulfanyl group which may have a substituent, arylsulfanyl group which may have a substituent, alkyl which may have a substituent A sulfinyl group, an arylsulfinyl group which may have a substituent, an alkylsulfonyl group which may have a substituent, an arylsulfonyl group which may have a substituent, an acyl group which may have a substituent, May have a substituent An alkoxycarbonyl group, an optionally substituted carbamoyl group, an optionally substituted sulfamoyl group, an optionally substituted amino group, an optionally substituted phosphinoyl group, and a substituent A heterocyclic group, a halogen group and the like which may have

  The alkyl group which may have a substituent is preferably an alkyl group having 1 to 30 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, a decyl group, or a dodecyl group. , Octadecyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, 1-ethylpentyl group, cyclopentyl group, cyclohexyl group, trifluoromethyl group, 2-ethylhexyl group, phenacyl group, 1-naphthoylmethyl Group, 2-naphthoylmethyl group, 4-methylsulfanylphenacyl group, 4-phenylsulfanylphenacyl group, 4-dimethylaminophenacyl group, 4-cyanophenacyl group 4-methylphenacyl group, 2-methylphenacyl group , 3-fluorophenacyl group, 3-trifluoromethylphenacyl group, - Nitorofenashiru group and the like.

  The aryl group which may have a substituent is preferably an aryl group having 6 to 30 carbon atoms, and includes a phenyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group, a 9-anthryl group, and a 9-phenanthryl group. 1-pyrenyl group, 5-naphthacenyl group, 1-indenyl group, 2-azurenyl group, 9-fluorenyl group, terphenyl group, quarterphenyl group, o-, m-, and p-tolyl group, xylyl group, o -, M-, and p-cumenyl, mesityl, pentarenyl, binaphthalenyl, tarnaphthalenyl, quarternaphthalenyl, heptaenyl, biphenylenyl, indacenyl, fluoranthenyl, acenaphthylenyl, aceanthrylenyl , Phenalenyl group, fluorenyl group, anthryl group, bianthracenyl group, tarant Senyl group, quarteranthracenyl group, anthraquinolyl group, phenanthryl group, triphenylenyl group, pyrenyl group, chrysenyl group, naphthacenyl group, preadenyl group, picenyl group, perylenyl group, pentaphenyl group, pentacenyl group, tetraphenylenyl group, Examples include a hexaphenyl group, a hexacenyl group, a ruvicenyl group, a coronenyl group, a trinaphthylenyl group, a heptaphenyl group, a heptacenyl group, a pyranthrenyl group, and an oberenyl group.

  The alkenyl group which may have a substituent is preferably an alkenyl group having 2 to 10 carbon atoms, and examples thereof include a vinyl group, an allyl group, and a styryl group.

  The alkynyl group which may have a substituent is preferably an alkynyl group having 2 to 10 carbon atoms, and examples thereof include an ethynyl group, a propynyl group, and a propargyl group.

  The alkoxy group which may have a substituent is preferably an alkoxy group having 1 to 30 carbon atoms, for example, methoxy group, ethoxy group, propyloxy group, isopropyloxy group, butoxy group, isobutoxy group, sec-butoxy group. Group, tert-butoxy group, pentyloxy group, isopentyloxy group, hexyloxy group, heptyloxy group, octyloxy group, 2-ethylhexyloxy group, decyloxy group, dodecyloxy group, octadecyloxy group, ethoxycarbonylmethyl group, 2-ethylhexyloxycarbonylmethyloxy group, aminocarbonylmethyloxy group, N, N-dibutylaminocarbonylmethyloxy group, N-methylaminocarbonylmethyloxy group, N-ethylaminocarbonylmethyloxy group, N-octylami Carbonyl methyl group, N- methyl -N- benzylaminocarbonyl methyloxy group, a benzyloxy group, and a cyanomethyloxy group.

  The aryloxy group which may have a substituent is preferably an aryloxy group having 6 to 30 carbon atoms, for example, a phenyloxy group, a 1-naphthyloxy group, a 2-naphthyloxy group, or a 2-chlorophenyloxy group. 2-methylphenyloxy group, 2-methoxyphenyloxy group, 2-butoxyphenyloxy group, 3-chlorophenyloxy group, 3-trifluoromethylphenyloxy group, 3-cyanophenyloxy group, 3-nitrophenyloxy group 4-fluorophenyloxy group, 4-cyanophenyloxy group, 4-methoxyphenyloxy group, 4-dimethylaminophenyloxy group, 4-methylsulfanylphenyloxy group, 4-phenylsulfanylphenyloxy group, and the like.

  The alkylthioxy group which may have a substituent is preferably a thioalkoxy group having 1 to 30 carbon atoms, such as methylthioxy group, ethylthioxy group, propylthioxy group, isopropylthioxy group, butylthioxy group, isobutyl. Thioxy group, sec-butylthioxy group, tert-butylthioxy group, pentylthioxy group, isopentylthioxy group, hexylthioxy, heptylthioxy group, octylthioxy group, 2-ethylhexylthioxy group, decylthioxy group, dodecyl Examples include a thioxy group, an octadecyl thioxy group, and a benzyl thioxy group.

  The arylthioxy group which may have a substituent is preferably an arylthioxy group having 6 to 30 carbon atoms, such as a phenylthioxy group, a 1-naphthylthioxy group, a 2-naphthylthioxy group, 2-chlorophenylthioxy group, 2-methylphenylthioxy group, 2-methoxyphenylthioxy group, 2-butoxyphenylthioxy group, 3-chlorophenylthioxy group, 3-trifluoromethylphenylthioxy group, 3- Cyanophenylthioxy group, 3-nitrophenylthioxy group, 4-fluorophenylthioxy group, 4-cyanophenylthioxy group, 4-methoxyphenylthioxy group, 4-dimethylaminophenylthioxy group, 4-methyl Examples thereof include a sulfanylphenylthioxy group and a 4-phenylsulfanylphenylthioxy group.

  The acyloxy group which may have a substituent is preferably an acyloxy group having 2 to 20 carbon atoms, such as an acetyloxy group, a propanoyloxy group, a butanoyloxy group, a pentanoyloxy group, or trifluoromethylcarbonyl. Examples thereof include an oxy group, a benzoyloxy group, a 1-naphthylcarbonyloxy group, and a 2-naphthylcarbonyloxy group.

  The alkylsulfanyl group which may have a substituent is preferably an alkylsulfanyl group having 1 to 20 carbon atoms, such as methylsulfanyl group, ethylsulfanyl group, propylsulfanyl group, isopropylsulfanyl group, butylsulfanyl group, hexyl. Examples include a sulfanyl group, a cyclohexylsulfanyl group, an octylsulfanyl group, a 2-ethylhexylsulfanyl group, a decanoylsulfanyl group, a dodecanoylsulfanyl group, an octadecanoylsulfanyl group, a cyanomethylsulfanyl group, and a methoxymethylsulfanyl group.

  The arylsulfanyl group which may have a substituent is preferably an arylsulfanyl group having 6 to 30 carbon atoms, such as a phenylsulfanyl group, a 1-naphthylsulfanyl group, a 2-naphthylsulfanyl group, or a 2-chlorophenylsulfanyl group. 2-methylphenylsulfanyl group, 2-methoxyphenylsulfanyl group, 2-butoxyphenylsulfanyl group, 3-chlorophenylsulfanyl group, 3-trifluoromethylphenylsulfanyl group, 3-cyanophenylsulfanyl group, 3-nitrophenylsulfanyl group 4-fluorophenylsulfanyl group, 4-cyanophenylsulfanyl group, 4-methoxyphenylsulfanyl group, 4-methylsulfanylphenylsulfanyl group, 4-phenylsulfanylphenyl Sulfanyl group, 4-dimethylamino-phenylsulfanyl group and the like.

  The alkylsulfinyl group which may have a substituent is preferably an alkylsulfinyl group having 1 to 20 carbon atoms, for example, methylsulfinyl group, ethylsulfinyl group, propylsulfinyl group, isopropylsulfinyl group, butylsulfinyl group, hexyl. Examples thereof include a sulfinyl group, a cyclohexylsulfinyl group, an octylsulfinyl group, a 2-ethylhexylsulfinyl group, a decanoylsulfinyl group, a dodecanoylsulfinyl group, an octadecanoylsulfinyl group, a cyanomethylsulfinyl group, and a methoxymethylsulfinyl group.

  The arylsulfinyl group which may have a substituent is preferably an arylsulfinyl group having 6 to 30 carbon atoms, for example, phenylsulfinyl group, 1-naphthylsulfinyl group, 2-naphthylsulfinyl group, 2-chlorophenylsulfinyl group. 2-methylphenylsulfinyl group, 2-methoxyphenylsulfinyl group, 2-butoxyphenylsulfinyl group, 3-chlorophenylsulfinyl group, 3-trifluoromethylphenylsulfinyl group, 3-cyanophenylsulfinyl group, 3-nitrophenylsulfinyl group 4-fluorophenylsulfinyl group, 4-cyanophenylsulfinyl group, 4-methoxyphenylsulfinyl group, 4-methylsulfanylphenylsulfinyl group, 4-phenylsulfanylphenyl Sulfinyl group, 4-dimethylaminophenyl sulfinyl group and the like.

  The alkylsulfonyl group which may have a substituent is preferably an alkylsulfonyl group having 1 to 20 carbon atoms, for example, methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, isopropylsulfonyl group, butylsulfonyl group, hexyl. Examples include a sulfonyl group, a cyclohexylsulfonyl group, an octylsulfonyl group, a 2-ethylhexylsulfonyl group, a decanoylsulfonyl group, a dodecanoylsulfonyl group, an octadecanoylsulfonyl group, a cyanomethylsulfonyl group, and a methoxymethylsulfonyl group.

  The arylsulfonyl group which may have a substituent is preferably an arylsulfonyl group having 6 to 30 carbon atoms, such as a phenylsulfonyl group, a 1-naphthylsulfonyl group, a 2-naphthylsulfonyl group, and a 2-chlorophenylsulfonyl group. 2-methylphenylsulfonyl group, 2-methoxyphenylsulfonyl group, 2-butoxyphenylsulfonyl group, 3-chlorophenylsulfonyl group, 3-trifluoromethylphenylsulfonyl group, 3-cyanophenylsulfonyl group, 3-nitrophenylsulfonyl group 4-fluorophenylsulfonyl group, 4-cyanophenylsulfonyl group, 4-methoxyphenylsulfonyl group, 4-methylsulfanylphenylsulfonyl group, 4-phenylsulfanylphenylsulfonyl group, 4-dimethylamino Enirusuruhoniru group, and the like.

  The acyl group which may have a substituent is preferably an acyl group having 2 or more and 20 or less carbon atoms. For example, acetyl group, propanoyl group, butanoyl group, trifluoromethylcarbonyl group, pentanoyl group, benzoyl group, 1- Naphthoyl group, 2-naphthoyl group, 4-methylsulfanylbenzoyl group, 4-phenylsulfanylbenzoyl group, 4-dimethylaminobenzoyl group, 4-diethylaminobenzoyl group, 2-chlorobenzoyl group, 2-methylbenzoyl group, 2-methoxy Benzoyl group, 2-butoxybenzoyl group, 3-chlorobenzoyl group, 3-trifluoromethylbenzoyl group, 3-cyanobenzoyl group, 3-nitrobenzoyl group, 4-fluorobenzoyl group, 4-cyanobenzoyl group, 4-methoxy A benzoyl group etc. are mentioned.

  The alkoxycarbonyl group which may have a substituent is preferably an alkoxycarbonyl group having 2 to 20 carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a butoxycarbonyl group, a hexyloxycarbonyl group, Octyloxycarbonyl group, decyloxycarbonyl group, octadecyloxycarbonyl group, phenoxycarbonyl group, trifluoromethyloxycarbonyl group, 1-naphthyloxycarbonyl group, 2-naphthyloxycarbonyl group, 4-methylsulfanylphenyloxycarbonyl group, 4 -Phenylsulfanylphenyloxycarbonyl group, 4-dimethylaminophenyloxycarbonyl group, 4-diethylaminophenyloxycarbonyl group, 2-chlorophenyloxycarbonyl Bonyl group, 2-methylphenyloxycarbonyl group, 2-methoxyphenyloxycarbonyl group, 2-butoxyphenyloxycarbonyl group, 3-chlorophenyloxycarbonyl group, 3-trifluoromethylphenyloxycarbonyl group, 3-cyanophenyloxycarbonyl Group, 3-nitrophenyloxycarbonyl group, 4-fluorophenyloxycarbonyl group, 4-cyanophenyloxycarbonyl group, 4-methoxyphenyloxycarbonyl group and the like.

  The carbamoyl group which may have a substituent is preferably a carbamoyl group having 1 to 30 carbon atoms in total, for example, N-methylcarbamoyl group, N-ethylcarbamoyl group, N-propylcarbamoyl group, N-butylcarbamoyl group. Group, N-hexylcarbamoyl group, N-cyclohexylcarbamoyl group, N-octylcarbamoyl group, N-decylcarbamoyl group, N-octadecylcarbamoyl group, N-phenylcarbamoyl group, N-2-methylphenylcarbamoyl group, N-2 -Chlorophenylcarbamoyl group, N-2-isopropoxyphenylcarbamoyl group, N-2- (2-ethylhexyl) phenylcarbamoyl group, N-3-chlorophenylcarbamoyl group, N-3-nitrophenylcarbamoyl group, N-3-cyano Phenylcarbamo Group, N-4-methoxyphenylcarbamoyl group, N-4-cyanophenylcarbamoyl group, N-4-methylsulfanylphenylcarbamoyl group, N-4-phenylsulfanylphenylcarbamoyl group, N-methyl-N-phenylcarbamoyl group N, N-dimethylcarbamoyl group, N, N-dibutylcarbamoyl group, N, N-diphenylcarbamoyl group and the like.

  The sulfamoyl group which may have a substituent is preferably a sulfamoyl group having 0 to 30 carbon atoms in total, for example, sulfamoyl group, N-alkylsulfamoyl group, N-arylsulfamoyl group, N, N -Dialkylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group and the like can be mentioned. More specifically, N-methylsulfamoyl group, N-ethylsulfamoyl group, N-propylsulfamoyl group, N-butylsulfamoyl group, N-hexylsulfamoyl group, N-cyclohexylsulfur group. Famoyl group, N-octylsulfamoyl group, N-2-ethylhexylsulfamoyl group, N-decylsulfamoyl group, N-octadecylsulfamoyl group, N-phenylsulfamoyl group, N-2- Methylphenylsulfamoyl group, N-2-chlorophenylsulfamoyl group, N-2-methoxyphenylsulfamoyl group, N-2-isopropoxyphenylsulfamoyl group, N-3-chlorophenylsulfamoyl group, N-3-nitrophenylsulfamoyl group, N-3-cyanophenylsulfamoyl group, N-4-methoxyphenyl Nylsulfamoyl group, N-4-cyanophenylsulfamoyl group, N-4-dimethylaminophenylsulfamoyl group, N-4-methylsulfanylphenylsulfamoyl group, N-4-phenylsulfanylphenylsulfamoyl Group, N-methyl-N-phenylsulfamoyl group, N, N-dimethylsulfamoyl group, N, N-dibutylsulfamoyl group, N, N-diphenylsulfamoyl group and the like.

The amino group which may have a substituent is preferably an amino group having 0 to 50 carbon atoms in total, for example, —NH ₂ , N-alkylamino group, N-arylamino group, N-acylamino group, N -Sulfonylamino group, N, N-dialkylamino group, N, N-diarylamino group, N-alkyl-N-arylamino group, N, N-disulfonylamino group and the like can be mentioned. More specifically, N-methylamino group, N-ethylamino group, N-propylamino group, N-isopropylamino group, N-butylamino group, N-tert-butylamino group, N-hexylamino group, N-cyclohexylamino group, N-octylamino group, N-2-ethylhexylamino group, N-decylamino group, N-octadecylamino group, N-benzylamino group, N-phenylamino group, N-2-methylphenylamino Group, N-2-chlorophenylamino group, N-2-methoxyphenylamino group, N-2-isopropoxyphenylamino group, N-2- (2-ethylhexyl) phenylamino group, N-3-chlorophenylamino group, N-3-nitrophenylamino group, N-3-cyanophenylamino group, N-3-trifluoromethylphenyla Group, N-4-methoxyphenylamino group, N-4-cyanophenylamino group, N-4-trifluoromethylphenylamino group, N-4-methylsulfanylphenylamino group, N-4-phenylsulfanylphenylamino Group, N-4-dimethylaminophenylamino group, N-methyl-N-phenylamino group, N, N-dimethylamino group, N, N-diethylamino group, N, N-dibutylamino group, N, N-diphenyl Amino group, N, N-diacetylamino group, N, N-dibenzoylamino group, N, N- (dibutylcarbonyl) amino group, N, N- (dimethylsulfonyl) amino group, N, N- (diethylsulfonyl) Amino group, N, N- (dibutylsulfonyl) amino group, N, N- (diphenylsulfonyl) amino group, morpholino group, 3, - dimethyl morpholino group, and a carbazolyl group.

  The phosphinoyl group which may have a substituent is preferably a phosphinoyl group having 2 to 50 carbon atoms in total, for example, dimethylphosphinoyl group, diethylphosphinoyl group, dipropylphosphinoyl group, diphenylphosphino group. Yl group, dimethoxyphosphinoyl group, diethoxyphosphinoyl group, dibenzoylphosphinoyl group, bis (2,4,6-trimethylphenyl) phosphinoyl group and the like.

  The heterocyclic group that may have a substituent is preferably an aromatic or aliphatic heterocyclic ring containing a nitrogen atom, an oxygen atom, a sulfur atom, or a phosphorus atom. For example, thienyl group, benzo [b] thienyl group, naphtho [2,3-b] thienyl group, thiantenyl group, furyl group, pyranyl group, isobenzofuranyl group, chromenyl group, xanthenyl group, phenoxathinyl group, 2H-pyrrolyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolizinyl group, isoindolyl group, 3H-indolyl group, indolyl group, 1H-indazolyl group, purinyl group, 4H- Quinolidinyl group, isoquinolyl group, quinolyl group, phthalazinyl group, naphthyridinyl group, quinoxanilyl group, quinazolinyl group, cinnolinyl group, pteridinyl group, 4aH-carbazolyl group, carbazolyl group, β-carbolinyl group, phenanthridinyl group, acridinyl group, perimidinyl group Nyl group, phenanthrolinyl group, phenazinyl group, phenalsadinyl group, isothiazolyl group, phenothiazinyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, isochromanyl group, chromanyl group, pyrrolidinyl group, pyrrolinyl group, imidazolidinyl group, imidazolinyl group, pyrazolidinyl group Group, pyrazolinyl group, piperidyl group, piperazinyl group, indolinyl group, isoindolinyl group, quinuclidinyl group, morpholinyl group, thioxanthryl group and the like.

  Examples of the halogen group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

  Furthermore, the alkyl group which may have a substituent mentioned above, the aryl group which may have a substituent, the alkenyl group which may have a substituent, the alkynyl group which may have a substituent, a substituent An alkoxy group that may have a substituent, an aryloxy group that may have a substituent, an alkylthioxy group that may have a substituent, an arylthioxy group that may have a substituent, and a substituent. An acyloxy group which may have a substituent, an alkylsulfanyl group which may have a substituent, an arylsulfanyl group which may have a substituent, an alkylsulfinyl group which may have a substituent, and a substituent. Good arylsulfinyl group, alkylsulfonyl group which may have a substituent, arylsulfonyl group which may have a substituent, acyl group which may have a substituent, alkoxycarbonyl which may have a substituent Base The carbamoyl group which may have a substituent, the sulfamoyl group which may have a substituent, the amino group which may have a substituent, and the heterocyclic group which may have a substituent may be further substituted. It may be substituted with a group.

  Examples of such a substituent include halogen groups such as fluorine atom, chlorine atom, bromine atom and iodine atom, alkoxy groups such as methoxy group, ethoxy group and tert-butoxy group, phenoxy group and p-tolyloxy group. Aryloxy group, alkoxycarbonyl group such as methoxycarbonyl group, butoxycarbonyl group, phenoxycarbonyl group, acyloxy group such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group , Acyl group such as methoxalyl group, alkylsulfanyl group such as methylsulfanyl group, tert-butylsulfanyl group, arylsulfanyl group such as phenylsulfanyl group, p-tolylsulfanyl group, methylamino group, cyclohexyl Alkylamino group such as mino group, dimethylamino group, diethylamino group, morpholino group, dialkylamino group such as piperidino group, arylamino group such as phenylamino group, p-tolylamino group, methyl group, ethyl group, tert-butyl group In addition to alkyl groups such as dodecyl group, phenyl groups, p-tolyl groups, xylyl groups, cumenyl groups, naphthyl groups, anthryl groups, phenanthryl groups, etc., hydroxy groups, carboxy groups, formyl groups, mercapto groups, Sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammonium group, dimethylsulfonyl group, Triphenylphenacylphosphoniumyl group And the like.

Among these, X has an alkyl group which may have a substituent, an aryl group which may have a substituent, and a substituent from the viewpoint of improving solvent solubility and absorption efficiency in the long wavelength region. An alkenyl group which may have a substituent, an alkynyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an alkylthioxy which may have a substituent A group, an arylthioxy group which may have a substituent, and an amino group which may have a substituent are preferable.
Moreover, although n in General formula (3) represents the integer of 0-5, the integer of 0-2 is preferable.

  Hereinafter, although the specific example of an oxime compound represented by General formula (3) is shown below, this invention is not limited to these.

  The oxime compound represented by the general formula (3) has a function as a photopolymerization initiator that is decomposed by light and initiates and accelerates polymerization of the photopolymerizable compound. In particular, the oxime compound has excellent sensitivity to a light source of 365 nm or 405 nm.

  Examples of onium salt compounds include S.I. I. Schlesinger, Photogr. Sci. Eng. 18, 387 (1974), T .; S. Bal et al, Polymer, 21, 423 (1980), diazonium salts described in U.S. Pat. No. 4,069,055, ammonium salts described in JP-A-4-365049, U.S. Pat. No. 4,069, No. 055, No. 4,069,056, phosphonium salts described in European Patent Nos. 104 and 143, U.S. Pat. Nos. 339,049 and 410,201, JP Examples include iodonium salts described in JP-A No. -150848 and JP-A-2-296514.

  The iodonium salt that can be suitably used in the present invention is a diaryl iodonium salt, and is preferably substituted with two or more electron donating groups such as an alkyl group, an alkoxy group, and an aryloxy group from the viewpoint of stability. . In addition, as another preferable form of the sulfonium salt, an iodonium salt in which one substituent of the triarylsulfonium salt has a coumarin or an anthraquinone structure and absorption at 300 nm or more is preferable.

Examples of the sulfonium salt that can be suitably used in the present invention include European Patent Nos. 370,693, 390,214, 233,567, 297,443, 297,442, and U.S. Pat. 933,377, 161,811, 410,201, 339,049, 4,760,013, 4,734,444, 2,833,827, Germany Examples thereof include sulfonium salts described in the specifications of Patent Nos. 2,904,626, 3,604,580, and 3,604,581, and are preferably electron withdrawing groups from the viewpoint of stability. It is preferably substituted. The electron withdrawing group preferably has a Hammett value greater than zero. Preferred electron-withdrawing groups include halogen atoms and carboxylic acids.
Other preferable sulfonium salts include sulfonium salts in which one substituent of the triarylsulfonium salt has a coumarin or anthraquinone structure and absorbs at 300 nm or more. As another preferable sulfonium salt, a sulfonium salt in which the triarylsulfonium salt has an allyloxy group or an arylthio group as a substituent and has absorption at 300 nm or more can be mentioned.

  Moreover, as an onium salt compound, J.M. V. Crivello et al, Macromolecules, 10 (6), 1307 (1977), J. MoI. V. Crivello et al, J.A. Polymer Sci. , Polymer Chem. Ed. , 17, 1047 (1979), a selenonium salt described in C.I. S. Wen et al, Teh, Proc. Conf. Rad. Curing ASIA, p478 Tokyo, Oct (1988), and onium salts such as arsonium salts.

  Examples of the acylphosphine (oxide) compound include Irgacure 819, Darocur 4265, Darocur TPO and the like manufactured by Ciba Specialty Chemicals.

  As the photopolymerization initiator (C) used in the present invention, from the viewpoint of exposure sensitivity, a trihalomethyltriazine compound, a benzyldimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, phosphine Oxide compounds, metallocene compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-benzene-iron complexes and salts thereof, halomethyl oxa Compounds selected from the group consisting of diazole compounds and 3-aryl substituted coumarin compounds are preferred.

  More preferred are trihalomethyltriazine compounds, α-aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, oxime compounds, triallylimidazole dimers, onium compounds, benzophenone compounds, acetophenone compounds, and trihalo compounds. Most preferred is at least one compound selected from the group consisting of a methyltriazine compound, an α-aminoketone compound, an oxime compound, a triallylimidazole dimer, and a benzophenone compound.

  In particular, when the polymerizable composition of the present invention is used for the production of a solid-state imaging device of a color filter, it is necessary to form fine pixels with a sharp shape, and therefore a residue is left in the unexposed area as well as curability. It is important that it is developed without any problems. From such a viewpoint, an oxime compound is particularly preferable. In particular, when fine pixels are formed in a solid-state imaging device, stepper exposure is used for curing exposure, but this exposure machine may be damaged by halogen, and the amount of photopolymerization initiator added must be kept low. Therefore, in view of these points, it can be said that it is most preferable to use an oxime compound as the photopolymerization initiator (C) in order to form a finely colored pattern such as a solid-state imaging device.

  The content of the (C) photopolymerization initiator contained in the polymerizable composition of the present invention is preferably 0.1% by mass or more and 50% by mass or less with respect to the total solid content of the polymerizable composition. Preferably they are 0.5 mass% or more and 30 mass% or less, More preferably, they are 1 mass% or more and 20 mass% or less. Within this range, good sensitivity and pattern formability can be obtained.

The polymerizable composition of the present invention may further contain optional components described in detail below, if necessary.
Hereinafter, optional components that the polymerizable composition may contain will be described.

[Polymerization inhibitor]
In the present invention, it is preferable to add a polymerization inhibitor in order to prevent unnecessary polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during production or storage of the polymerizable composition.
Examples of the polymerization inhibitor that can be used in the present invention include phenolic hydroxyl group-containing compounds, N-oxide compounds, piperidine 1-oxyl free radical compounds, pyrrolidine 1-oxyl free radical compounds, N-nitrosophenylhydroxylamines, diazonium. Examples include compounds, and cationic dyes, sulfide group-containing compounds, nitro group-containing compounds, and transition metal compounds such as FeCl ₃ and CuCl ₂ .

Further preferred embodiments are as follows.
The phenolic hydroxyl group-containing compound is hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t-butylphenol), A compound selected from the group consisting of 2,2′-methylenebis (4-methyl-6-tert-butylphenol), phenol resins, and cresol resins is preferred.

  N-oxide compounds are 5,5-dimethyl-1-pyrroline N-oxide, 4-methylmorpholine N-oxide, pyridine N-oxide, 4-nitropyridine N-oxide, 3-hydroxypyridine N-oxide, picoline A compound selected from the group consisting of acid N-oxide, nicotinic acid N-oxide, and isonicotinic acid N-oxide is preferred.

  Piperidine 1-oxyl free radical compounds are converted to piperidine 1-oxyl free radical, 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1 -Oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimide A compound selected from the group consisting of -2,2,6,6-tetramethylpiperidine 1-oxyl free radical and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical Is preferred.

  The pyrrolidine 1-oxyl free radical compounds are preferably 3-carboxyproxyl free radicals (3-carboxy-2,2,5,5-tetramethylpyrrolidine 1-oxyl free radical).

  The N-nitrosophenylhydroxylamines are preferably compounds selected from the group consisting of N-nitrosophenylhydroxylamine primary cerium salts and N-nitrosophenylhydroxylamine aluminum salts.

  A compound in which the diazonium compounds are selected from the group consisting of 4-diazophenyldimethylamine hydrogen sulfate, 4-diazodiphenylamine tetrafluoroborate, and 3-methoxy-4-diazodiphenylamine hexafluorophosphate Is preferred.

  Preferably, the cationic dye is a compound selected from the group consisting of crystal violet, methyl violet, ethyl violet and Victoria pure blue BOH.

  Although the suitable polymerization inhibitor which can be used for this invention is illustrated below, this invention is not restrict | limited to these. In addition, as a phenol type polymerization inhibitor, the following exemplary compound (P-1)-(P-24) is mentioned.

  Examples of the amine polymerization inhibitor include the following exemplary compounds (N-1) to (N-7).

  Examples of the sulfur polymerization inhibitor include the following exemplary compounds (S-1) to (S-5).

  Examples of the phosphite polymerization inhibitor include the following exemplary compounds (R-1) to (R-5).

  Furthermore, each compound shown below can also be used as a suitable polymerization inhibitor.

  Among the above exemplified compounds, hydroquinone, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4-thiobis (3-methyl-6-t- Butylphenol), 2,2′-methylenebis (4-methyl-6-tert-butylphenol) phenolic hydroxyl group-containing compounds, piperidine 1-oxyl free radical compounds, or 2,2,6,6-tetramethylpiperidine 1- Oxyl free radical, 4-oxo-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido- 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-maleimide-2,2 , 6,6-tetramethylpiperidine 1-oxyl free radical, and piperidine 1-oxyl free radical compound of 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, or N-nitrosophenyl hydroxyl N-nitrosophenylhydroxylamine compounds of amine cerium salt and N-nitrosophenylhydroxylamine aluminum salt, more preferably 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-oxo- 2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, 4-acetamido-2,2,6,6- Tetramethylpiperidine 1-oxyl free radical, -Piperidine 1-oxyl free radical compound of maleimide-2,2,6,6-tetramethylpiperidine 1-oxyl free radical and 4-phosphonoxy-2,2,6,6-tetramethylpiperidine 1-oxyl free radical, Or an N-nitrosophenylhydroxylamine primary cerium salt and an N-nitrosophenylhydroxylamine aluminum salt, more preferably -nitrosophenylhydroxylamine primary cerium salt and N-nitrosophenylhydroxylamine compound. N-nitrosophenylhydroxylamine compound of amine aluminum salt.

A preferable addition amount of the polymerization inhibitor is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.01 parts by mass or more and 8 parts by mass with respect to 100 parts by mass of the (C) photopolymerization initiator. Or less, and most preferably in the range of 0.05 parts by mass or more and 5 parts by mass or less.
By setting it as the above range, the curing reaction in the non-image area is sufficiently suppressed and the curing reaction in the image area is sufficiently promoted, and the image formability and sensitivity are improved.

[Sensitizer]
The polymerizable composition of the present invention may contain a sensitizer for the purpose of improving the radical generation efficiency of the radical initiator and increasing the photosensitive wavelength.
As the sensitizer that can be used in the present invention, a sensitizer that sensitizes the above-described (B) photopolymerization initiator by an electron transfer mechanism or an energy transfer mechanism is preferable.

Examples of the sensitizer include those belonging to the compounds listed below and having an absorption wavelength in a wavelength region of 300 nm to 450 nm.
That is, for example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), Thioxanthones (isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, Toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squaryu (Eg, squalium), acridine orange, coumarins (eg, 7-diethylamino-4-methylcoumarin), ketocoumarins, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes Carbazoles, porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, etc. Examples include aromatic ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

  More preferable examples of the sensitizer that can be used in the present invention include compounds represented by the following general formulas (e-1) to (e-4).

In formula (e-1), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ¹ represents a basic nucleus of the dye in combination with adjacent A ¹ and an adjacent carbon atom. R ⁵¹ and R ⁵² each independently represents a hydrogen atom or a monovalent nonmetallic atomic group, and R ⁵¹ and R ⁵² are bonded to each other to form an acidic nucleus of the dye. May be. W represents an oxygen atom or a sulfur atom.

In formula (e-2), Ar ¹ and Ar ² each independently represent an aryl group and are linked via a bond with —L ² —. Here -L ² - represents -O- or -S-. Moreover, W is synonymous with what was shown to Formula (e-1).

In the formula (e-3), A ² represents a sulfur atom or NR ⁵⁹ , L ³ represents a nonmetallic atomic group that forms a basic nucleus of the dye together with the adjacent A ² and carbon atom, and R ⁵³ , R ⁵⁴ , R ⁵⁵ , R ⁵⁶ , R ⁵⁷ and R ⁵⁸ each independently represents a monovalent non-metallic atomic group, and R ⁵⁹ represents an alkyl group or an aryl group.

In formula (e-4), A ³ and A ⁴ each independently represent —S— or —NR ⁶² , and R ⁶² represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group. , L ⁴ and L ⁵ each independently represent a nonmetallic atomic group which forms a basic nucleus of a dye in cooperation with adjacent A ³ , A ⁴ and adjacent carbon atoms, and R ⁶⁰ and R ⁶¹ each independently Represents a monovalent non-metallic atomic group, or can be bonded to each other to form an aliphatic or aromatic ring.

The content of the sensitizer in the polymerizable composition is preferably 0.1% by mass or more and 20% by mass or less in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency. More preferably, the content is 5% by mass or more and 15% by mass or less.
A sensitizer may be used individually by 1 type and may use 2 or more types together.

Further, as a preferable sensitizer that can be contained in the polymerizable composition, in addition to the sensitizer, a compound represented by the following general formula (II) and a compound represented by the general formula (III) are selected. At least one kind.
These may be used individually by 1 type, and may use 2 or more types together.

In general formula (II), R ¹¹ and R ¹² each independently represents a monovalent substituent, and R ¹³ , R ¹⁴ , R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom or a monovalent substituent. To express. n represents an integer of 0 to 5, n ′ represents an integer of 0 to 5, and n and n ′ are not both 0. When n is 2 or more, a plurality of R ¹¹ may be the same or different. When n ′ is 2 or more, a plurality of R ¹² may be the same or different. In the general formula (II), the isomer by the double bond is not limited to either.

The compound represented by the general formula (II) preferably has a molar extinction coefficient ε at a wavelength of 365 nm of 500 mol ⁻¹ · L · cm ⁻¹ or more, and ε at a wavelength of 365 nm of 3000 mol ⁻¹ · L · cm ^{−. 1} or more is more preferable, and ε at a wavelength of 365 nm is most preferably 20000 mol ⁻¹ · L · cm ⁻¹ or more. It is preferable that the value of the molar extinction coefficient ε at each wavelength is in the above range because the sensitivity improvement effect is high from the viewpoint of light absorption efficiency.

Although the preferable specific example of a compound represented by general formula (II) is illustrated below, this invention is not limited to these.
Note that in this specification, a chemical formula may be described by a simplified structural formula, and a solid line or the like that does not clearly indicate an element or a substituent particularly represents a hydrocarbon group.

In general formula (III), A represents an aromatic ring or a hetero ring which may have a substituent, X ² represents an oxygen atom, a sulfur atom, or —N (R ²³ ) —, and Y represents an oxygen atom. , sulfur atom, or -N ^{(R 23)} - represents a. R ²¹ , R ²² , and R ²³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A, R ²¹ , R ²² , and R ²³ are bonded to each other to form an aliphatic group Or you may form an aromatic ring.

In the general formula (III), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group. When R ²¹ , R ²² and R ²³ represent a monovalent nonmetal atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted aromatic group It is preferably a heterocyclic residue, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, a hydroxyl group, or a halogen atom.

In the compound represented by formula (III), Y is preferably an oxygen atom or —N (R ²³ ) — from the viewpoint of improving the decomposition efficiency of the photopolymerization initiator. R ²³ represents a hydrogen atom or a monovalent nonmetallic atomic group. Further, Y is most preferably —N (R ²³ ) —.

  Hereinafter, although the preferable specific example of a compound represented by general formula (III) is shown, this invention is not limited to this. Further, it is not clear about an isomer by a double bond connecting an acidic nucleus and a basic nucleus, and the present invention is not limited to either isomer.

[Co-sensitizer]
It is also preferred that the polymerizable composition further contains a co-sensitizer.
In the present invention, the co-sensitizer further enhances the sensitivity of (C) the photopolymerization initiator and the sensitizer to actinic radiation, or suppresses the inhibition of polymerization inhibition of (B) the polymerizable compound by oxygen. Have.

  Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. No. 60-84305, JP-A 62-18537, JP-A 64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides such as thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142772, No. 56-75643, such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercapto. And naphthalene.

  Other examples of the co-sensitizer include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in JP-B-48-42965 (eg, tributyltin acetate), JP-B 55- Examples include a hydrogen donor described in Japanese Patent No. 34414, a sulfur compound (eg, trithiane) described in Japanese Patent Laid-Open No. 6-308727, and the like.

  The content of these co-sensitizers is 0.1% by mass or more and 30% by mass or less with respect to the mass of the total solid content of the polymerizable composition from the viewpoint of improving the curing rate due to the balance between polymerization growth rate and chain transfer. The range of 1 mass% or more and 25 mass% or less is more preferable, and the range of 0.5 mass% or more and 20 mass% or less is still more preferable.

[Binder polymer]
In the polymerizable composition, a binder polymer can be further used as necessary for the purpose of improving the film properties. As the binder, a linear organic polymer is preferably used. As such a “linear organic polymer”, a known one can be arbitrarily used. Preferably, a linear organic polymer that is soluble or swellable in water or weak alkaline water is selected in order to enable water development or weak alkaline water development. The linear organic polymer is selected and used not only as a film forming agent but also according to the use as water, weak alkaline water or an organic solvent developer. For example, when a water-soluble organic polymer is used, water development becomes possible. Examples of such linear organic polymers include radical polymers having a carboxylic acid group in the side chain, such as JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, and JP-B-sho. Nos. 54-25957, JP-A-54-92723, JP-A-59-53836, JP-A-59-71048, ie, a monomer having a carboxyl group alone or Resin copolymerized, monomer having acid anhydride alone or copolymerized, acid anhydride unit hydrolyzed, half-esterified or half-amidated, epoxy resin with unsaturated monocarboxylic acid and acid anhydride Examples include modified epoxy acrylate. Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Similarly, there is an acidic cellulose derivative having a carboxylic acid group in the side chain. In addition, those obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group are useful.

  In the present invention, when a copolymer is used as the binder polymer (for example, alkali-soluble resin), a monomer other than the monomers listed above can also be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (12).

(1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic esters having an aliphatic hydroxyl group such as methacrylic esters.
(2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

(3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.
(4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.
(7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.
(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.

(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.
(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598, and the like can be mentioned.

  Among these, a (meth) acrylic resin having an allyl group, a vinyl ester group, and a carboxyl group in the side chain and a side chain described in JP-A Nos. 2000-187322 and 2002-62698 are doubled. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

Also, Japanese Patent Publication No. 7-12004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Publication No. 63-287944, Japanese Patent Publication No. 63-287947. Urethane-based binder polymers containing acid groups described in Japanese Patent Application Laid-Open No. 1-271741, Japanese Patent Application No. 10-116232, and acid groups and double compounds described in Japanese Patent Application Laid-Open No. 2002-107918. A urethane-based binder polymer having a bond in the side chain is very excellent in strength, and is advantageous in terms of printing durability and suitability for low exposure.
In addition, an acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in European Patent 993966, European Patent 1204000, Japanese Patent Application Laid-Open No. 2001-318463, and the like is preferable because of its excellent balance of film strength and developability.
In addition, polyvinyl pyrrolidone, polyethylene oxide, and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

The weight average molecular weight of the binder polymer that can be used in the polymerizable composition of the present invention is preferably 5,000 or more, more preferably 10,000 to 300,000, and the number average molecular weight is preferably It is 1,000 or more, More preferably, it is the range of 2,000 or more and 250,000 or less. The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, more preferably 1.1 or more and 10 or less.
These binder polymers may be any of random polymers, block polymers, graft polymers and the like.

The binder polymer that can be used in the present invention can be synthesized by a conventionally known method. Solvents used in the synthesis include, for example, tetrahydrofuran, ethylene dichloride, cyclohexanone, methyl ethyl ketone, acetone, methanol, ethanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, diethylene glycol dimethyl ether, 1-methoxy. Examples include 2-propanol, 1-methoxy-2-propyl acetate, N, N-dimethylformamide, N, N-dimethylacetamide, toluene, ethyl acetate, methyl lactate, ethyl lactate, dimethyl sulfoxide, and water. These solvents are used alone or in combination of two or more.
Examples of the radical polymerization initiator used when synthesizing the binder polymer that can be used in the polymerizable composition of the present invention include known compounds such as an azo initiator and a peroxide initiator.

  In the total solid content of the polymerizable composition, the content of the binder polymer is preferably 1% to 40% by mass, more preferably 3% to 30% by mass, and more preferably 4% to 20%. More preferably, it is at most mass%.

[Adhesion improver]
In the polymerizable composition, an adhesion improver can be added in order to improve adhesion to a hard surface such as a support. Examples of the adhesion improver include a silane coupling agent and a titanium coupling agent.

  Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ- (2-aminoethyl) aminopropyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxy. Silane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyl Triethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ-aminopropyltrimethoxysilane / hydrochloride, γ-glycidoxypro Pyrtrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, vinyltriacetoxysilane, γ- Chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) silane, octadecyldimethyl [3- (trimethoxysilyl) propyl ] Ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethyl Chlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N- (3-acryloxy-2-hydroxy Propyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane, (acryloxymethyl) methyldimethoxysilane , Etc.

  Among them, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxysilane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, γ-aminopropyl Triethoxysilane and phenyltrimethoxysilane are preferable, and γ-methacryloxypropyltrimethoxysilane is most preferable.

  The addition amount of the adhesion improver is preferably 0.5% by mass or more and 30% by mass or less, and more preferably 0.7% by mass or more and 20% by mass or less in the total solid content of the polymerizable composition.

[Diluent]
The polymerizable composition may use various organic solvents as a diluent.
The organic solvent used here is acetone, methyl ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride, tetrahydrofuran, toluene, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether. , Acetylacetone, cyclohexanone, diacetone alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxyethanol, diethylene glycol monomethyl ether , Diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, methyl lactate, lactic acid There are ethyl and the like.
These solvents can be used alone or in combination. The concentration of the solid content with respect to the organic solvent is preferably 2 to 60% by mass.

[Other additives]
Furthermore, in order to improve the physical properties of the cured film, known additives such as inorganic fillers, plasticizers, and oil sensitizers may be added to the polymerizable composition.
Examples of plasticizers include dioctyl phthalate, didodecyl phthalate, triethylene glycol dicaprylate, dimethyl glycol phthalate, tricresyl phosphate, dioctyl adipate, dibutyl sebacate, and triacetyl glycerin. , 10% by mass or less can be added with respect to the total mass of the polymerizable compound and the binder polymer.

  The polymerizable composition of the present invention can be suitably used for forming a light-shielding color filter because it has high curing sensitivity and can form a high-definition light-shielding film pattern in which residues in unexposed areas are suppressed.

<Light-shielding color filter>
The light-shielding color filter of the present invention is formed using the above-described polymerizable composition of the present invention. The light-shielding color filter formed using the polymerizable composition of the present invention can suppress a phenomenon in which a region (step) in which the film thickness is thinner in the peripheral part than in the central part is generated, and the central part and the peripheral part are shielded from light. Performance can be improved.

In the present invention, the step refers to a step observed in a light-shielding color filter having a side of about 200 μm or more formed by applying, exposing and developing a polymerizable composition. When the light-shielding color filter is observed from above the film surface with an optical microscope, the step may be observed as a line that is substantially similar to the pattern edge of the light-shielding color filter.
FIG. 1 is a diagram schematically showing a state in which a step occurs in the light-shielding color filter 10. The solid line represents the pattern edge 1 of the light-shielding color filter, and the broken line represents step 2. Actually, the broken line is observed as a solid line. The film thickness of the light-shielding color filter is the area inside the step in the area outside the step (the area between the pattern edge 1 and step 2 in FIG. 1). It is thinner than (the region surrounded by step 2 in FIG. 1). In other words, the area outside the step (hereinafter also referred to as “step area”) has a low light shielding ability, and thus causes noise when used as a light-shielding color filter for a solid-state imaging element. Adversely affect.
In addition, when a light-shielding color filter is formed using the polymerizable composition of the present invention, a phenomenon in which a region (step region) in which the film thickness is thinner than the central portion can be suppressed in the periphery of the light-shielding color filter can be suppressed. It is possible to suppress a decrease in the light shielding ability.

The film thickness of the light-shielding color filter is not particularly limited, but is preferably 0.2 μm or more and 50 μm or less, more preferably 0.5 μm or more and 30 μm or less, from the viewpoint of obtaining the effect of the present invention more effectively. More preferably, it is 7 μm or more and 20 μm or less.
The size (length of one side) of the light-shielding color filter is preferably 0.5 mm or more and 5 mm or less, more preferably 0.7 mm or more and 4 mm or less from the viewpoint of obtaining the effect of the present invention more effectively. 9 mm or more and 3.5 mm or less are still more preferable.

<Light-shielding color filter and manufacturing method thereof>
Next, the light-shielding color filter of the present invention and the manufacturing method thereof will be described.
The light-shielding color filter of the present invention is characterized in that it has a colored pattern formed using the polymerizable composition of the present invention on a support.
Hereinafter, the light-shielding color filter of the present invention will be described in detail through its manufacturing method.

  The method for producing a light-shielding color filter of the present invention comprises a step of forming a polymerizable composition layer by applying the polymerizable composition of the present invention on a support (hereinafter referred to as “polymerizable composition layer forming step” as appropriate). And a step of exposing the polymerizable composition layer through a mask (hereinafter abbreviated as “exposure step” as appropriate), and developing and coloring the polymerizable composition layer after exposure. And a step of forming a pattern (hereinafter abbreviated as “development step” as appropriate).

Specifically, the polymerizable composition of the present invention is applied directly or via another layer to a support (substrate) to form a polymerizable composition layer (polymerizable composition layer forming step). Then, it is exposed through a predetermined mask pattern, only the coating film portion irradiated with light is cured (exposure process), and developed with a developer (development process) to form a pattern-like film composed of pixels. The light-shielding color filter of the invention can be manufactured.
Hereinafter, each process in the manufacturing method of the light-shielding color filter of this invention is demonstrated.

[Polymerizable composition layer forming step]
In the polymerizable composition layer forming step, the polymerizable composition of the present invention is applied on a support to form a polymerizable composition layer.

Examples of the support that can be used in this step include a photoelectric conversion element substrate used for an imaging element or the like, such as a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like. These substrates may have black stripes that separate pixels.
Further, an undercoat layer may be provided on these supports, if necessary, in order to improve adhesion to the upper layer, prevent diffusion of substances, or flatten the substrate surface.

  As a coating method of the polymerizable composition of the present invention on the support, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, screen printing method and the like can be applied.

  When manufacturing a color filter for a solid-state imaging device, the coating film thickness of the polymerizable composition is preferably 0.35 μm or more and 1.5 μm or less, and preferably 0.40 μm or more and 1. 0 μm or less is more preferable.

  The polymerizable composition coated on the support is usually dried under conditions of 70 ° C. or higher and 110 ° C. or lower and about 2 minutes or longer and 4 minutes or shorter to form a polymerizable composition layer.

[Exposure process]
In the exposure step, the polymerizable composition layer formed in the polymerizable composition layer forming step is exposed through a mask, and only the coating film portion irradiated with light is cured.
The exposure is preferably performed by irradiation of radiation, and as radiation that can be used for exposure, ultraviolet rays such as g-line and i-line are preferably used, and a high-pressure mercury lamp is more preferable. The irradiation intensity is preferably 5 mJ or more and 1500 mJ or less, more preferably 10 mJ or more and 1000 mJ or less, and most preferably 10 mJ or more and 800 mJ or less.

[Development process]
Subsequent to the exposure step, an alkali development treatment (development step) is performed, and the light non-irradiated part in the exposure step is eluted in an alkaline aqueous solution. Thereby, only the photocured part remains.
As the developer, an organic alkali developer that does not damage the underlying circuit or the like is desirable. The development temperature is usually from 20 ° C. to 30 ° C., and the development time is from 20 seconds to 90 seconds.

  Examples of the alkali used in the developer include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5, 4, 0. ] -7-Undecene is used as an alkaline aqueous solution diluted with pure water so that the concentration is 0.001 to 10% by mass, preferably 0.01 to 1% by mass. The In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  In the method for producing a light-shielding color filter of the present invention, after the above-described polymerizable composition layer forming step, exposure step, and development step are performed, the formed colored pattern is heated and / or if necessary. A curing step of curing by exposure may be included.

Since the light-shielding color filter of the present invention uses the polymerizable composition of the present invention, the formed colored pattern exhibits high adhesion to the support substrate, and the cured composition has excellent development resistance. In addition, it is possible to form a high-resolution pattern that is excellent in exposure sensitivity, has good adhesion to the substrate of the exposed portion, and gives a desired cross-sectional shape.
Therefore, it can be suitably used for a solid-state imaging device such as a liquid crystal display device or a CCD, and is particularly suitable for a high-resolution CCD device or a CMOS that exceeds 1 million pixels. In other words, the light-shielding color filter of the present invention is preferably applied to a solid-state image sensor.
The light-shielding color filter of the present invention can be used as, for example, a light-shielding color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

<Solid-state imaging device>
The solid-state imaging device of the present invention is configured to include a color filter having the light-shielding color filter of the present invention described above and a patterned film composed of pixels of other colors (three colors or four colors) as necessary. The
Since the solid-state imaging device of the present invention includes the light-shielding color filter of the present invention in which a decrease in light-shielding ability at the peripheral portion is suppressed, noise can be reduced and color reproducibility can be improved.
The configuration of the solid-state imaging device of the present invention is a configuration provided with the light-shielding color filter of the present invention, and is not particularly limited as long as it is a configuration that functions as a solid-state imaging device. The present invention has a light receiving element composed of a plurality of photodiodes and polysilicon forming a light receiving area of an image pickup element (CCD image sensor, CMOS image sensor, etc.), and the present invention is provided on the surface opposite to the light receiving element forming surface of the support The structure etc. with which this light-shielding color filter was provided are mentioned.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples unless it exceeds the gist thereof. Unless otherwise specified, “part” and “%” are based on mass.

(Preparation of polymerizable composition)
<Preparation of carbon black dispersion A>
The following composition 1 was subjected to a high viscosity dispersion treatment with two rolls to obtain a dispersion. The viscosity of the dispersion at this time was 70000 mPa · s.
Then, the following composition 2 was added to this dispersion, and it stirred for 3 hours using the homogenizer on 3000 rpm conditions. The obtained mixed solution was subjected to a fine dispersion treatment for 4 hours with a disperser using 0.3 mm zirconia beads (trade name: Dispermat manufactured by GETZMANN), and carbon black dispersion A (hereinafter referred to as CB dispersion A). Was written). At this time, the viscosity of the mixed solution was 37 mPa · s.

(Composition 1)
-Average primary particle size 15 nm carbon black (Pigment Black 7) 23 parts-Specific alkali-soluble resin shown in Table 1 or comparative resin propylene glycol monomethyl ether acetate 45% solution 22 parts-Solsperse 5000 (manufactured by Geneca) (dispersant) 2 parts

(Composition 2)
22 parts of propylene glycol monomethyl ether acetate 45% solution of specific alkali-soluble resin or comparative resin shown in Table 1 (BzMA / MAA = 70/30, Mw: 30000)
・ 200 parts of propylene glycol monomethyl ether acetate

<Preparation of Titanium Black Dispersion A>
The following composition 3 was subjected to a high viscosity dispersion treatment with two rolls to obtain a dispersion. The viscosity of the dispersion at this time was 40,000 mPa · s.
In addition, you may knead | mix for 30 minutes with a kneader before a high-viscosity dispersion process.

<Composition 3>
-Average primary particle size 75nm Titanium black 13M-C 39 parts (Mitsubishi Materials Corporation) (Pigment Black 35)
-8 parts of a propylene glycol monomethyl ether acetate solution of the specific alkali-soluble resin shown in Table 1-Solsperse 5000 (manufactured by Zeneca) (dispersant) 1 part

The following composition 4 was added to the obtained dispersion, and the mixture was stirred for 3 hours using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was finely dispersed for 4 hours with a disperser (trade name: Dispermat GETZMANN Co., Ltd.) using 0.3 mm zirconia beads, and titanium black dispersion A (hereinafter referred to as TB dispersion). A.) was obtained.
At this time, the viscosity of the mixed solution was 7.0 mPa · s.

<Composition 4>
・ 8 parts of propylene glycol monomethyl ether acetate solution of specific alkali-soluble resin shown in Table 1 ・ 200 parts of propylene glycol monomethyl ether acetate

<Preparation of titanium black dispersion B>
In the same manner as Titanium Black Dispersion A, except that Ako Kasei Co., Ltd. Tilack D was used instead of “Titanium Black 13M-C manufactured by Mitsubishi Materials Corporation” used in Titanium Black Dispersion A. Titanium black dispersion B was prepared.

(Example 1-1 to Example 1-16 and Comparative Example 1-1 to Comparative Example 1-3)
<Preparation of Polymerizable Compositions A-1 to A-12, B-1, C-1, D-1, E-1, and Comparative Compositions A′-1 to A′-3>
The components of the following compositions A to E are mixed with a stirrer, and polymerizable compositions A-1 to A-12, B-1, C-1, D-1, E-1, and comparative composition A ′. −1 to A′-3 were prepared.

(Composition A)
-Methacrylate / acrylic acid copolymer (binder polymer) 1.6 parts by mass-Dipentaerythritol hexaacrylate (polymerizable compound) 2.3 parts by mass-Ethoxylated pentaerythritol tetraacrylate (polymerizable compound) 0.8 parts by mass -24 parts by mass of CB dispersion A or TB dispersion A listed in Table 1 below-10 parts by mass of propylene glycol monomethyl ether acetate (diluent)-8 parts by mass of ethyl-3-ethoxypropionate-photopolymerization initiator : Compounds described in the following Table 1 As an amount / polymerization inhibitor described in the following Table 1, 0.01 parts by mass of 4-methoxyphenol

(Composition B)
The composition was the same as the composition A except that the “TB dispersion A described in Table 1” was used instead of the “TB dispersion A described in Table 1” used in the composition A.

(Composition C)
20 parts by mass of the TB dispersion A (see Table 1) used in the polymerizable composition A-1 "TB dispersion A shown in Table 1 or 24 parts by mass of TB dispersion A" used in the above composition A The composition was the same as that of Composition A except that 1.6 parts by mass of the methacrylate / acrylic acid copolymer (binder polymer) was changed to 5.0 parts by mass.

(Composition D)
In the composition A, the TB dispersion A used in the polymerizable composition A-1 ("TB dispersion A shown in Table 1 or 24 parts by mass of TB dispersion A") used (see Table 1) 45 masses The composition was the same as that of Composition A except that 1.6 parts by mass of the methacrylate / acrylic acid copolymer (binder polymer) in Composition A was changed to 0.652 parts by mass.

(Composition E)
45 parts by mass of the TB dispersion A (see Table 1) using the “CB dispersion A or TB dispersion A shown in Table 1 or 24 parts by mass” used in the composition A in the polymerizable composition A-1. Further, 1.6 parts by mass of the methacrylate / acrylic acid copolymer (binder polymer) in the composition A is changed to 0 parts by mass, and dipentaerythritol hexaacrylate (polymerizable compound) in the composition A is changed to 2. The composition was the same as the composition A except that 3 parts by mass was changed to 0.582 parts by mass.

(Example 2-1 to Example 2-12 and Comparative Example 2-1 to Comparative Example 2-3)
<Preparation of Polymerizable Compositions Y-1 to Y-12 and Y'-1 to Y'-3>
Components of the following composition Y were mixed with a stirrer to prepare polymerizable compositions Y-1 to Y-12 and Y′-1 to Y′-3.

(Composition Y)
Dipentaerythritol hexaacrylate (polymerizable compound) 2.3 parts by mass CB dispersion A or TB dispersion A shown in Table 2 below, 24 parts by mass Propylene glycol monomethyl ether acetate (diluent) 10 parts by mass -Ethyl-3-ethoxypropionate 8 parts by mass-Photopolymerization initiator: compounds described in Table 2 below As the amount shown in Table 2 below-polymerization inhibitor, 0.01 parts by mass of 4-methoxyphenol

In Tables 1 and 2, “TB” indicates titanium black and “CB” indicates carbon black. The photopolymerization initiators listed in Tables 1 and 2 are as follows.
In Tables 1 and 2, “Exemplary Compound 2 to Exemplary Compound 31” shown as the specific alkali-soluble resins are shown in the above “Chemical Formula 5” to “Chemical Formula 11” as specific examples of the specific alkali-soluble resin, respectively. It corresponds to Exemplified Compound 2 to Exemplified Compound 31.
In Tables 1 and 2, Comparative Compound 1 shown as the specific alkali-soluble resin is a benzyl (meth) acrylate / (meth) acrylic acid copolymer propylene glycol monomethyl ether acetate solution (BzMA / MAA = 70 / 30, Mw: 30000, solid content 40% by mass).

Compound 6

[Evaluation]
Polymerizable composition or comparative composition (A-1 to A-12, B-1, C-1, D-1, E-1, A'-1 to A'-3) obtained as described above. , Y-1 to Y-12, and Y′-1 to Y′-3) were evaluated as follows. The results are shown in Tables 1 and 2 above.

-Exposure sensitivity evaluation-
First, the polymerizable composition or the comparative composition (A-1 to A-12, B-1, C-1, D-1, E-1, A′-1 to A ′) obtained as described above. -3, Y-1 to Y-12, and Y'-1 to Y'-3) were evaluated by the following methods.

Using each polymerizable composition, the coating rotation speed of spin coating was adjusted so that the film thickness after heat treatment on a hot plate at a surface temperature of 120 ° C. for 120 seconds after coating was 1.0 μm, and was applied onto a silicon wafer. Uniform coating was performed to obtain a 1.0 μm coating film.
Then, i-line stepper, FPA-3000iS + through a photomask having a pattern of 3mm square using (Canon Co., Ltd.), the exposure amount of 100 mJ / cm ² or more 5000 mJ / cm ² or less in the range, 100 mJ Irradiation was performed while changing in steps of / cm ² .
After irradiation, paddle development is performed at 23 ° C. for 60 seconds using a tetramethylammonium hydroxide (TMAH) 0.3% aqueous solution, and then rinsed with pure water for 20 seconds in a spin shower. Washed with pure water. Thereafter, the adhering water droplets were removed with high-level air, and the substrate was naturally dried to obtain a black image pattern.
About the obtained black image pattern, it evaluated on the following reference | standard using the optical microscope.

In the above exposure step, the film thickness after development in the region irradiated with light was measured to be the minimum exposure amount that was 95% or more with respect to the film thickness 100% before exposure, and this was evaluated as exposure sensitivity. .
A smaller exposure sensitivity value indicates higher sensitivity.

-Evaluation of storage stability (stability over time)-
Moreover, the storage stability of each polymerizable composition obtained as described above was evaluated by the following method.
That is, after each polymerizable composition was stored at room temperature for 1 month, the degree of viscosity change was evaluated according to the following criteria.

-Criteria-
○: Viscosity change of 0% to less than 3% Δ: Viscosity change of 3% to less than 10% ×: Viscosity change of 10% or more

-Developability evaluation-
Furthermore, the developability of each polymerizable composition obtained as described above was evaluated by the following method.
That is, in the exposure process in the sensitivity evaluation, the presence or absence of a residue in a region not irradiated with light (unexposed portion) was observed with an SEM, and developability was evaluated. The evaluation criteria are as follows.

-Evaluation criteria-
○: Residue was not confirmed at all in the unexposed area. Δ: Residue was slightly confirmed at the unexposed area, but there was no practical problem. confirmed.

-Step evaluation-
The obtained light-shielding film pattern (pattern formed from the polymerizable composition) was photographed with an optical microscope (100 times magnification), and the width of the step region was measured. Specifically, as shown in FIG. 1, in the light shielding film (light shielding color filter) 10, a pattern edge 1 which is an end portion of a pattern formed of a polymerizable composition and a step region (light shielding color filter peripheral portion). The width of the boundary line 2 with respect to the region where the film thickness is thinner than the central portion in FIG. It shows that the narrower the width of the step region, the better the light shielding ability of the central part and the peripheral part.

  As is clear from Table 1 and Table 2, the polymerizable composition of the present invention has good exposure sensitivity and storage stability, and in both cases, no residue was observed in the unexposed area, and good developability was exhibited. Here, since the cured composition is excellent in development resistance, it can be seen that the polymerizable composition of the present invention is excellent in curability. Moreover, it turns out that the polymeric composition of this invention has sufficient light-shielding property required for the light-shielding color filter for solid-state image sensors.

Furthermore, when an oxime compound is used as a photopolymerization initiator (Examples 1-1 to 1-8, 1-11 to 1-12), an oxime compound is not used (Example 1-9, It can be seen that the exposure sensitivity and stability over time are more excellent than those of 1-10).
Examples 1-1 to 1-13, Examples 1-15, and Examples in which the content of titanium black with respect to the total solid content of the polymerizable composition is in the range of 40% by mass to 80% by mass The results that the step region width is wider in Examples 2-1 to 2-12 than in Examples 1-14 and 1-16, which are outside this range, are obtained. For this reason, when the content of titanium black with respect to the total solid content of the polymerizable composition is within the range of 40% by mass or more and 80% by mass, a better center part and It can be said that the shading ability of the peripheral part is obtained.

(Example 3-1)
<Production of solid-state image sensor>
-Preparation of chromatic coloring polymerizable composition-
In the polymerizable composition Y-1 prepared in Example 2-1, the colored polymerizable composition R for red (R) was similarly used except that the black pigment, titanium black, was replaced with the following chromatic pigment. -1, green (G) colored polymerizable composition G-1, and blue (B) colored polymerizable composition B-1.

Chromatic pigment for forming colored pixels for each color of RGB, pigment for red (R) C.I. I. Pigment Red 254
-Green (G) pigment C.I. I. Pigment Green 36 and C.I. I. Pigment Yellow 219 30/70 [mass ratio] mixture and blue (B) pigment C.I. I. Pigment Blue 15: 6 and C.I. I. 30/70 [mass ratio] mixture with pigment violet 23

-Fabrication of color filters for solid-state image sensors-
The light-shielding color filter prepared in Example 2-1 was used as a black matrix, and the colored polymerizable composition R-1 for red (R) was used on the black matrix, as described in Example 2-1. A red (R) colored pattern of 1.6 × 1.6 μm was formed in the same manner as the method. Further, using the colored polymerizable composition G-1 for green (G) in the same manner, the colored polymerizable composition B-1 for green (G) and blue (B) of 1.6 × 1.6 μm was used. A blue (B) chromatic coloring pattern was sequentially formed to produce a color filter for a solid-state imaging device.

-Evaluation-
When a full-color color filter was incorporated into a solid-state imaging device, it was confirmed that the solid-state imaging device has a high light-shielding property of the light-shielding color filter, high resolution, and excellent color separation.

It is a schematic diagram which shows a mode that the step arose in the light-shielding color filter.

Explanation of symbols

1 Pattern edge 2 Step 10 Light blocking color filter

Claims (6)

  (A) A polymerizable composition containing a titanium black dispersion comprising an alkali-soluble resin having at least one unsaturated double bond and titanium black, (B) a polymerizable compound, and (C) a photopolymerization initiator. object.   The polymerizable composition according to claim 1, wherein the (C) photopolymerization initiator is an oxime compound.   The polymerizable composition according to claim 1 or 2, wherein the content of titanium black with respect to the total solid content of the polymerizable composition is 40% by mass or more and 80% by mass or less.   The polymerizable composition according to claim 1, wherein the polymerizable composition is used for forming a light-shielding color filter.   A light-shielding color filter having a colored region formed on the support using the polymerizable composition according to claim 4.   A solid-state imaging device comprising the light-shielding color filter according to claim 5.