JP2009079121A - Pigment dispersion composition, photocurable composition, color filter and method for producing color filter - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a pigment dispersion composition that contains a pigment dispersant having high pigment dispersibility and dispersion stability after dispersion even in the case of containing a pigment in a high concentration, has excellent color characteristics and in constituting a color filter, has excellent development properties and surface smoothness of picture element and a high contrast, a photocurable composition and a color filter having excellent color characteristics and a high contrast and to provide a method for producing the same. <P>SOLUTION: The pigment dispersion composition comprises (A) a polymer compound that has a cyclic structure as a partial structure obtained by direct binding of a group to be dissociated with an alkali and a weight-average molecular weight of ≥1,000 and ≤100,000 and (B) a pigment. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a pigment dispersion composition, a photocurable composition, a color filter, and a method for producing a color filter.

  In recent years, the use of color filters in liquid crystal display (LCD) applications has tended to expand not only to monitors but also to televisions (TVs). With this trend of expanding applications, advanced color characteristics such as chromaticity and contrast. Has come to be required. Similarly, in image sensor (solid-state imaging device) applications, advanced color characteristics such as reduction in color unevenness and improvement in color resolution are required.

  In response to the above requirements, it is required to disperse the pigment in a finer state (good dispersibility) and to disperse in a stable state (good dispersion stability). If the dispersibility is insufficient, fringes (jagged edges) and surface irregularities occur in the formed colored resist film, the chromaticity and dimensional accuracy of the produced color filter are reduced, and the contrast is remarkably high. There is a problem of deterioration.

  In addition, when the dispersion stability is insufficient, in the color filter manufacturing process, the uniformity of the film thickness particularly in the coating process of the colored photosensitive composition is reduced, or the photosensitive sensitivity in the exposure process is reduced. Or the alkali solubility in the development process is likely to be reduced. Furthermore, when the dispersion stability of the pigment is poor, there is also a problem that the constituent components of the colored photosensitive composition are aggregated with the passage of time, the viscosity is increased, and the pot life is extremely shortened.

In order to solve such a problem, a polymer pigment dispersant in which an organic dye and a polymer are combined has been proposed (see Patent Document 1).
However, since the surface area of the pigment particles is increased when the pigment particle size is reduced, the cohesive force between the pigment particles is increased, and it is difficult to achieve both dispersibility and dispersion stability at a high level.

  In producing a color filter using the pigment dispersion composition, the radiation-sensitive composition is applied on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed in advance, and then dried. The coated film is irradiated with radiation in a desired pattern (hereinafter referred to as “exposure”) and developed to obtain pixels of each color.

  However, the color filter manufactured in this manner is likely to cause residue and background contamination on the unexposed substrate or the light shielding layer in the development process, and the post-baked pixels after development have poor surface smoothness. There was a problem that the physical properties of the coating film were inferior. Moreover, the degree of deterioration of residues, background stains and surface smoothness on the substrate or the light-shielding layer tends to become more prominent as the concentration of the pigment contained in the photocurable composition increases. With a photocurable composition, it was difficult to achieve a sufficient color density.

Further, for the purpose of imparting alkali developability, a pigment dispersion composition using a polymer compound into which an acid group such as methacrylic acid is introduced as an alkali-soluble resin is known (see Patent Document 2 and Patent Document 3). It was still insufficient to achieve both the dispersibility of the pigment and the developability when used as a color filter.
JP-A-4-139262 Japanese Patent No. 3094403 JP 2000-56118 A

  The present invention has been made in view of the above, and has a pigment dispersant having high pigment dispersibility and dispersion stability after dispersion even when the pigment is contained at a high concentration, and has good color characteristics, color When constituting a filter, a pigment dispersion composition, a photocurable composition, which is excellent in developability and surface smoothness of a pixel and can obtain high contrast, a color filter having good color characteristics and high contrast, and its An object is to provide a manufacturing method.

That is, the present invention is as follows.
<1> containing (A) a polymer compound having a cyclic structure in which a group dissociated by an alkali is directly bonded as a partial structure, having a weight average molecular weight of 1,000 to 100,000, and (B) a pigment. A pigment dispersion composition characterized by the above.
<2> Alkali directly bonded to a cyclic structure in a polymer compound having a weight average molecular weight of 1,000 to 100,000 having a partial structure of a cyclic structure in which a group dissociated by alkali (A) is directly bonded The pigment dispersion composition as described in <1> above, wherein the content of the repeating unit containing a group dissociated by is 5 to 50% by mass.

<3> The acid value of a polymer compound having a weight average molecular weight of 1,000 or more and 100,000 or less having a cyclic structure in which a group dissociated by an alkali directly bonded as (A) is 50 mgKOH / g or more and 300 mgKOH / G or less, The pigment dispersion composition as described in <1> or <2> above.
<4> A photocuring comprising the pigment dispersion composition according to any one of <1> to <3>, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator. Sex composition.

<5> A color filter having a coloring pattern using the photocurable composition according to <4>.
<6> A step of forming a photosensitive film by applying the photocurable composition according to the above <4> directly or via another layer on a substrate, pattern exposure on the formed photosensitive film, and And a step of forming a colored pattern by performing development.

  According to the present invention, even when the pigment is contained at a high concentration, the pigment dispersant having high pigment dispersibility and dispersion stability after dispersion, having good color characteristics, and forming a color filter, Providing a pigment dispersion composition, a photocurable composition, a color filter having good color characteristics and a high contrast, and a method for producing the same it can.

As a method for solving the problem of residue and background stains on the unexposed portion of the substrate or the light shielding layer in the development step of the curable composition, an alkali-soluble resin having an acid group such as methacrylic acid is conventionally used as a pigment. A method of adding to a dispersion composition is known.
However, when a large amount of acid groups are introduced into the polymer compound, the alkali solubility is improved and the developability is improved, but on the contrary, there is a problem that the pigment dispersion stability is deteriorated.

  In general, when a basic pigment derivative is used, the acid group in the polymer compound is adsorbed to the pigment and does not function as a developable group, resulting in a decrease in developability. In addition, the pigments may be adsorbed.

  In addition, when a basic polymer type dispersant is used for the purpose of improving dispersibility, an acid group and a basic group are introduced into the dispersant when an acid group is introduced into the polymer compound in order to impart developability. Coexist, and the dispersing agent is gelled, and as a result, the pigments are adsorbed.

  In the present invention, by introducing an acid group into a hydrophobic cycloalkyl group, an aromatic group, etc., the cyclic structure causes a decrease in dispersion stability due to the acid group, which is the above-mentioned problem, and causes gelation. Acid-base reactions are inhibited. Therefore, the dispersion stability of the dispersion composition resulting from the acid group is not deteriorated. Moreover, since the acid group expresses the developability inherent to the acid group by contacting with a large amount of alkali, the curable composition of the present invention containing the dispersion composition having such an acid group is used as a color filter. When used, it is considered that good developability can be imparted by the introduced acid group. In particular, the use of a polymer compound having an acid group directly bonded to a cyclic structure is considered to have a great effect.

  Hereinafter, the pigment dispersion composition, the photocurable composition, the color filter, and the method for producing the color filter of the present invention will be described in detail.

(Pigment dispersion composition)
The pigment dispersion composition of the present invention has a weight average molecular weight of 1,000 or more having a group dissociated by at least one alkali in the organic solvent (hereinafter sometimes referred to as “acid group” as appropriate) on the cyclic structure. It contains 100,000 or less polymer compound (hereinafter sometimes referred to as “specific polymer compound” as appropriate) and at least one pigment.

By using this specific polymer compound, a highly dispersible pigment dispersion composition can be obtained. Further, when the pigment dispersion composition is used for a color filter, a color filter having excellent developability and surface smoothness can be obtained.
Hereafter, each component which comprises the pigment dispersion composition of this invention is demonstrated.

<(A) Specific polymer compound>
The pigment dispersant of the present invention contains a specific polymer compound having an acid group directly bonded to a cyclic structure and having a weight average molecular weight of 1,000 or more and 100,000 or less.
Since the pigment dispersion composition of the present invention contains (A) the specific polymer compound, the dispersion state of the pigment in the organic solvent is improved, and for example, a color filter is configured using the pigment dispersion composition. In some cases, high developability and surface smoothness can be exhibited even when the pigment is contained at a high concentration.

(A) Examples of the acid group in the specific polymer compound include phenolic hydroxyl group, carboxylic acid group, sulfonic acid group, sulfonamide group, sulfonylimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, and (alkylsulfonyl). (Alkylcarbonyl) imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris (alkyl A sulfonyl) methylene group, a group having a fluorinated alcohol group, and the like.
Of these acid groups, a carboxylic acid group is preferred from the viewpoints of developability and ease of introduction.

  The amount of the repeating unit containing an acid group is preferably 5 to 50% by mass and more preferably 5 to 30% by mass in the total solid content of the (A) specific polymer compound.

  Here, the (A) specific polymer compound is preferably a compound having a monomer represented by the following general formula (GI).

  In General Formula (G-1), X represents a hydrogen atom or a methyl group. W represents a single bond, a single linking group selected from the following atomic groups, or a linking group formed by arbitrarily combining two or more thereof. Q represents a cyclic structure which may have a substituent. n represents an integer of 1 to 3.

Z ¹ and Z ² represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, or a hydroxy group. Z ³ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 20 carbon atoms.

  Examples of the substituent other than the acid group that can be introduced into Q in the general formula (G-1) include an alkyl group, a cycloalkyl group, a halogen atom, an alkoxy group, and an alkoxycarbonyl group, and an alkyl group, a halogen atom, An alkoxy group is more preferable.

  The general formula (GI) is preferably represented by the following general formulas (G-II) to (GV).

  In the general formulas (G-II) to (GV), X, Q and n have the same meanings as X, Q and n in the general formula (GI).

  Specific examples of general formulas (GI) to (GV) are shown below.

  Among the above specific examples, G-4, G-5, G-6, G-8, G-9, G-13, G-14, G-15, G-19, G-20, G-21, More preferred are monomers represented by G-23, G-24, G-25, G-26, G-27, G-28, G-30, G-33, G-35, G-38, Monomers represented by G-4, G-5, G-6, G-9, G-14, G-20, G-25, and G-26 are more preferred.

The (A) specific polymer compound of the present invention can be synthesized by polymerizing monomers as described above, or can be synthesized by reacting a precursor polymer compound with a low molecular compound having an acid group. it can.
The (A) specific polymer compound of the present invention is more preferably at least one selected from a block polymer, a graft polymer, and a terminal-modified polymer.

  The (A) specific polymer compound of the present invention is considered to act to adsorb on the pigment surface and prevent reaggregation in the dispersion step. Therefore, the specific polymer compound (A) of the present invention may be a linear random copolymer, but a block polymer, graft polymer, and terminal-modified polymer that are more effective may be mentioned as preferred structures. it can.

(Linear type random copolymer)
The linear random copolymer is obtained by subjecting a monomer containing an acid group represented by the above general formulas (GI) to (GV) to any other copolymerizable monomer or any other polymerization method such as radical polymerization. Obtainable. Other copolymerizable monomers will be described in detail in the section of block type polymer. (1) Monomer having organic dye structure or heterocyclic structure, (2) Monomer having acidic group, (3) Basic A monomer having a nitrogen atom, (4) a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group, (5) Monomers containing ionic functional groups, (6) (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, Monomers such as styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile Can be arbitrarily selected.
In addition, it is preferable to include one or more selected from the monomer groups (1) to (3).

  The preferred weight average molecular weight of the linear random copolymer is not particularly limited, but is preferably in the range of 1,000 to 100,000, more preferably in the range of 3,000 to 50,000. When the weight average molecular weight is 1,000 or more, a stabilizing effect can be obtained more effectively, and when the weight average molecular weight is 100,000 or less, it is more effectively adsorbed and has good dispersibility. Can be demonstrated.

(Block type polymer)
Although it does not specifically limit as a block type polymer, The block type polymer which consists of a pigment adsorption block (a), the block (b) which has an acid group, and the block (c) which does not adsorb | suck to a pigment is mentioned.
Although it does not restrict | limit especially as a monomer which comprises a pigment adsorption block (a), For example, the monomer which has a functional group which can adsorb | suck to a pigment is mentioned. Specific examples include a monomer having an organic dye structure or a heterocyclic structure, a monomer having an acidic group, and a monomer having a basic nitrogen atom.

  Examples of the monomer having an organic dye structure or a heterocyclic structure include, for example, phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, anthanthrone Ron, flavanthrone, perinone, perylene, and thioindigo dye structures such as thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadi Azole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolino , Mention may be made of benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, a monomer having a heterocyclic structure anthraquinone. More specifically, although not particularly limited, monomers having the following structures can be exemplified.

The monomer having an acidic group may include a vinyl monomer having a carboxyl group and a vinyl monomer having a sulfonic acid group or a phosphoric acid group.
Examples of the vinyl monomer having a carboxyl group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and acrylic acid dimer. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group. Of these, (meth) acrylic acid is particularly preferable from the viewpoints of copolymerizability, cost, solubility, and the like.

  Examples of the vinyl monomer having a sulfonic acid group include 2-acrylamido-2-methylpropanesulfonic acid, and examples of the vinyl monomer having a phosphoric acid group include phosphoric acid mono (2-acryloyloxyethyl ester) and phosphoric acid. And mono (1-methyl-2-acryloyloxyethyl ester).

  The acid group of the present invention is introduced separately from the acid group described above.

  Examples of the monomer having a basic nitrogen atom include vinyl pyridine, vinyl imidazole, vinyl triazole and the like as monomers having a heterocyclic ring, and (meth) acrylic acid ester as N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylate, N, N-dimethylaminohexyl (meth) acrylate, ( (Meth) acrylic acid N, N-diethylaminoethyl, (meth) acrylic acid N, N-diisopropylaminoethyl, (meth) acrylic acid N, N-di-n-butylaminoethyl, (meth) acrylic acid N, N- Di-i-butylaminoethyl, morpholinoethyl (meth) acrylate, piperidy (meth) acrylate Ethyl, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyrrolidylaminoethyl (meth) acrylate, and N, N-methylphenylaminoethyl (meth) acrylate, and the like ( As meta) acrylamides, N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N′-dimethylaminoethyl) methacrylamide, N- (N ′, N′-diethylaminoethyl) acrylamide N- (N ′, N′-diethylaminoethyl) methacrylamide, N- (N ′, N′-dimethylaminopropyl) acrylamide, N- (N ′, N′-dimethylaminopropyl) methacrylamide, N- ( N ', N'-diethylaminopropyl) acrylamide, N- (N', N'-diethylaminopropyl) methacrylate Luamide, 2- (N, N-dimethylamino) ethyl (meth) acrylamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide , Morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl-2-pyrrolidyl (meth) acrylamide, etc., and styrenes include N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene, etc. .

  Moreover, it is also possible to use a monomer having a urea group, a urethane group, a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a hydroxyl group. Specific examples include monomers having the following structure.

  Furthermore, a monomer containing an ionic functional group can be used. Examples of ionic vinyl monomers (anionic vinyl monomers, cationic vinyl monomers) include, as anionic vinyl monomers, alkali metal salts of vinyl monomers having the acidic group, organic amines (for example, triethylamine, dimethylaminoethanol, etc.) As a cationic vinyl monomer, the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom). Benzyl halides such as benzyl chloride and benzyl bromide; alkylsulfonic acid esters such as methanesulfonic acid (alkyl group: C1-18); arylsulfonic acid alkyl esters such as benzenesulfonic acid and toluenesulfonic acid (alkyl group: C1); -18); Dia sulfate Kill (alkyl group: C1 -4) that is quaternized with such, like dialkyl diallyl ammonium salts.

  The monomer having a functional group capable of adsorbing to the pigment can be appropriately selected according to the type of pigment to be dispersed, and these may be used alone or in combination of two or more.

Examples of the monomer constituting the block (b) having an acid group include those already described. Preferably, it is composed of monomers represented by the above general formulas (GI) to (GV).
The monomer having an acid group can be appropriately selected depending on the type of pigment to be dispersed, and these may be used alone or in combination of two or more.

  The monomer constituting the block (c) that is not adsorbed on the pigment is not particularly limited, and examples thereof include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, and fumaric acid diesters. Itaconic acid diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile and the like can be mentioned. These monomers may be used independently and may use 2 or more types together.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid t-octyl, (meth) acrylic acid dodecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid acetoxyethyl, (meth) acrylic acid phenyl, (meth) 4-hydroxybutyl acrylate, 2-methoxyethyl (meth) acrylate, (meth) a 2-ethoxyethyl laurate, 2- (2-methoxyethoxy) ethyl (meth) acrylate, 2-chloroethyl (meth) acrylate, vinyl (meth) acrylate, 2-phenylvinyl (meth) acrylate, (meth ) 1-propenyl acrylate, allyl (meth) acrylate, 2-allyloxyethyl (meth) acrylate, propargyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth ) Diethylene glycol monoethyl ether acrylate, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene Glycol monoethyl ether, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxy polyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acryl Trifluoroethyl acid, octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate, tribromo (meth) acrylate Examples thereof include phenyloxyethyl and (meth) acrylic acid γ-butyrolactone.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N- Methylo Acrylamide, N- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, such as N- allyl (meth) acrylamide.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

  Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.

Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.
Examples of (meth) acrylonitrile include methacrylonitrile and acrylonitrile.

  As a method for obtaining the block polymer in the present invention, a conventionally known method can be used. For example, living polymerization, iniferter method and the like are known, and as another method, in radical polymerization of a monomer having a pigment adsorption group or a monomer having no pigment adsorption group, thiolcarboxylic acid or 2 A polymer obtained by polymerizing a compound containing a thioester and a thiol group in a molecule such as -acetylthioethyl ether or 10-acetylthiodecanethiol is treated with an alkali such as sodium hydroxide or ammonia. A method is also known in which a polymer having a thiol group at one end and radical polymerization of the monomer component of the other block in the presence of the resulting polymer having a thiol group at one end is known. Among these, living polymerization is preferable.

  The weight average molecular weight of the block polymer is not particularly limited, but is preferably in the range of 1,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight is 1,000 or more, a stabilizing effect can be obtained more effectively, and when the weight average molecular weight is 100,000 or less, it is more effectively adsorbed and has good dispersibility. Can be demonstrated.

(Graft type polymer)
For the graft polymer, the acid group of the present invention may be contained in either the main chain or the branch or both. As a method for synthesizing a graft polymer, as described in New Polymer Experiments Vol. 2 (Kyoritsu Shuppan, 1995), a general method is (1) a method of polymerizing a branch monomer from a main chain polymer, ( 2) A method of bonding a branched polymer to a main chain polymer (3) A method of copolymerizing a main chain monomer with a branched polymer can be used.

That is, the graft-type polymer that can be used in the present invention is a monomer 1 containing an acid group represented by the above general formulas (GI) to (G-III) in either the main chain or the branch or both. It is obtained by copolymerizing more than one species with other copolymerizable monomers.
Examples of other copolymerizable monomers include (1) monomers having an organic dye structure or a heterocyclic structure, (2) monomers having an acidic group, (3) monomers having a basic nitrogen atom, and (4) urea. A group having 4 or more carbon atoms, a urethane group, a coordinating oxygen atom, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group, (5) a monomer containing an ionic functional group, 6) (Meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins One or more types of monomers such as styrene, maleimides and (meth) acrylonitrile can be arbitrarily selected.

As a preferable form in the graft type polymer of the present invention, the following forms may be mentioned.
1. Monomers represented by the aforementioned (1) to (6), monomers containing acid groups represented by the above general formulas (GI) to (GV), and polymerizable oligomers (hereinafter referred to as macromonomers). Graft type polymer as copolymerization component (particularly preferably including (1))
2. The monomer represented by the above (1) to (6) and the polymerizable oligomer (hereinafter referred to as macromonomer) containing the acid group represented by the general formulas (GI) to (GV) are copolymerized. Graft type polymer as component (particularly preferably including (1))
3. Monomers represented by the aforementioned formulas (1) to (6), monomers containing acid groups represented by the general formulas (GI) to (GV), general formulas (GI) to (G- Graft type polymer (particularly preferably including (1)) having a polymerizable oligomer (hereinafter referred to as macromonomer) containing an acid group shown in V) as a copolymerization component

  A preferred structure of the macromonomer is shown below.

In General Formula (6), ^R76 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and W is the same as W in General Formula (GI). A represents a repeating unit composed of a radical polymerizable monomer such as (meth) acrylic acid ester, (meth) acrylonitrile, styrene derivative, (meth) acrylamides and the like.
Specific examples of the macromonomer represented by the general formula (6) include the following.

  The macromonomer containing an acid group represented by the general formulas (GI) to (GV) is represented by (GI) to (GV) in the repeating unit of A in the general formula (6). A monomer having a repeating unit composed of the indicated monomers.

The weight average molecular weight of the graft polymer is not particularly limited, but is preferably in the range of 1,000 to 100,000, and more preferably in the range of 5,000 to 50,000. When the weight average molecular weight is 1,000 or more, a stabilizing effect can be obtained more effectively, and when the weight average molecular weight is 100,000 or less, it is more effectively adsorbed and has good dispersibility. Can be demonstrated.
In particular, the weight average molecular weight of the branch is preferably 300 to 30,000. More preferably, it is 1,000-20,000. When the molecular weight of the branch portion is in the above range, the developability is particularly good and the development latitude is wide.

(Terminal modified polymer)
The terminal-modified polymer is a polymer having a repeating unit having the acid group of the present invention in the main chain and having a functional group having a high affinity for the pigment at the terminal. That is, as the main chain, the above-mentioned linear random copolymer can be used as it is. As the monomer used for copolymerization, for example, the above-mentioned “monomer having acid group (b)” and “monomer (c) constituting a block not adsorbed to the pigment” are used as the radical polymerizable monomer. be able to. The terminal-modified polymer that can be used in the present invention is a polymer obtained by subjecting the terminal of this linear random copolymer to the modification described below.

A method for synthesizing a polymer having a functional group at the end of the polymer is not particularly limited, and examples thereof include the following methods and a combination thereof.
1. 1. A method of synthesizing by polymerization (for example, radical polymerization, anionic polymerization, cationic polymerization, etc.) using a functional group-containing polymerization initiator. Method of synthesizing by radical polymerization using a functional group-containing chain transfer agent The functional group introduced here is an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, Examples thereof include groups having a coordinated oxygen atom, hydrocarbon groups having 4 or more carbon atoms, alkoxysilyl groups, epoxy groups, isocyanate groups, hydroxyl groups, and ionic functional groups.

  Examples of the chain transfer agent capable of introducing a functional group at the polymer terminal include mercapto compounds (for example, thioglycolic acid, thiomalic acid, thiosalicylic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, N- ( 2-mercaptopropionyl) glycine, 2-mercaptonicotinic acid, 3- [N- (2-mercaptoethyl) carbamoyl] propionic acid, 3- [N- (2-mercaptoethyl) amino] propionic acid, N- (3- Mercaptopropionyl) alanine, 2-mercaptoethanesulfonic acid, 3-mecaptopropanesulfonic acid, 4-mercaptobutanesulfonic acid, 2-mercaptoethanol, 3-mercapto-1,2-propanediol, 1-mercapto-2-propanol 3-mercapto-2-butano , Mercaptophenol, 2-mercaptoethylamine, 2-mercaptoimidazole, 2-mercapto-3-pyridinol, benzenethiol, toluenethiol, mercaptoacetophenone, naphthalenethiol, naphthalenemethanethiol, etc.) or oxidized products of these mercapto compounds Examples thereof include disulfide compounds and halogen compounds (for example, 2-iodoethanesulfonic acid, 3-iodopropanesulfonic acid, etc.).

  Moreover, as a polymerization initiator which can introduce | transduce a functional group into a polymer terminal, for example, 2,2'-azobis (2-cyanopropanol), 2,2'-azobis (2-cyanopentanol), 4,4'- Azobis (4-cyanovaleric acid), 4,4′-azobis (4-cyanovaleric acid chloride), 2,2′-azobis [2- (5-methyl-2-imidazolin-2-yl) propane], 2 , 2′-azobis [2- (2-imidazolin-2-yl) propane], 2,2′-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane], 2, 2'-azobis {2- [1- (2-hydroxyethyl) -2-imidazolin-2-yl] propane}, 2,2'-azobis [2-methyl-N- (2-hydroxyethyl) -propionamide ] Or this Like derivatives of.

  The molecular weight of the terminal-modified polymer is preferably a weight average molecular weight of 1,000 to 50,000. When the number average molecular weight is 1,000 or more, the steric repulsion effect as a pigment dispersant can be more effectively obtained, and when it is 50,000 or less, the steric effect is more effectively suppressed, and the pigment The adsorption time can be shortened.

  (A) The specific polymer compound is preferably added in an amount of 0.5 to 100% by weight, more preferably 3 to 100% by weight, particularly 5 to 80% by weight based on the pigment. preferable. When these polymer compounds are used as a pigment dispersant within the above range, a sufficient pigment dispersion effect can be obtained. However, the optimum addition amount of the polymer compound is appropriately adjusted depending on the combination of the type of pigment used, the type of solvent, and the like.

(A) The specific polymer compound is preferably a polymer compound having a weight average molecular weight of 1,000 or more and 100,000 or less. Among the above-mentioned compounds, a graft polymer and a terminal-modified polymer are preferable. Graft type polymer containing copolymer units derived from monomer having structure, organic dye structure, heterocyclic structure, acidic group, group having basic nitrogen atom, urea group, or urethane group as terminal group A terminal-modified polymer is particularly preferable.
A high molecular compound may be used independently and may be used in mixture of 2 or more types.

  The weight average molecular weight of the (A) specific polymer compound is preferably 3,000 to 100,000, more preferably 5,000 to 50,000, and 10,000 to 30,000. More preferably it is. By setting it as the said range, it is excellent in dispersion stability as a pigment dispersant, and can adsorb | suck with a pigment effectively.

(A) The specific polymer compound is preferably added in an amount of 0.5 to 100 parts by weight, more preferably 3 to 100 parts by weight, and more preferably 5 to 80 parts by weight with respect to 100 parts by weight of the pigment. Part is particularly preferred.
When these polymer compounds are used as a pigment dispersant within the above range, a sufficient pigment dispersion effect can be obtained. However, the optimum addition amount of the polymer compound is appropriately adjusted depending on the combination of the type of pigment used, the type of solvent, and the like.

(A) As an acid value of a high molecular compound, 50-300 mgKOH / g is preferable, More preferably, it is 50-200 mgKOH / g.
The acid value is based on the measurement of the amount (mg) of potassium hydroxide required to neutralize the compound. By adjusting the number of acid groups possessed by the monomer, the molecular weight of the monomer, the composition ratio of the monomers, etc., and controlling the number of acid groups possessed by the resin, a resin having a desired acid value can be obtained.

<(B) Pigment>
The pigment dispersion composition of the present invention contains at least one (B) pigment in an organic solvent.
As the pigment that can be used in the pigment dispersion composition of the present invention, conventionally known various inorganic pigments or organic pigments can be used. Moreover, considering that it is preferable that the pigment has a high transmittance regardless of whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle size as small as possible, and considering handling properties. Then, it is preferably a pigment having an average primary particle diameter of 0.01 to 0.3 μm, more preferably 0.01 to 0.15 μm. When the particle size is within the above range, the transmittance is high, the color characteristics are good, and it is effective for forming a color filter with high contrast.
The average primary particle diameter is obtained by observing with an SEM or TEM, measuring 100 particle sizes in a portion where the particles are not aggregated, and calculating an average value.

  Examples of the inorganic pigment include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony And metal oxides such as the above, and complex oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 52: 1, 52: 2, 53: 1, 57: 1, 60: 1, 63: 1, 66, 67, 81: 1, 81: 2, 81: 3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254, 255, 264, 270, 272, 279,
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 17 , 175,176,177,179,180,181,182,185,187,188,193,194,199,213,214
C. I. Pigment Orange 2, 5, 13, 16, 17: 1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73
C. I. Pigment Green 7, 10, 36, 37
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, 66, 79, 79 Cl substituent was changed to OH Stuff, 80
C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42
C. I. Pigment Brown 25, 28
C. I. Pigment Black 1, 7 and the like.

Among these, the pigments that can be preferably used include the following. However, the present invention is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37;
C. I. Pigment Black 1, 7

  These organic pigments can be used alone or in various combinations in order to increase color purity. Specific examples of the above combinations are shown below. For example, as a red pigment, an anthraquinone pigment, a perylene pigment, a diketopyrrolopyrrole pigment alone or at least one of them, a disazo yellow pigment, an isoindoline yellow pigment, a quinophthalone yellow pigment, or a perylene red pigment , A mixture with an anthraquinone red pigment, a diketopyrrolopyrrole red pigment, or the like can be used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177, and perylene pigments include C.I. I. Pigment red 155, C.I. I. Pigment Red 224, and diketopyrrolopyrrole pigments include C.I. I. Pigment Red 254, and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 139 or C.I. I. Mixing with Pigment Red 177 is preferred. The mass ratio of the red pigment to the other pigment is preferably 100: 5 to 100: 80. If it is less than 100: 4, it may be difficult to suppress the light transmittance from 400 nm to 500 nm, and the color purity may not be improved. Further, when the ratio is 100: 81 or more, the coloring power may decrease. Particularly, the mass ratio is optimally in the range of 100: 10 to 100: 65. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  Further, as the green pigment, one kind of halogenated phthalocyanine pigment can be used alone or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment or an isoindoline yellow pigment can be used. . For example, C.I. I. Pigment Green 7, 36, 37 and C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 180 or C.I. I. Mixing with Pigment Yellow 185 is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 200. When the mass ratio is less than 100: 5, it is difficult to suppress the light transmittance of 400 to 450 nm, and the color purity may not be increased. On the other hand, when the ratio exceeds 100: 200, the dominant wavelength tends to be longer and the deviation from the NTSC target hue may become large. The mass ratio is particularly preferably in the range of 100: 20 to 100: 150.

As the blue pigment, a single phthalocyanine pigment or a mixture of this and a dioxazine purple pigment can be used. As a particularly preferred example, C.I. I. Pigment blue 15: 6 and C.I. I. A mixture with pigment violet 23 can be mentioned.
The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 100, more preferably 100: 70 or less.

Moreover, as a pigment suitable for black matrix use, carbon black, graphite, titanium black, iron oxide, titanium oxide alone or a mixture thereof can be used, and a combination of carbon black and titanium black is preferable.
The mass ratio of carbon black to titanium black is preferably in the range of 100: 0 to 100: 60. If it is 100: 61 or more, the dispersion stability may decrease.

In the present invention, when a dye is used as the colorant, a photocurable composition that is uniformly dissolved is obtained.
There is no restriction | limiting in particular as dye which can be used as a coloring agent, The well-known dye conventionally used as a color filter use can be used. For example, Japanese Patent Application Laid-Open No. 64-90403, Japanese Patent Application Laid-Open No. 64-91102, Japanese Patent Application Laid-Open No. 1-94301, Japanese Patent Application Laid-Open No. 6-11614, No. 2592207, US Pat. No. 4,808,501. Specification, US Pat. No. 5,667,920, US Pat. No. 5,059,500, JP-A-5-333207, JP-A-6-35183, JP-A-6-51115 JP-A-6-194828, JP-A-8-21599, JP-A-4-249549, JP-A-10-123316, JP-A-11-302283, JP-A-7-286107, JP 2001-4823, JP-A-8-15522, JP-A-8-29771, JP-A-8-146215, JP-A-11-3434. 7, JP-A-8-62416, JP-A-2002-14220, JP-A-2002-14221, JP-A-2002-14222, JP-A-2002-14223, JP-A-8-302224 JP-A-8-73758, JP-A-8-179120, JP-A-8-151531, and the like.

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, A dye such as xanthene, phthalocyanine, benzopyran, or indigo can be used.

  As content in the pigment dispersion composition of a pigment, 1-30 mass% is preferable with respect to the total solid (mass) of this composition, and 3-20 mass% is more preferable. When the pigment content is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.

(Pigment processing)
It is preferable to use the pigment of the present invention that has been subjected to a refinement treatment in advance. The finer primary particles of the pigment are well known by mechanically kneading with i) a pigment, ii) a water-soluble inorganic salt, and iii) a water-soluble organic solvent that does not substantially dissolve the inorganic salt with a kneader. (Salt milling method). In this step, if necessary, iv) a pigment-coated polymer compound may be used at the same time.

  i) Examples of the pigment include the same pigments as described above.

  ii) The water-soluble inorganic salt is not particularly limited as long as it is soluble in water, and sodium chloride, barium chloride, potassium chloride, sodium sulfate, and the like can be used. Sodium is preferably used. The amount of the inorganic salt used for salt milling is preferably 1 to 30 times by weight, more preferably 5 to 25 times by weight of the organic pigment, and the water content is preferably 1% or less from the viewpoint of both processing efficiency and production efficiency. This is because the finer efficiency is higher as the amount ratio of the inorganic salt to the organic pigment is larger, but the processing amount of one pigment is reduced.

iii) A small amount of a water-soluble organic solvent that does not substantially dissolve the inorganic salt serves to wet the organic pigment and the inorganic salt, dissolves (mixes) in water, and substantially uses the inorganic salt used. If it does not melt | dissolve in it, it will not specifically limit. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether. Acetate, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol Monoethyl ether, liquid polypropylene glycol or the like is used.
However, if it is adsorbed to the pigment by using a small amount and does not flow away into the wastewater, benzene, toluene, xylene, ethylbenzene, chlorobenzene, nitrobenzene, aniline, pyridine, quinoline, tetrahydrofuran, dioxane, ethyl acetate, isopropyl acetate, butyl acetate, hexane , Heptane, octane, nonane, decane, undecane, dodecane, cyclohexane, methylcyclohesasan, halogenated hydrocarbon, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, etc. Two or more kinds of solvents may be mixed and used as necessary.

  The addition amount of the water-soluble organic solvent is preferably 5 to 50 parts by weight with respect to 100 parts by weight of the inorganic salt. More preferably, it is 10 to 40 parts by weight, and optimally 15 to 35 parts by weight. When the addition amount is less than 5 parts by weight, uniform kneading becomes difficult and the particle size may become uneven. When the addition amount is 50 parts by weight or more, the kneaded composition becomes too soft, and it becomes difficult to apply shear to the kneaded composition, so that a sufficient refinement effect may not be obtained.

The water-soluble organic solvent may be added all at the beginning of salt milling, or may be added in divided portions. A water-soluble organic solvent may be used independently and can also use 2 or more types together.
Although there is no particular limitation on the operating conditions of the wet pulverizing apparatus in the present invention, the operating conditions in the case where the apparatus is a kneader are as follows. 200 rpm is preferable, and a relatively large biaxial rotation ratio is preferable because the grinding effect is large. The operation time is preferably 1 to 8 hours in combination with the dry grinding time, and the internal temperature of the apparatus is preferably 50 to 150 ° C. Further, the water-soluble inorganic salt that is a pulverization medium preferably has a pulverization particle size of 5 to 50 μm, a sharp particle size distribution, and a spherical shape.

  iv) The pigment-coated polymer compound should preferably be solid at room temperature, water-insoluble, and at least partially soluble in a water-soluble organic solvent used as a wetting agent during salt milling. A natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or a polymer compound ((A) specific polymer compound) having an acid group of the present invention on a cyclic structure is used.

When using a dried treated pigment, the compound used is preferably solid at room temperature. The natural resin is typically rosin, and the modified natural resin includes rosin derivatives, fiber derivatives, rubber derivatives, protein derivatives and oligomers thereof. Examples of the synthetic resin include epoxy resin, acrylic resin, maleic acid resin, butyral resin, polyester resin, melamine resin, phenol resin, polyurethane resin, and the like. Examples of synthetic resins modified with natural resins include rosin-modified maleic acid resins and rosin-modified phenolic resins.
Synthetic resins include polyamidoamine and its salt, polycarboxylic acid and its salt, high molecular weight unsaturated acid ester, polyurethane, polyester, poly (meth) acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate Is mentioned.
(A) As the specific polymer compound, the above-described polymer compound can be used.
The timing of adding these resins may be added all at the beginning of salt milling, or may be added in divided portions.

<Pigment derivative>
A pigment derivative is added to the pigment dispersion composition of the present invention as necessary. The pigment is introduced into the photocurable composition as fine particles by adsorbing the pigment derivative with a part having affinity with the dispersant or a polar group introduced onto the pigment surface and using this as the adsorption point of the dispersant. Therefore, the reaggregation can be prevented, and it is effective to construct a color filter having high contrast and excellent transparency.

  Specifically, the pigment derivative is a compound in which an organic pigment is used as a base skeleton, and an acidic group, a basic group, or an aromatic group is introduced into a side chain as a substituent. Specific examples of organic pigments include quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindolinone pigments, quinoline pigments, diketopyrrolopyrrole pigments, and benzoimidazolone pigments. Is mentioned. In general, light yellow aromatic polycyclic compounds such as naphthalene series, anthraquinone series, triazine series and quinoline series which are not called pigments are also included. Examples of the dye derivative include JP-A-11-49974, JP-A-11-189732, JP-A-10-245501, JP-A-2006-265528, JP-A-8-295810, and JP-A-11-199796. JP, 2005-234478, JP 2003-240938, JP 2001-356210, etc. can be used.

  As content in the pigment dispersion composition of the pigment derivative based on this invention, 1-30 weight part is preferable with respect to 100 weight part of pigments, and 3-20 weight part is more preferable. When the content is within the above range, while maintaining the viscosity low, the dispersion can be performed well and the dispersion stability after the dispersion can be improved, and the color characteristics with high transmittance can be obtained. When producing a filter, it can be configured to have high contrast with good color characteristics.

  The timing of adding the pigment derivative may be added during salt milling or may be added during dispersion.

  The dispersion method is, for example, using a bead disperser using zirconia beads or the like (for example, a disperse mat made by GETZMANN Co., Ltd.) that has been previously mixed with a pigment and a dispersant and previously dispersed with a homogenizer or the like. This can be done by fine dispersion. The dispersion time is preferably about 3 to 6 hours.

<Dispersant>
The pigment dispersion composition of the present invention contains at least one dispersant. With this dispersant, the dispersibility of the pigment can be improved.
As the dispersant, the above-described specific polymer compound (A) can be used. As a result, the dispersion state of the pigment in the organic solvent is improved, and, for example, when a color filter is configured using the pigment dispersion composition of the present invention, high developability even when the pigment is contained at a high concentration. Surface smoothness can be expressed.
(A) When the specific polymer compound is used as a dispersant, the above-described polymer compound can be used.

  In addition to (A) the specific polymer compound, conventionally known dispersants such as pigment dispersants and surfactants and other components can be added as necessary.

Known dispersants (pigment dispersants) include polymer dispersants such as polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth). Acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative, 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 according to the structure.

  The ratio of the pigment-coated polymer compound and the dispersant is not particularly limited. However, when the dispersant is a polymer dispersant, 10/90 to 90/10 is preferable, and 20/80 to 80/20 is more preferable. preferable.

  A preferred embodiment of the pigment dispersion composition of the present invention is a pigment dispersion obtained by dispersing a processed pigment coated with a polymer compound having a weight average molecular weight of 1,000 or more, a pigment derivative, and a dispersant in an organic solvent. It is a composition. (A) The specific polymer compound may be used as a pigment-coated polymer compound added during pigment processing or as a dispersant, but is preferably used as a dispersant.

  In the case of a polymer dispersant, the addition amount of the dispersant is preferably 0.5 to 100% by mass, more preferably 3 to 100% by mass, and more preferably 5 to 80% by mass with respect to the pigment. % Is particularly preferred. When the amount of the pigment dispersant is within the above range, a sufficient pigment dispersion effect can be obtained. However, the optimum addition amount of the dispersant is appropriately adjusted depending on the combination of the type of pigment used, the type of solvent, and the like.

-Preparation of pigment dispersion composition-
The preparation mode of the pigment dispersion composition of the present invention is not particularly limited. For example, the pigment, the pigment dispersant, and the solvent are mixed with a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, or the like. It can be obtained by performing fine dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 to 1 mm.

  Before performing bead dispersion, knead and disperse using a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder while applying strong shearing force. It is also possible to perform processing.

  For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.

  The pigment dispersion composition of the present invention is suitably used for a photocurable composition used for producing a color filter.

(Photocurable composition)
The photocurable composition of the present invention comprises the above-described pigment dispersion composition of the present invention, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator, and other components as necessary. May be included. Hereinafter, each component will be described in detail.

<Alkali-soluble resin>
The alkali-soluble resin is a linear organic polymer, and promotes at least one alkali-solubility in a molecule (preferably a molecule having an acrylic copolymer or a styrene copolymer as a main chain). It can be appropriately selected from alkali-soluble resins having a group (for example, carboxyl group, phosphoric acid group, sulfonic acid group, etc.). Of these, more preferred are those which are soluble in an organic solvent and can be developed with a weak alkaline aqueous solution.

  For example, a known radical polymerization method can be applied to the production of the alkali-soluble resin. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, etc. when producing an alkali-soluble resin by radical polymerization can be easily set by those skilled in the art, and the conditions are determined experimentally. It can also be done.

  As said linear organic high molecular polymer, the polymer which has carboxylic acid in a side chain is preferable. For example, it is described in JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-59-71048. Methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer, maleic acid copolymer, partially esterified maleic acid copolymer, etc., as well as in the side chain Preferred examples include acidic cellulose derivatives having a carboxylic acid, polymers having a hydroxyl group, an acid anhydride added to the polymer, and a polymer having a (meth) acryloyl group in the side chain.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymers and multi-component copolymers composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomers are preferable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. The polymer can be used by mixing in an arbitrary amount.

  In addition to the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer Etc.

  As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable. Here, (meth) acrylic acid is a general term that combines acrylic acid and methacrylic acid, and (meth) acrylate is also a general term for acrylate and methacrylate.

Examples of other monomers copolymerizable with the (meth) acrylic acid include alkyl (meth) acrylates, aryl (meth) acrylates, and vinyl compounds. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, pentyl ( Examples include meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, tolyl (meth) acrylate, naphthyl (meth) acrylate, cyclohexyl (meth) acrylate, and the like. it can.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyl toluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinyl pyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, CH _2. = CR ¹ R ² , CH ₂ = C (R ¹ ) (COOR ³ ) [wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ² is an aromatic group having 6 to 10 carbon atoms. Represents a hydrocarbon ring, and R ³ represents an alkyl group having 1 to 8 carbon atoms or an aralkyl group having 6 to 12 carbon atoms. ], Etc. can be mentioned.

These other copolymerizable monomers can be used singly or in combination of two or more. Preferred other copolymerizable monomers are selected from CH ₂ ═CR ¹ R ² , CH ₂ ═C (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one, and particularly preferably CH ₂ ═CR ¹ R ² and / or CH ₂ ═C (R ¹ ) (COOR ³ ).

  As content in the photocurable composition of alkali-soluble resin, 1-15 mass% is preferable in the total solid of this composition, More preferably, it is 2-12 mass%, Most preferably, it is 3 -10 mass%.

<Photopolymerizable compound>
As the photopolymerizable compound, a compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure is preferable, and a tetrafunctional or higher functional acrylate compound is more preferable.

Examples of the compound having at least one addition-polymerizable ethylenically unsaturated group and having a boiling point of 100 ° C. or higher at normal pressure include, for example, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, Monofunctional acrylates and methacrylates such as phenoxyethyl (meth) acrylate; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) Ether, tri (acryloyloxyethyl) isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, and the addition of ethylene oxide and propylene oxide followed by (meth) acrylate conversion, poly (pentaerythritol or dipentaerythritol poly ( (Meth) acrylate, urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191 Polyfunctional acrylates and methacrylates such as polyester acrylates described in JP-B-52-30490 and epoxy acrylates which are reaction products of epoxy resins and (meth) acrylic acid can be mentioned.
Furthermore, the Japan Adhesion Association Vol. 20, No. 7, pages 300 to 308, those introduced as photocurable monomers and oligomers can also be used.

  In addition, a compound which has been (meth) acrylated after adding ethylene oxide or propylene oxide to the polyfunctional alcohol described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof. Can be used.

Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are via ethylene glycol and propylene glycol residues are preferable. These oligomer types can also be used.

Also, urethane acrylates such as those described in JP-B-48-41708, JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B-58-49860, Urethane compounds having an ethylene oxide skeleton described in JP-B-56-17654, JP-B-62-39417, and JP-B-62-39418 are also suitable. Further, by using addition 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, It is possible to obtain a photopolymerizable composition having a very high photosensitive speed. Commercially available products include urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.), UA-7200 "(manufactured by Shin-Nakamura Chemical Co., Ltd., DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA- 306T, UA-306I, AH-600, T-600, AI-600 (manufactured by Kyoeisha) and the like.
Further, ethylenically unsaturated compounds having an acid group are also suitable. Examples of commercially available products include TO-756, which is a carboxyl group-containing trifunctional acrylate manufactured by Toagosei Co., Ltd., and a carboxyl group-containing pentafunctional acrylate. Some TO-1382 and the like can be mentioned.

The photopolymerizable compound can be used in combination of two or more, in addition to being used alone.
As content in the photocurable composition of a photopolymerizable compound, 20-200 mass% is preferable in the total solid of this composition, More preferably, it is 50-120 mass%. When the content of the photopolymerizable compound is within the above range, the curing reaction can be sufficiently performed.

<Photopolymerization initiator>
Examples of the photopolymerization initiator include halomethyl oxadiazole described in JP-A-57-6096, halomethyl-s-triazine described in JP-B-59-1281, JP-A-53-133428, and the like. Isoactive halogen compounds, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in each specification such as US Pat. No. US Pat. No. 4,318791 and European Patent Publication EP-88050A, described in US Pat. No. 4,1994,420 Aromatic ketone compounds such as benzophenones, (thio) xanthone or acridine compounds described in Fr-2456541, coumarin or biimidazole compounds described in JP-A-10-62986, JP-A-8 Sulfonium organoboron complexes such as 015521 , Etc. can be mentioned.

  Examples of the photopolymerization initiator include acetophenone series, ketal series, benzophenone series, benzoin series, benzoyl series, xanthone series, active halogen compounds (triazine series, halomethyloxadiazole series, coumarin series) acridine series, biimidazole series An oxime ester type is preferable.

  Examples of the acetophenone photopolymerization initiator include 2,2-diethoxyacetophenone, p-dimethylaminoacetophenone, 2-hydroxy-2-methyl-1-phenyl-propan-1-one, p-dimethylaminoacetophenone, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, Suitable examples include 2-tolyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1. be able to.

  Preferable examples of the ketal photopolymerization initiator include benzyl dimethyl ketal and benzyl-β-methoxyethyl acetal.

  Preferred examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, 4,4′-dichlorobenzophenone, and the like. Can do.

  Preferred examples of the benzoin-based or benzoyl-based photopolymerization initiator include benzoin isopropyl ether, zenzoin isobutyl ether, benzoin methyl ether, methyl o-benzoyl bezoate, and the like.

  Preferable examples of the xanthone photopolymerization initiator include diethylthioxanthone, diisopropylthioxanthone, monoisopropylthioxanthone, chlorothioxanthone, and the like.

  Examples of the active halogen photopolymerization initiator (triazine, oxadiazole, coumarin) include 2,4-bis (trichloromethyl) -6-p-methoxyphenyl-s-triazine, 2,4-bis. (Trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl) -1,3-butadienyl-s-triazine, 2, 4-bis (trichloromethyl) -6-biphenyl-s-triazine, 2,4-bis (trichloromethyl) -6- (p-methylbiphenyl) -s-triazine, p-hydroxyethoxystyryl-2,6-di (Trichloromethyl) -s-triazine, methoxystyryl-2,6-di (trichloromethyl-s-triazine, 3,4-dimethoxy Tyryl-2,6-di (trichloromethyl) -s-triazine, 4-benzoxolane-2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN, N- ( Diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) -s-triazine, 4- (pN, N- (diethoxycarbonylamino) -phenyl) -2,6-di (chloromethyl) ) -S-triazine, 2-trichloromethyl-5-styryl-1,3,4-oxodiazole, 2-trichloromethyl-5- (cyanostyryl) -1,3,4-oxodiazole, 2-trichloro Methyl-5- (naphth-1-yl) -1,3,4-oxodiazole, 2-trichloromethyl-5- (4-styryl) styryl-1,3,4-oxodiazole, 3-methyl- -Amino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-chloro-5-diethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin, 3-butyl A preferred example is -5-dimethylamino-((s-triazin-2-yl) amino) -3-phenylcoumarin.

  Preferable examples of the acridine photopolymerization initiator include 9-phenylacridine, 1,7-bis (9-acridinyl) heptane, and the like.

  Examples of the biimidazole photopolymerization initiator include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl) -4,5-diphenylimidazolyl dimer, Preferred examples include 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer.

  In addition to the above, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, O-benzoyl-4 ′-(benzmercapto) benzoyl-hexyl-ketoxime, 2,4,6-trimethylphenyl Examples thereof include carbonyl-diphenyl phosphonyl oxide and hexafluorophospho-trialkylphenyl phosphonium salt.

In this invention, it is not limited to the above photoinitiator, Other well-known things can also be used. For example, vicinal polykettle aldonyl compounds described in US Pat. No. 2,367,660, and α-carbonyl compounds described in US Pat. Nos. 2,367,661 and 2,367,670. An acyloin ether described in US Pat. No. 2,448,828, an α-hydrocarbon substituted aromatic acyloin compound described in US Pat. No. 2,722,512, US Pat. , 046,127 and 2,951,758, the triarylimidazole dimer / p-aminophenyl ketone combination described in US Pat. No. 3,549,367, Benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516; C. S. Perkin II (1979) 1653-1660, J. MoI. C. S. Examples include Perkin II (1979) 156-162, Journal of Photopolymer Science and Technology (1995) 202-232, and JP-A 2000-66385.
Moreover, these photoinitiators can also be used together.

  As content in the photocurable composition of a photoinitiator, 0.1-10.0 mass% is preferable in the total solid of this composition, More preferably, it is 0.5-5.0 mass%. It is. When the content of the photopolymerization initiator is within the above range, the polymerization reaction can proceed well to form a film with good strength.

<Sensitizing dye>
In the present invention, it is preferable to add a sensitizing dye as necessary. Exposure to a wavelength that can be absorbed by the sensitizing dye promotes radical generation reaction of the polymerization initiator component and polymerization reaction of the polymerizable compound thereby. Examples of such a sensitizing dye include a known spectral sensitizing dye or dye, or a dye or pigment that absorbs light and interacts with a photopolymerization initiator.

(Spectral sensitizing dye or dye)
Spectral sensitizing dyes or dyes preferred as sensitizing dyes used in the present invention are polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal). ), Cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), thiazines (eg thionine, methylene blue, toluidine blue), acridines (eg acridine orange, chloroflavin) , Acriflavine), phthalocyanines (eg, phthalocyanine, metal phthalocyanine), porphyrins (eg, tetraphenylporphyrin, central metal-substituted porphyrin), chlorophylls (eg, chlorophyll) Chlorophyllin, center metal-substituted chlorophyll), metal complexes (for example, the following compound), anthraquinones (e.g., anthraquinone), squaryliums (e.g., squarylium), and the like.

The example of a more preferable spectral sensitizing dye or dye is illustrated below.
A styryl dye described in JP-B-37-13034; a cationic dye described in JP-A-62-143044; a quinoxalinium salt described in JP-B-59-24147; described in JP-A-64-33104 A new methylene blue compound; anthraquinones described in JP-A No. 64-56767; benzoxanthene dyes described in JP-A No. 2-1714; acridines described in JP-A Nos. 2-226148 and 2-226149 Pyryllium salts described in JP-B-40-28499; Cyanines described in JP-B-46-42363; Benzofuran dyes described in JP-A-2-63053; JP-A-2-85858, JP-A-2-216154 Conjugated ketone dyes disclosed in Japanese Patent Publication No. 57-10605; Azocinnamylidene derivatives described in Japanese Patent No. 0321; cyanine dyes described in Japanese Patent Laid-Open No. 1-287105; Japanese Patent Laid-Open Nos. 62-31844, 62-31848, 62-1443043 Xanthene dyes described above; aminostyryl ketone described in JP-B-59-28325; dye described in JP-A-2-17943; merocyanine dye described in JP-A-2-244050; described in JP-B-59-28326 Merocyanine dyes described in JP-A-59-89303; merocyanine dyes described in JP-A-8-129257; benzopyran dyes described in JP-A-8-334897.

(Dye having a maximum absorption wavelength at 350 to 450 nm)
Other preferred embodiments of the sensitizing dye include dyes belonging to the following compound group and having a maximum absorption wavelength at 350 to 450 nm.
For example, polynuclear aromatics (eg, pyrene, perylene, triphenylene), xanthenes (eg, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), cyanines (eg, thiacarbocyanine, oxacarbocyanine), merocyanine (Eg, merocyanine, carbomerocyanine), thiazines (eg, thionine, methylene blue, toluidine blue), acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squalium (eg, , Squalium).

  More preferable examples of the sensitizing dye include compounds represented by the following general formulas (XIV) to (XVIII).

(In General Formula (XIV), A ¹ represents a sulfur atom or NR ⁵⁰ , R ⁵⁰ represents an alkyl group or an aryl group, and L ² 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. W represents an oxygen atom or a sulfur atom.)
Preferred specific examples [(F-1) to (F-5)] of the compound represented by the general formula (XIV) are shown below.

(In the general formula (XV), Ar ¹ and Ar ² each independently represent an aryl group, and are linked via a bond with —L ³ —, where L ³ represents —O— or —S—. W is synonymous with that shown in the general formula (XIV).)
Preferable examples of the compound represented by the general formula (XV) include the following [(F-6) to (F-8)].

(In General Formula (XVI), A ² represents a sulfur atom or NR ⁵⁹ , L ⁴ represents a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ² and a 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.)
Preferable examples of the compound represented by the general formula (XVI) include the following [(F-9) to (F-11)].

(In General Formula (XVII), A ³ and A ⁴ each independently represent —S— or —NR ⁶³ , R ⁶³ represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, and L ⁵ and L ⁶ each independently represent a nonmetallic atomic group that forms a basic nucleus of a dye in combination with adjacent A ³ and A ⁴ and adjacent carbon atoms, and R ⁶¹ and R ⁶² each independently (It can be a monovalent non-metallic atomic group or can be bonded to each other to form an aliphatic or aromatic ring.)
Preferable examples of the compound represented by the general formula (XVII) include the following [(F-12) to (F-15)].

  In addition, examples of suitable sensitizing dyes used in the present invention include those represented by the following formula (XVIII).

(In General Formula (XVIII), A represents an aromatic ring or a hetero ring which may have a substituent, X represents an oxygen atom or a sulfur atom or —N (R ¹ ) —, and Y represents an oxygen atom or —N (R ¹ ) — R ¹ , R ² , and R ³ each independently represent a hydrogen atom or a monovalent non-metallic atomic group, and A, R ¹ , R ² , and R ³ are Can be bonded to each other to form an aliphatic or aromatic ring.)

Here, when R ¹ , R ² , and R ³ represent a monovalent nonmetallic atomic group, they preferably represent a substituted or unsubstituted alkyl group or aryl group.
Next, preferred examples of R ¹ , R ² and R ³ will be specifically described. Examples of preferable alkyl groups include linear, branched, and cyclic alkyl groups having 1 to 20 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, Butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, hexadecyl, octadecyl, eicosyl, isopropyl, isobutyl, s-butyl, Examples thereof include t-butyl group, isopentyl group, neopentyl group, 1-methylbutyl group, isohexyl group, 2-ethylhexyl group, 2-methylhexyl group, cyclohexyl group, cyclopentyl group and 2-norbornyl group. Of these, linear alkyl groups having 1 to 12 carbon atoms, branched alkyl groups having 3 to 12 carbon atoms, and cyclic alkyl groups having 5 to 10 carbon atoms are more preferable.

As the substituent of the substituted alkyl group, a monovalent non-metallic atomic group other than hydrogen is used. Preferred examples include halogen atoms (—F, —Br, —Cl, —I), hydroxyl groups, alkoxy groups. Group, aryloxy group, mercapto group, alkylthio group, arylthio group, alkyldithio group, aryldithio group, amino group, N-alkylamino group, N, N-dialkylamino group, N-arylamino group, N, N-diaryl Amino group, N-alkyl-N-arylamino group, acyloxy group, carbamoyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, N, N-dialkylcarbamoyloxy group, N, N-diarylcarbamoyloxy Group, N-alkyl-N-arylcarbamoyloxy group, alkylsulfoxy , Arylsulfoxy group, acyloxy group, acylthio group, acylamino group, N-alkylacylamino group, N-arylacylamino group, ureido group, N-alkylureido group, N, N-dialkylureido group, N-arylureido Group, N, N-diarylureido group, N-alkyl-N-arylureido group, N-alkylureido group, N-arylureido group, N-alkyl-N-alkylureido group, N-alkyl-N-arylureido Group, N, N-dialkyl-N-alkylureido group, N, N-dialkyl-N-arylureido group, N-aryl-N-alkylureido group, N-aryl-N-arylureido group, N, N- Diaryl-N-alkylureido group, N, N-diaryl-N-arylureido group, N- Alkyl-N-aryl-N-alkylureido group, N-alkyl-N-aryl-N-arylureido group, alkoxycarbonylamino group, aryloxycarbonylamino group, N-alkyl-N-alkoxycarbonylamino group, N- Alkyl-N-aryloxycarbonylamino group, N-aryl-N-alkoxycarbonylamino group, N-aryl-N-aryloxycarbonylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group , Carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N, N-diarylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, alkylsulfinyl group, arylsulfinyl group Nyl group, alkylsulfonyl group, arylsulfonyl group, sulfo group (—SO ₃ H) and its conjugate base group (hereinafter referred to as sulfonate group), alkoxysulfonyl group, aryloxysulfonyl group, sulfinamoyl group, N-alkylsulfina Moyl group, N, N-dialkylsulfinamoyl group, N-arylsulfinamoyl group, N, N-diarylsulfinamoyl group, N-alkyl-N-arylsulfinamoyl group, sulfamoyl group, N-alkylsulfato group Famoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N, N-diarylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono group (—PO ₃ H ₂₎ and its conjugated base group (hereinafter referred to as phosphonato group), a dialkyl phosphonate Group _{(-PO 3 (alkyl) 2)} , diaryl phosphono group _{(-PO 3 (aryl) 2)} , alkyl aryl phosphono group _{(-PO 3 (alkyl) (aryl} )), monoalkyl phosphono group (-PO ₃ H (alkyl)) and its conjugate base group (hereinafter referred to as alkylphosphonate group), monoarylphosphono group (—PO ₃ H (aryl)) and its conjugate base group (hereinafter referred to as arylphosphonate group). ), A phosphonooxy group (—OPO ₃ H ₂₎ and its conjugate base group (hereinafter referred to as phosphonatoxy group), a dialkylphosphonooxy group (—OPO ₃ (alkyl) ₂ ), a diarylphosphonooxy group (—OPO ₃ (—OPO ₃ ( _{aryl) 2),} alkylaryl phosphono group _{(-OPO 3 (alkyl) (aryl} )), Monoarukiruho Honookishi group _(-OPO 3 H (alkyl)) and its conjugated base group (hereinafter referred to as alkylphosphonato group), monoarylphosphono group _(-OPO 3 H (aryl)) and its conjugated base group (hereinafter And cyano group, nitro group, aryl group, heteroaryl group, alkenyl group, alkynyl group, and silyl group.
Specific examples of the alkyl group in these substituents include the alkyl groups described above, and these may further have a substituent.

  Specific examples of the aryl group include phenyl group, biphenyl group, naphthyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, chloromethylphenyl group, hydroxyphenyl group, methoxyphenyl group. , Ethoxyphenyl group, phenoxyphenyl group, acetoxyphenyl group, benzoyloxyphenyl group, methylthiophenyl group, phenylthiophenyl group, methylaminophenyl group, dimethylaminophenyl group, acetylaminophenyl group, carboxyphenyl group, methoxycarbonylphenyl Group, ethoxyphenylcarbonyl group, phenoxycarbonylphenyl group, N-phenylcarbamoylphenyl group, phenyl group, cyanophenyl group, sulfophenyl group, sulfonatophenyl group, phosphonopheny Group, and a phosphate Hona preparative phenyl group.

  As the heteroaryl group, a group derived from a monocyclic or polycyclic aromatic ring containing at least one of nitrogen, oxygen and sulfur atoms is used, and as a particularly preferred example of the heteroaryl ring in the heteroaryl group, Is, for example, thiophene, thiathrene, furan, pyran, isobenzofuran, chromene, xanthene, phenoxazine, pyrrole, pyrazole, isothiazole, isoxazole, pyrazine, pyrimidine, pyridazine, indolizine, isoindolizine, indolizine, indazole, indazole, Purine, quinolidine, isoquinoline, phthalazine, naphthyridine, quinazoline, sinoline, pteridine, carbazole, carboline, phenanthrine, acridine, perimidine, phenanthrolin, phthalazine, phenalazine, phenoxazine, flaza , Include phenoxazine and the like, it may be further benzo-fused or may have a substituent.

Examples of alkenyl groups include vinyl, 1-propenyl, 1-butenyl, cinnamyl, 2-chloro-1-ethenyl, etc. Examples of alkynyl include ethynyl, 1 -Propynyl group, 1-butynyl group, trimethylsilylethynyl group and the like. Examples of G ¹ in the acyl group (G ¹ CO—) include hydrogen and the above alkyl groups and aryl groups. Among these substituents, even more preferred are halogen atoms (—F, —Br, —Cl, —I), alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, N-alkylamino groups, N, N— Dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group, acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamoyl group, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group Group, N-arylsulfide Moyl group, N-alkyl-N-arylsulfamoyl group, phosphono group, phosphonato group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonato group, monoaryl phosphono group, aryl phospho Examples thereof include a nato group, a phosphonooxy group, a phosphonatoxy group, an aryl group, an alkenyl group, and an alkylidene group (such as a methylene group).

  On the other hand, examples of the alkylene group in the substituted alkyl group include divalent organic residues obtained by removing any one of the hydrogen atoms on the alkyl group having 1 to 20 carbon atoms. Can include linear alkylene groups having 1 to 12 carbon atoms, branched chains having 3 to 12 carbon atoms, and cyclic alkylene groups having 5 to 10 carbon atoms.

Specific examples of preferred substituted alkyl groups as R ¹ , R ² , or R ³ obtained by combining the above substituents and alkylene groups include chloromethyl group, bromomethyl group, 2-chloroethyl group, trifluoromethyl group, methoxy Methyl group, methoxyethoxyethyl group, allyloxymethyl group, phenoxymethyl group, methylthiomethyl group, tolylthiomethyl group, ethylaminoethyl group, diethylaminopropyl group, morpholinopropyl group, acetyloxymethyl group, benzoyloxymethyl group, N -Cyclohexylcarbamoyloxyethyl group, N-phenylcarbamoyloxyethyl group, acetylaminoethyl group, N-methylbenzoylaminopropyl group, 2-oxoethyl group, 2-oxopropyl group, carboxypropyl group, methoxy Rubonylethyl group, allyloxycarbonylbutyl group, chlorophenoxycarbonylmethyl group, carbamoylmethyl group, N-methylcarbamoylethyl group, N, N-dipropylcarbamoylmethyl group, N- (methoxyphenyl) carbamoylethyl group, N-methyl -N- (sulfophenyl) carbamoylmethyl group, sulfobutyl group, sulfonatopropyl group, sulfonatobutyl group, sulfamoylbutyl group, N-ethylsulfamoylmethyl group, N, N-dipropylsulfamoylpropyl group, N- Tolylsulfamoylpropyl group, N-methyl-N- (phosphonophenyl) sulfamoyloctyl group, phosphonobutyl group, phosphonatohexyl group, diethylphosphonobutyl group, diphenylphosphonopropyl group, methylphosphonobutyl group, Methyl Phosphonatobutyl group, tolylphosphonohexyl group, tolylphosphonatohexyl group, phosphonooxypropyl group, phosphonatoxybutyl group, benzyl group, phenethyl group, α-methylbenzyl group, 1-methyl-1-phenylethyl group, p -Methylbenzyl group, cinnamyl group, allyl group, 1-propenylmethyl group, 2-butenyl group, 2-methylallyl group, 2-methylpropenylmethyl group, 2-propynyl group, 2-butynyl group, 3-butynyl group, etc. Can be mentioned.

Specific examples of preferred aryl groups as R ¹ , R ² , or R ³ include those in which 1 to 3 benzene rings form a condensed ring, and those in which a benzene ring and a 5-membered unsaturated ring form a condensed ring Specific examples include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, an indenyl group, an acenaphthenyl group, and a fluorenyl group. Among these, a phenyl group and a naphthyl group are more preferable. preferable.

Specific examples of preferred substituted aryl groups as R ^{1, R 2,} or R ³ is a substituent on the ring-forming carbon atoms of the aryl group described above, (other than a hydrogen atom) a monovalent non-metallic atomic group What has is used. Examples of preferred substituents include the aforementioned alkyl groups, substituted alkyl groups, and those previously shown as substituents in the substituted alkyl group. Preferred examples of such a substituted aryl group include biphenyl group, tolyl group, xylyl group, mesityl group, cumenyl group, chlorophenyl group, bromophenyl group, fluorophenyl group, chloromethylphenyl group, trifluoromethylphenyl group. Hydroxyphenyl group, methoxyphenyl group, methoxyethoxyphenyl group, allyloxyphenyl group, phenoxyphenyl group, methylthiophenyl group, tolylthiophenyl group, ethylaminophenyl group, diethylaminophenyl group, morpholinophenyl group, acetyloxyphenyl group, Benzoyloxyphenyl group, N-cyclohexylcarbamoyloxyphenyl group, N-phenylcarbamoyloxyphenyl group, acetylaminophenyl group, N-methylbenzoylaminophenyl group, cal Xiphenyl group, methoxycarbonylphenyl group, allyloxycarbonylphenyl group, chlorophenoxycarbonylphenyl group, carbamoylphenyl group, N-methylcarbamoylphenyl group, N, N-dipropylcarbamoylphenyl group, N- (methoxyphenyl) carbamoylphenyl group N-methyl-N- (sulfophenyl) carbamoylphenyl group, sulfophenyl group, sulfonatophenyl group, sulfamoylphenyl group, N-ethylsulfamoylphenyl group, N, N-dipropylsulfamoylphenyl group, N-tolylsulfamoylphenyl group, N-methyl-N- (phosphonophenyl) sulfamoylphenyl group, phosphonophenyl group, phosphonatophenyl group, diethylphosphonophenyl group, diphenylphosphonophenyl Methylphosphonophenyl group, methylphosphonatophenyl group, tolylphosphonophenyl group, tolylphosphonophenyl group, allylphenyl group, 1-propenylmethylphenyl group, 2-butenylphenyl group, 2-methylallylphenyl group, Examples include 2-methylpropenylphenyl group, 2-propynylphenyl group, 2-butynylphenyl group, 3-butynylphenyl group, and the like.

In addition, more preferable examples of R ² and R ³ include a substituted or unsubstituted alkyl group. Also, as more preferred examples of R ¹ include substituted or unsubstituted aryl group. The reason is not clear, but by having such a substituent, the interaction between the electronically excited state caused by light absorption and the initiator compound becomes particularly large, and the radical, acid or base of the initiator compound is generated. It is estimated that the efficiency is improved.

Next, A in the general formula (XVIII) will be described. A represents an aromatic ring or a heterocyclic ring which may have a substituent. Specific examples of the aromatic ring or heterocyclic ring which may have a substituent include R ¹ and R ² in the general formula (XVIII). , Or the same as those exemplified in the above description of R ³ .
Among them, preferable A includes an alkoxy group, a thioalkyl group, and an aryl group having an amino group, and particularly preferable A includes an aryl group having an amino group.

  Next, Y in the formula (XVIII) will be described. Y represents a nonmetallic atomic group necessary for forming a heterocyclic ring in cooperation with the above-described A and adjacent carbon atoms. Examples of such a heterocyclic ring include 5-, 6-, and 7-membered nitrogen-containing or sulfur-containing heterocyclic rings that may have a condensed ring, and preferably 5- or 6-membered heterocyclic rings.

Examples of nitrogen-containing heterocycles include L. G. Brooker et al., Journal of American Chemical Society, J. Am. Chem. Soc., Vol. 73 (1951), p. Any of those known to constitute a basic nucleus in merocyanine dyes described in 5326-5358 and references can be suitably used.
Specific examples include thiazoles (for example, thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole, 5-phenylthiazole, 4,5-dimethylthiazole, 4,5-diphenylthiazole, 4,5- Di (p-methoxyphenylthiazole), 4- (2-thienyl) thiazole, 4,5-di (2-furyl) thiazole, etc.), benzothiazoles (for example, benzothiazole, 4-chlorobenzothiazole, 5-chloro Benzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole, 4-methylbenzothiazole, 5-methylbenzothiazole, 6-methylbenzothiazole, 5-bromobenzothiazole, 4-phenylbenzothiazole, 5-phenylbenzothiazole 4-methoxybenzo Azole, 5-methoxybenzothiazole, 6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole, 5,6-dimethoxybenzothiazole, 5,6-dioxymethylenebenzothiazole, 5-hydroxybenzothiazole, 6-hydroxybenzothiazole, 6-dimethylaminobenzothiazole, 5-ethoxycarbonylbenzothiazole, etc.), naphthothiazoles (for example, naphtho [1,2 ] Thiazole, naphtho [2,1] thiazole, 5-methoxynaphtho [2,1] thiazole, 5-ethoxynaphtho [2,1] thiazole, 8-methoxynaphtho [1,2] thiazole, 7-methoxynaphtho [ , 2] thiazole, etc.), thianaphtheno-7,6,4,5-thiazoles (eg 4-methoxythianaphtheno-7,6,4,5-thiazole etc.), oxazoles (eg 4-methyl Oxazole, 5-methyl oxazole, 4-phenyl oxazole, 4,5-diphenyl oxazole, 4-ethyl oxazole, 4,5-dimethyl oxazole, 5-phenyl oxazole, etc.), benzoxazoles (benzoxazole, 5-chlorobenzoxazole) 5-methylbenzoxazole, 5-phenylbenzoxazole, 6-methylbenzoxazole, 5,6-dimethylbenzoxazole, 4,6-dimethylbenzoxazole, 6-methoxybenzoxazole, 5-methoxybenzoxazole, 4-ethoxyben Zooxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole, 5-hydroxybenzoxazole, 6-hydroxybenzoxazole, etc.),

  Naphthoxazoles (eg, naphtho [1,2] oxazole, naphtho [2,1] oxazole, etc.), selenazoles (eg, 4-methylselenazole, 4-phenylselenazole, etc.), benzoselenazoles ( For example, benzoselenazole, 5-chlorobenzoselenazole, 5-methoxybenzoselenazole, 5-hydroxybenzoselenazole, tetrahydrobenzoselenazole, etc.), naphthoselenazoles (for example, naphtho [1,2] selenazole, Naphtho [2,1] selenazole, etc.], thiazolines (for example, thiazoline, 4-methylthiazoline, 4,5-dimethylthiazoline, 4-phenylthiazoline, 4,5-di (2-furyl) thiazoline, 4,5 -Diphenylthiazoline, 4,5-di (p-methoxyphenyl) thi Zoline, etc.), 2-quinolines (for example, quinoline, 3-methylquinoline, 5-methylquinoline, 7-methylquinoline, 8-methylquinoline, 6-chloroquinoline, 8-chloroquinoline, 6-methoxyquinoline, 6- Ethoxyquinoline, 6-hydroxyquinoline, 8-hydroxyquinoline, etc.), 4-quinolines (eg, quinoline, 6-methoxyquinoline, 7-methylquinoline, 8-methylquinoline, etc.), 1-isoquinolines (eg, Isoquinoline, 3,4-dihydroisoquinoline, etc.), 3-isoquinolines (eg, isoquinoline, etc.), benzimidazoles (eg, 1,3-dimethylbenzimidazole, 1,3-diethylbenzimidazole, 1-ethyl-3) -Phenylbenzimidazole, etc.), 3,3-dialkylin Renins (for example, 3,3-dimethylindolenine, 3,3,5-trimethylindolenine, 3,3,7-trimethylindolenine, etc.), 2-pyridines (for example, pyridine, 5-methylpyridine, Etc.), 4-pyridine (for example, pyridine etc.) and the like. Moreover, the substituents of these rings may combine to form a ring.

Examples of the sulfur-containing heterocycle include a dithiol partial structure in dyes described in JP-A-3-296759.
Specific examples include benzodithiols (eg, benzodithiol, 5-t-butylbenzodithiol, 5-methylbenzodithiol, etc.), naphthodithiols (eg, naphtho [1,2] dithiol, naphtho [2,1 Dithiols, etc.), dithiols (for example, 4,5-dimethyldithiols, 4-phenyldithiols, 4-methoxycarbonyldithiols, 4,5-dimethoxycarbonyldithiols, 4,5-diethoxycarbonyldithiols) 4,5-ditrifluoromethyldithiol, 4,5-dicyanodithiol, 4-methoxycarbonylmethyldithiol, 4-carboxymethyldithiol, etc.).

  Of the examples of the nitrogen-containing or sulfur-containing heterocycle formed by Y in cooperation with the above-mentioned A and the adjacent carbon atom in the general formula (XVIII) described above, the partial structure of the following general formula (XVIII-2) The dye having the structure represented by the formula is particularly preferable because it provides a photosensitive composition having high sensitizing ability and extremely excellent storage stability. The dye having the structure represented by the general formula (XVIII-2) is a compound described in detail in Japanese Patent Application No. 2003-31253 as a novel compound.

(In General Formula (XVIII-2), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom or a sulfur atom or -N (R ¹ )-. R ¹ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, and A and R ¹ , R ⁴ , R ⁵ and R ⁶ are bonded to each other to form an aliphatic group. Or aromatic ring can be formed.)
In formula (XVIII-2), A and ^{R 1} are the same as in the general formula (XVIII), ^{R 4} and ^{R 2} in the general formula (XVIII), ^{R 5} is ^{R 3} in the general formula (XVIII) And R ⁶ has the same meaning as R ¹ in formula (XVIII).

  Next, the compound represented by formula (XVIII-3), which is a preferred embodiment of the compound represented by formula (XVIII) used in the present invention, will be described.

In the general formula (XVIII-3), A represents an aromatic ring or a hetero ring which may have a substituent, and X represents an oxygen atom or a sulfur atom or -N (R ¹ )-. R ¹ , R ⁴ and R ⁵ are each independently a hydrogen atom or a monovalent nonmetallic atomic group, and A and R ¹ , R ⁴ and R ⁵ are each aliphatic or aromatic. Can be linked to form a ring. Ar represents an aromatic ring or a heterocyclic ring having a substituent. However, the substituent on the Ar skeleton needs to have a sum of Hammett values greater than zero. Here, the sum of the Hammett values is greater than 0 means that the substituent has one substituent, and the Hammett value of the substituent may be greater than 0, and has a plurality of substituents. The sum of Hammett values at may be greater than zero.

In formula (XVIII-3), A and ^{R 1} have the same meanings as in formula (XVIII), ^{R 4} and ^{R 2} in the general formula (XVIII), ^{R 5} is ^{R 3} in the general formula (XVIII) It is synonymous with. Ar represents an aromatic ring or heterocyclic ring having a substituent, and specific examples thereof include an aromatic ring or heterocyclic ring having a substituent among those previously described in the description of A in the general formula (XVIII). The specific example which concerns is mentioned similarly. However, as a substituent that can be introduced into Ar in the general formula (XVIII-3), it is essential that the sum of Hammett values is 0 or more. Examples of such a substituent include a trifluoromethyl group, Examples include a carbonyl group, an ester group, a halogen atom, a nitro group, a cyano group, a sulfoxide group, an amide group, and a carboxyl group. The Hammett values of these substituents are shown below. Trifluoromethyl group (—CF ₃ , m: 0.43, p: 0.54), carbonyl group (eg, —COHm: 0.36, p: 0.43), ester group (—COOCH ₃ , m: 0 .37, p: 0.45), halogen atom (eg, Cl, m: 0.37, p: 0.23), cyano group (—CN, m: 0.56, p: 0.66), sulfoxide group (e.g. _{-SOCH 3, m: 0.52, p} : 0.45), amide groups (e.g. _{-NHCOCH 3, m: 0.21, p} : 0.00), carboxyl group (-COOH, m: 0. 37, p: 0.45). The parenthesis represents the introduction position of the substituent in the aryl skeleton and the Hammett value, and (m: 0.50) is the Hammett value of 0.50 when the substituent is introduced at the meta position. Indicates that there is. Among these, preferable examples of Ar include a phenyl group having a substituent, and preferable substituents on the Ar skeleton include an ester group and a cyano group. The substitution position is particularly preferably located at the ortho position on the Ar skeleton.

  Preferred specific examples of the sensitizing dye represented by the general formula (XVIII) according to the present invention [Exemplary Compound (F1) to Illustrative Compound (F56)] are shown below, but the present invention is not limited to these. Absent.

  Among the sensitizing dyes applicable to the present invention, the compound represented by the general formula (XVIII) is preferable from the viewpoint of deep part curability.

  With respect to the above-mentioned sensitizing dye, various chemical modifications as described below can be performed for the purpose of improving the characteristics of the photocurable composition of the present invention. For example, by combining a sensitizing dye and an addition polymerizable compound structure (for example, an acryloyl group or a methacryloyl group) by a method such as a covalent bond, an ionic bond, or a hydrogen bond, It is possible to improve the effect of suppressing the unnecessary precipitation of the dye from the crosslinked cured film.

The content of the sensitizing dye is preferably 0.01 to 20% by mass, more preferably 0.01 to 10% by mass, based on the total solid content of the colored photosensitive composition for a color filter of the present invention. More preferably, it is 0.1-5 mass%.
When the content of the sensitizing dye is within this range, it is highly sensitive to the exposure wavelength of the ultra-high pressure mercury lamp, and it is preferable in terms of development margin and pattern formability as well as deep film curability.

<Solvent>
In general, the pigment dispersion composition and photocurable composition of the present invention can be suitably prepared using a solvent together with the above components.
Solvents include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, lactic acid 3 such as ethyl, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-oxypropionate, ethyl 3-oxypropionate -Oxypropionic acid alkyl esters; methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-oxypropionate, 2-oxypropion Ethyl, propyl 2-oxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-oxy-2- Methyl methyl propionate, ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, Methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutanoate, ethyl 2-oxobutanoate and the like; ethers such as diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether Ter, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; aromatic hydrocarbons such as toluene, xylene and the like.

Of these, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate, butyl Carbitol acetate, propylene glycol methyl ether acetate and the like are suitable.
You may use a solvent in combination of 2 or more types besides using it independently.

-Other components-
In the photocurable composition of the present invention, a chain transfer agent, a fluorine-based organic compound, a thermal polymerization initiator, a thermal polymerization component, a thermal polymerization inhibitor, other fillers, and other than the above alkali-soluble resin, if necessary. Various additives such as a polymer compound, a surfactant, an adhesion promoter, an antioxidant, an ultraviolet absorber, and an aggregation inhibitor can be contained.

<Chain transfer agent>
Examples of the chain transfer agent which can be added to the colored curable composition of the present invention include N, N-dialkylaminobenzoic acid alkyl esters such as N, N-dimethylaminobenzoic acid ethyl ester, 2-mercaptobenzothiazole, 2 -Mercapto compounds having a heterocyclic ring such as mercaptobenzoxazole and 2-mercaptobenzimidazole, and aliphatic polyfunctional mercapto compounds.
A chain transfer agent may be used individually by 1 type, and may use 2 or more types together.

<Fluorine organic compounds>
By containing a fluorinated organic compound, the liquid properties (particularly fluidity) of the coating liquid can be improved, and the uniformity of the coating thickness and the liquid-saving property can be improved. That is, the interfacial tension between the object to be coated and the coating liquid is reduced to improve the wettability to the object to be coated, and the coating property to the object to be coated is improved, so a thin film of about several μm can be formed with a small amount of liquid. Even if it is formed, it is effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  The fluorine content of the fluorine-based organic compound is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass in the total solid content of the light effect composition. is there. When the fluorine content is within the above range, it is effective in terms of coating thickness uniformity and liquid-saving properties, and the solubility in the composition is also good.

  As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used. Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, 780, 781, R30, R08, F-472SF, BL20, R- 61, R-90 (Dainippon Ink Co., Ltd.), Florard FC-135, FC-170C, FC-430, FC-431, Novec FC-4430 (Sumitomo 3M Limited), Asahi Guard AG7105, 7000, 950, 7600, Surflon S-112, S-113, S-131, S-141, S-145, S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801, 8 2 (manufactured by JEMCO (Ltd.)), and the like.

  The fluorine-based organic compound is particularly effective in preventing coating unevenness and thickness unevenness when the coating film is thinned. Further, it is also effective in slit coating that is liable to cause liquid breakage.

  0.001-2.0 mass% is preferable with respect to the total mass of a photocurable composition, and, as for the addition amount of a fluorine-type organic compound, More preferably, it is 0.005-1.0 mass%.

<Thermal polymerization initiator>
It is also effective to include a thermal polymerization initiator in the photocurable composition of the present invention. Examples of the thermal polymerization initiator include various azo compounds and peroxide compounds. Examples of the azo compounds include azobis compounds. Examples of the peroxide compounds include ketones. Examples thereof include peroxides, peroxyketals, hydroperoxides, dialkyl peroxides, diacyl peroxides, peroxyesters, peroxydicarbonates, and the like.

<Thermal polymerization component>
It is also effective to include a thermal polymerization component in the photocurable composition of the present invention. If necessary, an epoxy compound can be added to increase the strength of the coating film. The epoxy compound is a compound having two or more epoxy rings in the molecule, such as bisphenol A type, cresol novolac type, biphenyl type, and alicyclic epoxy compound. For example, as bisphenol A type, Epototo YD-115, YD-118T, YD-127, YD-128, YD-134, YD-8125, YD-7011R, ZX-1059, YDF-8170, YDF-170, etc. Toto Kasei Co., Ltd., Denacol EX-1101, EX-1102, EX-1103 and the like (manufactured by Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (manufactured by Daicel Chemical) and their similar The bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, and 600 (manufactured by Daicel UCB) can also be used. As cresol novolak type, Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (above manufactured by Tohto Kasei Co., Ltd.), Denacol EM-125, etc. (above manufactured by Nagase Kasei), Examples of cycloaliphatic epoxy compounds such as 3,5,3 ′, 5′-tetramethyl-4,4′diglycidylbiphenyl include Celoxide 2021, 2081, 2083, 2085, Epolide GT-301, GT-302, GT- 401, GT-403, EHPE-3150 (manufactured by Daicel Chemical), Santo Tote ST-3000, ST-4000, ST-5080, ST-5100 (manufactured by Toto Kasei) and the like. 1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid diester In addition, glycidyl esters such as Epototo YH-434 and YH-434L, which are amine type epoxy resins, and glycidyl esters obtained by modifying dimer acid in the skeleton of bisphenol A type epoxy resins can be used.

<Surfactant>
The photocurable composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coating properties. In addition to the above-mentioned fluorosurfactants, nonionic, cationic, and anionic Various surfactants of the system can be used. Among these, the above-mentioned fluorine-based surfactants and nonionic surfactants are preferable.

  Examples of nonionic surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters, and the like. Particularly preferred. Specifically, polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene octylphenyl ether, polyoxyethylene polystyrylated ether, polyoxyethylene triethyl ether Polyoxyethylene aryl ethers such as benzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonyl phenyl ether; polyoxyethylene dialkyl esters such as polyoxyethylene dilaurate and polyoxyethylene distearate, sorbitan fatty acid esters , Polyoxyethylene sorbitan fatty acid esters, ethylenediamine polyoxyethylene-polyoxypropylene Nonionic surfactants such as thione condensates, which are commercially available from Kao Corporation, Nippon Oil & Fats Co., Ltd., Takemoto Oil & Fat Co., Ltd., ADEKA Co., Ltd., Sanyo Kasei Co., Ltd. It can be used as appropriate. In addition to the above, the aforementioned dispersants can also be used.

  In addition to the above, various additives can be added to the photocurable composition. Specific examples of additives include ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone, and anti-aggregation agents such as sodium polyacrylate. Fillers such as glass and alumina; itaconic acid copolymers, crotonic acid copolymers, maleic acid copolymers, partially esterified maleic acid copolymers, acidic cellulose derivatives, and acid anhydrides added to hydroxyl group-containing polymers And alcohol-soluble nylon, alkali-soluble resins such as phenoxy resin formed from bisphenol A and epichlorohydrin.

  Further, when the alkali solubility of the uncured part is promoted and the developability of the pigment dispersion composition is further improved, the pigment dispersion composition may be an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less. Can be added. Specifically, for example, aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid; oxalic acid, malonic acid, succinic acid, Aliphatic dicarboxylic acids such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid, citraconic acid; Aliphatic tricarboxylic acids such as tricarballylic acid, aconitic acid, camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Hydratropic acid, hydrocinnamic acid, mandelic acid, phenyl succinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, other carboxylic acids such as umbellic acid.

<Thermal polymerization inhibitor>
The photocurable composition of the present invention, more further addition, it is preferable to keep the addition of thermal polymerization inhibitor include 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-t-butylphenol), 2-mercaptobenzimidazole, etc. Useful.

[Photocurable composition and color filter production method using the same]
The photocurable composition of the present invention contains an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator (preferably together with a solvent) in the pigment dispersion composition of the present invention described above, and if necessary, It can be prepared by mixing an additive such as a surfactant and mixing and dispersing using various mixers and dispersers.
The mixing and dispersing step preferably includes kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted.

An example of the manufacturing method of the photocurable composition of this invention is shown below.
A mixture of a pigment, a water-soluble organic solvent, and a water-soluble inorganic salt is mixed with a two-roll, three-roll, ball mill, tron mill, disper, kneader, kneader, homogenizer, blender, single- or twin-screw extruder, etc. Is used to grind the pigment while applying a strong shearing force, and the mixture is put into water and made into a slurry with a stirrer or the like. Subsequently, this slurry is filtered and washed with water to remove the water-soluble organic solvent and the water-soluble inorganic salt, and then dried to obtain a refined pigment.

The beads are dispersed with a pigment and a dispersant and / or a pigment derivative and a solvent. Using a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc., fine dispersion with beads made of 0.01 to 1 mm particle size glass, zirconia, etc., pigment dispersion composition Get. It is also possible to omit the process of making the pigment fine.
For details on kneading and dispersing, see T.W. C. “Paint Flow and Pigment Dispersion” by Patton (published by John Wiley and Sons, 1964) and the like.
And a photopolymerizable compound, a photoinitiator, an alkali-soluble resin, etc. are added to the pigment dispersion composition obtained as mentioned above, and the photocurable composition of this invention is obtained.

The photocurable composition of the present invention is applied to a substrate directly or via another layer by a coating method such as spin coating, slit coating, cast coating, roll coating, bar coating, etc., and a photocurable coating film The film is exposed through a predetermined mask pattern, and after the exposure, the uncured portion is developed and removed with a developer to form a pattern film composed of pixels of each color (three colors or four colors), and a color filter It can be.
In this case, ultraviolet rays such as g-line, h-line, i-line, and j-line are particularly preferable as the radiation to be used. For color filters for liquid crystal display devices, exposure using mainly h-line and i-line is preferable for proximity exposure machines and mirror projection exposure machines, and for color filters for solid-state imaging devices, i-line is mainly used for stepper exposure machines. It is preferable to do.

  The color filter of the present invention is formed on a substrate such as glass by using the above-described photocurable composition of the present invention, and the photocurable composition of the present invention is directly or via other layers. Then, after forming a coating film on the substrate by, for example, slit coating, the coating film is dried, subjected to pattern exposure, and development processing using a developer can be sequentially performed. Thereby, the color filter used for a liquid crystal display element and a solid-state image sensor has few process difficulties, and can be manufactured with high quality and low cost.

Examples of the substrate include non-alkali glass, soda glass, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these substrates, and solid-state imaging devices. Examples thereof include a photoelectric conversion element substrate such as a silicon substrate, and a plastic substrate. On these substrates, usually, a black matrix for isolating each pixel is formed, or a transparent resin layer is provided for promoting adhesion.
The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on its surface. In addition, the photo-curing property of the present invention is also applied to a driving substrate (hereinafter referred to as “TFT type liquid crystal driving substrate”) on which a thin film transistor (TFT) of a thin film transistor (TFT) type color liquid crystal display device is arranged. A color filter can be prepared by forming a patterned film made of the composition. The photomask used at that time is provided with a pattern for forming a through hole or a U-shaped depression in addition to a pattern for forming a pixel. Examples of the substrate in the TFT liquid crystal driving substrate include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide. These substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, gas phase reaction method, vacuum deposition, etc., if desired. For example, a substrate in which a passivation film such as a silicon nitride film is formed on the surface of a TFT liquid crystal driving substrate or a surface of the driving substrate can be used.

  A method for applying the photocurable composition of the present invention to a substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin method or a spinless coating method (hereinafter referred to as a slit nozzle coating method). Is preferred. In the slit nozzle coating method, the slit-and-spin coating method and the spinless coating method have different conditions depending on the size of the coated substrate. For example, when a fifth generation glass substrate (1100 mm × 1250 mm) is coated by the spinless coating method. The discharge amount of the photocurable composition from the slit nozzle is usually 500 to 2000 microliter / second, preferably 800 to 1500 microliter / second, and the coating speed is usually 50 to 300 mm / second. , Preferably it is 100-200 mm / sec. The solid content of the photocurable composition is usually 10 to 20%, preferably 13 to 18%. When a coating film of the photocurable composition of the present invention is formed on a substrate, the thickness of the coating film (after pre-baking treatment) is generally 0.3 to 5.0 μm, preferably 0.5 to 4 0.0 μm, most preferably 0.8 to 3.0 μm.

Usually, a pre-bake treatment is performed after coating. If necessary, vacuum treatment can be performed before pre-baking. As the conditions for vacuum drying, the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr.
The pre-bake treatment is performed in a temperature range of 50 to 140 ° C., preferably about 70 to 110 ° C., using a hot plate, an oven, or the like, and can be performed under conditions of 10 to 300 seconds. High frequency treatment or the like may be used in combination. High frequency processing can be used alone.

In the development process, the uncured portion after the exposure is eluted in the developer, and only the cured portion remains. The development temperature is usually 20 to 30 ° C., and the development time is 20 to 90 seconds.
Any developer can be used as long as it dissolves the coating film of the photo-curable photocurable composition in the uncured portion while not dissolving the cured portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used.

Examples of the organic solvent include the solvents described above that can be used when preparing the pigment dispersion composition or the photocurable composition of the present invention.
Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentrations of alkaline compounds such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene are 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass can be mentioned. An appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the alkaline aqueous solution.

The development method may be any of a dip method, a shower method, a spray method, and the like, and may be combined with a swing method, a spin method, an ultrasonic method, or the like. It is also possible to prevent uneven development by previously moistening the surface to be developed with water or the like before touching the developer. It is also possible to develop with the substrate tilted.
In the case of a solid-state image sensor, paddle development is also used.

After the development processing, after a rinsing step for washing and removing excess developer, drying is performed, and then heat treatment (post-baking) is performed to complete the curing.
The rinsing process is usually performed with pure water. However, to save liquid, pure water is used in the final cleaning. At the beginning of cleaning, used pure water is used, the substrate is tilted and cleaned, and ultrasonic irradiation is performed. Can be used together.

After rinsing, draining and drying are performed, and then a heat treatment is usually performed at about 200 ° C to 250 ° C. In this heat treatment (post-bake), the coating film after development is continuously or batch-treated using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so as to satisfy the above conditions. It can be done with a formula.
By sequentially repeating the above operation for each color in accordance with the desired number of hues, a color filter formed with a plurality of colored cured films can be produced.

The use of the pigment dispersion composition and the photocurable composition of the present invention has been mainly described for use in color filters, but it is also applicable to the formation of a black matrix that isolates each colored pixel constituting the color filter. be able to.
The black matrix is formed by exposing and developing the pigment dispersion composition of the present invention using a black pigment such as carbon black or titanium black as a pigment, and then further post-baking as necessary to promote film curing. Can be formed.

  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” is based on mass.

-Synthetic examples of specific polymer compounds-
−Synthesis of linear type−
(Synthesis of polymer 1)
27.0 g of BzMA, 126.0 g of MMA, 27.0 g of the compound (G-4), and 420.0 g of 1-methoxy-2-propanol were introduced into a nitrogen-substituted three-necked flask, and a stirrer (Shinto Kagaku Co., Ltd.) was introduced. ): Three-one motor), and heated to 90 ° C. while flowing nitrogen into the flask. To this was added 1.69 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. After 2 hours, 1.69 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% solution of polymer 1 was obtained.
As a result of measuring the weight average molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 20,000.
Further, from titration with sodium hydroxide, the acid value per solid content was 98 mgKOH / g, and the repeating unit composition ratio (mass ratio) determined from 1H-NMR was 15/70/15.
Similarly, polymers 2 to 6 having the compositions shown in Table 1 below were synthesized.

(Synthesis of polymer 7)
The compound (a-3) 21.0 g, MMA 98.0 g, the compound (G-20) 14.0 g, MAA 7.0 g and 1-methoxy-2-propanol 420.0 g were placed in a nitrogen-substituted three-necked flask. The mixture is introduced, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated while flowing nitrogen into the flask, and heated to 90 ° C. To this was added 1.69 g of 2,2-azobis (2,4-dimethylvaleronitrile) (V-65 manufactured by Wako Pure Chemical Industries, Ltd.), and the mixture was heated and stirred at 90 ° C. for 2 hours. After 2 hours, 1.69 g of V-65 was further added, and after 3 hours of heating and stirring, a 30% solution of polymer 7 was obtained.
As a result of measuring the weight average molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 15,000.
Further, from titration with sodium hydroxide, the acid value per solid content was 98 mgKOH / g, and the repeating unit composition ratio (mass ratio) determined from 1H-NMR was 15/70/10/5.

-Graft-type synthesis-
(Synthesis of polymer 8)
28.0 g of BzMA, 91.0 g of polymethyl methacrylate having a methacryloyl group at the terminal (AA-6: manufactured by Toa Gosei Co., Ltd.), 21.0 g of the compound (G-4), 2.9 g of n-dodecyl mercaptan and methoxypropylene glycol 327 g is introduced into a nitrogen-substituted three-necked flask, stirred with a stirrer (Shinto Kagaku Co., Ltd .: Three-One Motor), heated while flowing nitrogen into the flask, and heated to 78 ° C. To this, 0.8 g of 2,2-azobis (dimethyl 2-methylpropionate) (Wako Pure Chemical Industries, Ltd., V-601) was added, and the mixture was heated and stirred at 78 ° C. for 2 hours. Two hours later, 0.8 part of V-601 was further added, and after 3 hours of heating and stirring, a 30% solution of polymer 8 was obtained.
As a result of measuring the weight average molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 20,000.
From the titration using sodium hydroxide, the acid value per solid content was 98 mgKOH / g, and the repeating unit composition ratio (mass ratio) determined from 1H-NMR was 20/65/15.
Similarly, polymers 9 to 12 having the composition shown in Table 1 below were synthesized.

-Synthesis of terminal modified type-
(Synthesis of Precursor TM-1 of Polymer 13)
Dipentaerythritol hexakis (3-mercaptopropionate) (manufactured by Sakai Chemical Industry Co., Ltd., DPMP) 7.83 parts and itaconic acid 4.55 parts to 1-methoxy-2-propanol 28.90 parts It was dissolved and heated to 70 ° C. under a nitrogen stream. To this was added 0.04 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [Wako Pure Chemical Industries, Ltd., V-65] and heated for 3 hours. Furthermore, 0.04 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, the following 30% solution of the mercaptan compound (TM-1) according to the present invention was obtained.

(Synthesis of polymer 13)
A mixed solution of 5.03 parts of the TM-1 30% solution, 90.0 g of methyl methacrylate, 10.0 g of the compound (G-26), and 23.3 g of 1-methoxy-2-propanol was placed under a nitrogen stream. Heated to 90 ° C. While stirring this mixed solution, 0.7 g of dimethyl 2,2′-azobisisobutyrate [manufactured by Wako Pure Chemical Industries, Ltd., V-601], 26.8 g of 1-methoxy-2-propanol, 1-methoxy-2- A mixed solution of 47 g of propyl acetate was added dropwise over 2.5 hours. After completion of the dropwise addition, the mixture was reacted at 90 ° C. for 2.5 hours, and then a mixed solution of 0.23 g of dimethyl 2,2′-azobisisobutyrate and 20.0 g of 1-methoxy-2-propylacetate was added for another 2 hours. Reacted. 7.5 g of 1-methoxy-2-propanol and 105.0 g of 1-methoxy-2-propyl acetate were added to the reaction solution, and the mixture was cooled to room temperature to obtain a 30% solution of polymer 13.
As a result of measuring the weight average molecular weight of the obtained polymer compound by gel permeation chromatography (GPC) using polystyrene as a standard substance, it was 18,000.
From the titration using sodium hydroxide, the acid value per solid content was 100 mgKOH / g, and the repeating unit composition ratio (mass ratio) determined from 1H-NMR was 90/10.
Similarly, a polymer 14 having the composition shown in Table 1 below was synthesized.

The compounds in Table 1 are shown below.
MAA: methacrylic acid MMA: methyl methacrylate BzMA: benzyl methacrylate CHMA: cyclohexyl methacrylate DMAEMA: 2-dimethylaminoethyl methacrylate AA-6: methacryloylated polymethyl methacrylate oligomer (Mn = 6000, trade name: AA-) 6. Toa Gosei Chemical Industry Co., Ltd.)

(Example 1-1)
-Pigment dispersion composition-
Pigment C.I. I. 50 g of Pigment Green 36, 500 g of sodium chloride, and 100 g of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 9 hours. Next, the mixture is poured into about 3 liters of water, stirred for about 1 hour with a high speed mixer, filtered, washed with water to remove sodium chloride and solvent, dried and processed pigment coated with a polymer compound. Got.

<Preparation of pigment dispersion composition>
The components of the following composition (1) were mixed and mixed by stirring for 3 hours at 3,000 rpm using a homogenizer to prepare a mixed solution containing a pigment.
[Composition (1)]
・ Processed pigment (particle size 30 nm) 95 parts ・ Pigment derivative A (the following structural formula) 5 parts ・ Dispersant (30% 1-methoxy-2-propyl acetate solution) 100 parts ・ 1-methoxy-2-propyl acetate 750 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm ³ using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.

(Examples 1-2 to 1-13, Comparative Examples 1-1 to 1-2)
Examples 1-2 to 1-13 and Comparative Examples were the same as Example 1-1 except that the composition of the pigment dispersion composition obtained in Example 1-1 was changed as shown in Table 2. A pigment dispersion composition of 1-1 to 1-2 was obtained.

(Examples 1-14 to 1-18, Comparative Examples 1-3 to 1-4)
Pigment C.I. I. It adjusted like Example 1-1 except adding 25 g of specific high molecular compound (polymer) solutions of Table 2 with 50 g of pigment green 36, 500 g of sodium chloride, and 100 g of diethylene glycol.

[Evaluation of pigment dispersion composition]
The following evaluation was performed about the obtained pigment dispersion composition. The results are shown in Table 2.
(1) Measurement and Evaluation of Viscosity For the obtained pigment dispersion composition, using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE550L), the viscosity η ¹ of the pigment dispersion composition immediately after dispersion and after dispersion (room temperature The viscosity η ² of the pigment dispersion composition after 1 week was measured and the degree of thickening was evaluated. The evaluation results are shown in Table 2 below. Here, the low viscosity indicates that the increase in viscosity due to the dispersant is suppressed, and the dispersibility and dispersion stability of the pigment are good.

(2) Measurement and Evaluation of Contrast The obtained pigment dispersion composition was applied on a glass substrate, and a sample was prepared so that the thickness of the coating film after drying was 1 μm. Place this sample between two polarizing plates, measure the luminance when the polarizing plate is parallel and direct luminance (Topcon, BM-5), and contrast = luminance when parallel / luminance when orthogonal. Asked. The results of measurement evaluation are shown in Table 2 below. Here, a high contrast indicates that the pigment is uniformly dispersed in a highly refined state, and thus the transmittance, that is, the coloring power is high.

(3) Evaluation of developability The pigment dispersion composition was applied on a 100 mm × 100 mm glass substrate (product name: 1737, manufactured by Corning) so as to have a film thickness of 2.0 μm, and dried in an oven at 70 ° C. for 60 seconds. did. The film is immersed in a 1% aqueous solution of an alkaline developer (product name: CDK-1 manufactured by Fuji Film Electronics Materials Co., Ltd.), and then the up and down movement is repeated 20 times, so that the solubility and development of the film The presence or absence of suspension in the liquid was visually judged. The higher the score, the better the developability.
* Judgment method 1 to 20 times of vertical movement, developer is colored: 4
After 20 up and down motions, let stand for 1 minute and color the developer: 3
After 20 up and down movements, leave it for 5 minutes and color the developer: 2
After 20 up / down movements, the developer does not color even after being left for 5 minutes: 1

P-1: Methyl methacrylate / methacrylic acid = 85/15% by mass copolymer, weight average molecular weight 20,000, acid value 98 mgKOH / g
P-2: Hydrogenated rosin ester (Arakawa Chemical Co., Ltd., ester gum HP)
D-1: a-1 / AA-6 / MAA = 20/65/15% by mass of copolymer, weight average molecular weight 23,000, acid value 100 mgKOH / g
D-2: Methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene 2-hydroxyethyl methacrylate / benzyl methacrylate / N-phenylmaleimide = 15/10 / 11.2 / 10/35 / 18.8 mass % Copolymer, weight average molecular weight 25,000

From the results of Table 2, in Examples 1-1 to 1-18 using the pigment dispersion composition of the present invention, the pigment dispersibility and the dispersion stability after dispersion are excellent, the contrast is high, and the developability is good. I understand that.
It can also be seen that (A) Comparative Examples 1-1 to 1-4 containing no specific polymer compound have low contrast and poor dispersion stability and developability.

(Example 2-1)
-Pigment dispersion composition-
The pigment is C.I. I. A pigment dispersion composition (red) was prepared in the same manner as in Example 1-1 except that the pigment red 254 was used.

<Preparation of pigment dispersion composition>
The components of the following composition (4) were mixed and mixed by stirring for 3 hours at a rotational speed of 3,000 rpm using a homogenizer to prepare a mixed solution containing a pigment.
[Composition (4)]
・ Processed pigments listed in Table 3 110 parts ・ Dispersant listed in Table 3 250 parts (30% 1-methoxy-2-propyl acetate solution)
-Dispersant pigment derivative described in Table 3 20 parts-1-methoxy-2-propyl acetate ... 750 parts

  Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 6 hours with a bead disperser disperse mat (made by GETZMANN) using 0.3 mmφ zirconia beads, and then further a high-pressure disperser NANO with a decompression mechanism. The dispersion treatment was performed at a flow rate of 500 g / min under a pressure of 2000 kg / cm 3 using −3000-10 (manufactured by Nippon BEE Co., Ltd.). This dispersion treatment was repeated 10 times to obtain a pigment dispersion composition.

<Preparation of color filter using photocurable composition>
The obtained photocurable composition (color resist solution) is placed on a 100 mm × 100 mm glass substrate (Corning Corp., 1737) so that the x value and the y value which are indicators of color density are each 0.650. And dried in an oven at 90 ° C. for 60 seconds (pre-baking). Thereafter, the entire surface of the coating film was exposed at 200 mJ / cm ² (illuminance 20 mW / cm ² ), and the exposed coating film was 1% aqueous solution of alkali developer CDK-1 (manufactured by Fuji Film Electronics Materials Co., Ltd.). And rested for 60 seconds. After standing still, pure water was sprayed in a shower to wash away the developer. Then, the coating film that has been exposed and developed as described above is heated in an oven at 220 ° C. for 1 hour (post-baking) to form a colored pattern (colored resin film) for the color filter on the glass substrate, A colored filter substrate (color filter) was produced.

  In the same manner as in Example 2-1, except that the pigment, pigment derivative, polymer compound, and dispersant used in Example 2-1 were changed to the compounds shown in Table 3, Examples 2-2 to 2- 4. The pigment dispersion composition of Comparative Examples 2-1 to 2-2 was obtained. Using this, a photocurable composition was obtained in the same manner as in Example 2-1, and a color filter was produced.

The compounds listed in Table 3 are shown below.
P-1: Copolymer of methyl methacrylate / methacrylic acid = 85/15% by mass, weight average molecular weight 20,000, acid value 98 mgKOH / g
D-1: a-1 / AA-6 / MAA = 20/65/15% by mass of copolymer, weight average molecular weight 23,000, acid value 100 mgKOH / g

<Evaluation of color filter>
The produced colored filter substrate (color filter) was evaluated as follows. The results are shown in Table 3.

(1) Contrast A colored resin film for a color filter is sandwiched between polarizing plates on a glass substrate, and the luminance when the polarizing plate is parallel and the luminance when the polarizing plate is perpendicular are measured by (Topcon BM-5), and contrast = parallel. It calculated | required in the brightness | luminance at the time / brightness | luminance at the time of direct. The results of measurement evaluation are shown in Table 3. Here, a high contrast indicates that the pigment is uniformly dispersed in a highly refined state, and thus the transmittance, that is, the coloring power is high.

(2) Developer residue The substrate after development was observed with an optical microscope for the remaining amount of the unexposed portion on the glass substrate. ◯ when there is no residue in the unexposed area, △ when the residue is slightly confirmed in the unexposed area, but no problem in practical use, and X where the residue is remarkably confirmed in the unexposed area. did.

(3) Surface smoothness Using a slit coating apparatus provided with a slit head having a slit interval of 100 μm and an effective coating width of 500 mm, the suitability for slit coating was evaluated. After coating on 10 glass substrates (width 550 mm, length 650 mm, thickness 0.7 mm) by a usual method, the slit head was allowed to stand in the air for 5 minutes and forcedly dried. After waiting, a dummy dispense was applied for 3 seconds, and 10 slits were applied to the glass substrate intermittently. The spacing between the slit and the glass substrate was adjusted so that the coating thickness after post-baking was 2 μm, and the curable composition was applied at a coating speed of 100 mm / second. After the coating, prebaking was performed at 90 ° C. for 60 seconds on a hot plate, and then the number of streaky irregularities on the coated surface was visually counted using a sodium light source and evaluated according to the following criteria.
-Evaluation criteria-
○: No streak-like unevenness on the coated surface. Δ: 1-5 streaky unevennesses observed. X: 6 or more streaky unevennesses observed.

From the results of Table 3, it can be seen that in Examples 2-1 to 2-4 using the color filter of the present invention, high contrast is exhibited, residues in unexposed areas are suppressed, and surface smoothness is excellent.
Moreover, in Comparative Examples 2-1 to 2-2 not containing (A) the specific polymer compound, it can be seen that the contrast is low, the residue is seen in the unexposed part, and the surface smoothness is inferior.

  Next, an example of preparing a curable composition containing a pigment for forming a color filter for use in a solid-state imaging device will be described.

(Example 3-1)
-B1. Preparation of resist solution-
Components of the following composition were mixed and dissolved to prepare a resist solution.
<Composition of resist solution>
-Propylene glycol monomethyl ether acetate 19.20 parts-40% propylene glycol monomethyl ether acetate (PGMEA) solution of benzyl methacrylate / methacrylic acid / -2-hydroxyethyl methacrylate (molar ratio = 60/22/18) copolymer 30.51 parts-Dipentaerythritol hexaacrylate 12.20 parts (photopolymerizable compound containing ethylenically unsaturated double bond)
・ Polymerization inhibitor (p-methoxyphenol) 0.0061 part ・ Fluorosurfactant 0.83 part (F-475, manufactured by Dainippon Ink & Chemicals, Inc.)
・ TAZ-107 0.586 parts (manufactured by Midori Chemical Co .; trihalomethyltriazine photopolymerization initiator)

-B2. Fabrication of silicon wafer with undercoat layer
A 6 inch silicon wafer was heat-treated in an oven at 200 ° C. for 30 minutes. Next, the resist solution is applied onto the silicon wafer so that the dry film thickness is 1.5 μm, and further heated and dried in an oven at 220 ° C. for 1 hour to form an undercoat layer. A silicon wafer substrate with an undercoat layer Got.

-Preparation of pigment dispersion-
・ C. I. CI Pigment Green 36 (average primary particle size 30 nm) 95 parts Dispersant described in Table 4 (solid content concentration 30%) 35.5 parts Propylene glycol monomethyl ether acetate (solvent) 830 parts A pigment dispersion (P2) was prepared by mixing and dispersing for 15 hours with a bead mill.

-Preparation of curable composition (coating solution)-
Using the pigment dispersion (P2) obtained above, stirring and mixing were performed to obtain the following composition to prepare a solution of the curable composition.
<composition>
-Pigment dispersion (P2) 600 parts-Irgacure 907 5 parts (Ciba Specialty Chemicals, acetophenone photopolymerization initiator)
Dipentaerythritol hexaacrylate (photopolymerizable compound) 15 parts Propylene glycol monomethyl ether acetate 280 parts

[Production and Evaluation of Color Filter Using Curable Composition]
<Evaluation of pattern formation and sensitivity>
The curable composition prepared as described above was prepared using the B2. The coated film (colored layer) was coated on the undercoat layer of the silicon wafer with the undercoat layer obtained in step 1 so that the dry film thickness was 0.7 μm. Thereafter, heat treatment (pre-baking) was performed for 120 seconds using a 100 ° C. hot plate.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), various exposure doses in the range of 50 to 1200 mJ / cm ² through an Island pattern mask having a pattern of 1.5 μm square at a wavelength of 365 nm. And exposed.
Thereafter, the silicon wafer substrate on which the coating film after exposure is formed is placed on a horizontal rotary table of a spin shower developing machine (DW-30 type, manufactured by Chemitronics Co., Ltd.), and CD-2000 (Fuji Film Electronics Material). Paddle development was performed at 23 ° C. for 60 seconds to form a colored pattern on the silicon wafer.

  A silicon wafer on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and pure water is supplied from above the rotation center while rotating the silicon wafer at a rotation speed of 50 rpm by a rotating device. A rinsing process was performed by supplying a shower from a jet nozzle, followed by spray drying.

  The storage stability of the solution (coating liquid) of the curable composition prepared above and the developability of the curable composition layer formed on the glass substrate using the curable composition were evaluated. The evaluation results are shown in Table 4 below.

<Development evaluation>
In exposure and development, the presence or absence of a residue in a region where light was not irradiated (unexposed portion) was confirmed by post-baking with an optical microscope and SEM photograph observation, and developability was evaluated according to the following evaluation criteria.
-Evaluation criteria-
○: No residue was observed in the unexposed area.
Δ: A slight residue was confirmed in the unexposed area, but there was no practical problem.
X: Residue was remarkably confirmed in the unexposed part.
<Evaluation of dispersibility>
For the obtained pigment dispersion composition, using an E-type viscometer, the viscosity of the pigment dispersion composition immediately after dispersion and the viscosity of the pigment dispersion composition after one week at room temperature after dispersion are measured and increased. The degree of viscosity was evaluated. Here, the low viscosity indicates that the increase in viscosity due to the dispersant is suppressed, and the dispersibility and dispersion stability of the pigment are good.

(Examples 3-2 to 3-4 and Comparative Examples 3-1 to 3-2)
Examples 3-2 to 3-4 and Comparative Examples 3-1 to 3-3 were the same as Example 3-1, except that the dispersants used in Example 3-1 were replaced with the compounds listed in Table 4. -2 curable composition was obtained. Furthermore, each evaluation was performed in the same manner as in Example 3-1. The results are shown in Table 4.

The compounds listed in Table 4 are shown below.
D-1: a-1 / AA-6 / MAA = 20/65/15% by mass of copolymer, weight average molecular weight 23,000, acid value 100 mgKOH / g
D-2: Methacrylic acid / succinic acid mono (2-acryloyloxyethyl) / styrene 2-hydroxyethyl methacrylate / benzyl methacrylate / N-phenylmaleimide = 15/10 / 11.2 / 10/35 / 18.8 mass % Copolymer, weight average molecular weight 25,000

  From Table 4, it was revealed that the pigment dispersion composition of the present invention has good dispersion stability and that the photocurable composition has good developability even for solid-state imaging device applications.

Claims (6)

(A) containing a polymer compound having a cyclic structure formed by direct bonding of a group dissociating with an alkali as a partial structure, having a weight average molecular weight of 1,000 to 100,000, and (B) a pigment. Pigment dispersion composition. (A) A group dissociated by an alkali directly bonded to a cyclic structure in a polymer compound having a cyclic structure formed by directly bonding a group dissociated by an alkali as a partial structure and having a weight average molecular weight of 1,000 to 100,000. The pigment dispersion composition according to claim 1, wherein the content of the repeating unit containing is 5 to 50% by mass. The acid value of the polymer compound having a weight average molecular weight of 1,000 or more and 100,000 or less having a cyclic structure in which a group capable of dissociating with an alkali directly bonded as a partial structure is 50 mgKOH / g or more and 300 mgKOH / g or less. The pigment dispersion composition according to claim 1, wherein the pigment dispersion composition is a pigment dispersion composition. A photocurable composition comprising the pigment dispersion composition according to any one of claims 1 to 3, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator. object. A color filter comprising a colored pattern using the photocurable composition according to claim 4. Applying the photocurable composition according to claim 4 on a substrate directly or via another layer to form a photosensitive film, and performing pattern exposure and development on the formed photosensitive film And a step of forming a colored pattern by the method of manufacturing a color filter.