JP2009084451A - Pigment dispersion composition, photosensitive resin composition, color filter and method for producing the same, liquid crystal display device, and solid-state imaging device - Google Patents

Abstract

A pigment dispersion composition having excellent viscosity stability and high dispersion stability is provided. The present invention also provides a photosensitive resin composition that can form a high-performance film having high contrast and excellent heat resistance, using the pigment dispersion composition. Furthermore, the present invention provides a color filter having a colored region using the photosensitive resin composition, a method for producing the color filter, a liquid crystal display device including the color filter, and a solid-state imaging device.
A pigment dispersion composition comprising at least a pigment derivative represented by the following general formula (1), a resin, a solvent, and a pigment.
[Pig]-(ABC) _n General formula (1)
[In the above general formula (1), [Pig] represents a pigment mother nucleus structure. A represents one linking group selected from CH ₂ , CH ₂ O, CH ₂ S, O, CO, and COO. B represents a chain organic linking group. C represents one or more functional groups selected from an acidic functional group, a basic functional group, and a hydrogen bonding functional group. n represents an integer of 1 to 10. ]
[Selection figure] None

Description

  The present invention particularly relates to a pigment dispersion composition and a photosensitive resin composition suitable for producing a color filter used for a solid-state imaging device or a liquid crystal display device, a color filter using the same, a method for producing the same, a liquid crystal display device, The present invention also relates to a solid-state imaging device.

Pigments exhibit vivid color tone and high coloring power, and are widely used in many fields. For example, paints, printing inks, electrophotographic toners, ink-jet inks, color filters, and the like can be cited as applications, and now they are important compounds indispensable in daily life.
The general properties of pigments and the classification by use are described in Non-Patent Document 1, for example. Among the above-mentioned uses, high performance is required, and those that are particularly important in practical use include inkjet inks and color filters. In these applications, the pigment is used as a pigment dispersion by dispersing with a pigment derivative and a dispersion resin.

Generally, a color filter is used for a liquid crystal display and a solid-state image sensor.
In color filters for liquid crystal displays, higher image quality is required, and as one means for that purpose, improvement of color purity can be mentioned. In order to improve the color purity, a pigment dispersion composition having higher contrast and higher dispersion stability is required.
Further, in color filters for solid-state imaging devices, reduction of color unevenness and thinning of colored patterns are required. In order to reduce color unevenness, it is necessary to uniformly disperse the pigment as the pigment dispersion composition. Further, regarding the thinning of the colored pattern, it is required to increase the content of the colorant in the curable composition used for the production of the color filter in order to reduce the film thickness at the same color density as before. For this reason, in order to increase the concentration of the polymerizable compound as much as possible, it is necessary to stably disperse with a small amount of pigment derivative and dispersion resin as a pigment dispersion, and to reduce the pigment derivative amount and the dispersion resin amount.
As described above, there is a need for a pigment dispersion composition having high contrast and high dispersion stability for both liquid crystal displays and solid-state imaging devices.

Therefore, in recent years, pigment derivatives having acidic groups and basic groups have been developed for radiation sensitive compositions for color filters. In recent years, as a pigment composition having an acidic group, the coloring composition for a color filter has a phthalocyanine ring as a mother nucleus, a pigment derivative directly bonded with a sulfonic acid group (Patent Document 1), an anthraquinone as a mother nucleus, A pigment derivative having a sulfonic acid group directly attached (Patent Documents 2 and 3), a pigment derivative having a quinoline as a mother nucleus and having a sulfonic acid group directly attached (Patent Documents 4 and 5), and the like have been reported. As a pigment derivative having a group, a pigment derivative having a diketopyrrolopyrrole ring as a mother nucleus and having a sulfonamide linkage (Patent Document 6), a pigment derivative having quinacridone as a mother nucleus and having a sulfonamide linkage or a triazine linkage (Patent Document 7) and a pigment derivative (Patent Document 8) having anthraquinone as a mother nucleus and linked with sulfonamide or the like have been reported.
However, even in the case of these pigment dispersion compositions and photosensitive resin compositions, contrast and dispersion stability are not yet satisfactory, and development of new pigment derivatives and the like that can solve the above problems is required. .
“Pigment Dispersion Stabilization and Surface Treatment Technology / Evaluation” 2001, pages 123-224, Technical Information Association. JP 2001-356210 A JP 2002-22922 A JP 2006-265528 A JP 2004-91497 A JP 2005-234478 A JP 2001-51112 A JP 2007-79094 A JP-A-10-245502

An object of the present invention is to provide a pigment dispersion composition having excellent viscosity stability and high dispersion stability.
A further object of the present invention is to provide a photosensitive resin composition using such a pigment dispersion composition, which can form a high-performance film having high contrast and excellent heat resistance.
Another object of the present invention is to provide a color filter having a colored region using the photosensitive resin composition of the present invention, having high contrast and excellent heat resistance, a method for producing the same, and the color filter. An object of the present invention is to provide a liquid crystal display device and a solid-state imaging device.

The present inventors have found that the above problems can be achieved by the following method, and have reached the present invention.
<1> A pigment dispersion composition containing at least a pigment derivative represented by the following general formula (1), a resin, a solvent, and a pigment.
[Pig]-(ABC) _n General formula (1)
In the general formula (1), [Pig] represents a pigment mother nucleus structure. A represents one linking group selected from the group consisting of CH ₂ , CH ₂ O, CH ₂ S, O, CO, and COO. B represents a chain organic linking group. C represents one or more functional groups selected from the group consisting of an acidic functional group, a basic functional group, and a hydrogen bonding functional group. n represents an integer of 1 to 10.
<2> The pigment dispersion composition according to <1>, wherein B in the general formula (1) has 3 to 30 atoms constituting the main chain.
<3> The pigment dispersion composition according to <1>, wherein B in the general formula (1) has 5 to 30 atoms constituting the main chain.
<4> The pigment dispersion composition according to <1>, wherein B in the general formula (1) has 7 to 30 atoms constituting the main chain.
<5> The pigment dispersion composition according to any one of <1> to <4>, which is used for forming a colored region in a color filter.

<6> A photosensitive resin composition comprising the pigment dispersion composition according to any one of <1> to <5>, a photopolymerizable compound, and a photopolymerization initiator.
<7> A color filter having a colored region formed of the colored photosensitive composition according to <6> on a substrate.
<8> A curable layer forming step of forming the curable layer by applying the photosensitive resin composition according to <6> directly or via another layer to the support, and the curable coating formed. A method for producing a color filter, comprising: an exposure step of exposing a layer in a pattern through a mask; and a development step of developing the curable layer after exposure to form a colored pattern.
<9> A liquid crystal display element comprising the color filter according to <7>.
<10> A solid-state imaging device comprising the color filter according to <7>.

According to the present invention, a pigment dispersion composition having excellent viscosity stability and high dispersion stability can be provided.
Moreover, according to this invention, the photosensitive resin composition which can form the high-performance film which is high in contrast and excellent in heat resistance using such a pigment dispersion composition can be provided.
Furthermore, according to the present invention, a color filter having a colored region formed by using the photosensitive resin composition of the present invention, having high contrast and excellent heat resistance, a method for producing the same, and a liquid crystal provided with the color filter A display element and a solid-state imaging element can be provided.

Hereinafter, the present invention will be described in detail.
≪Pigment dispersion composition≫
The pigment dispersion composition of the present invention contains at least (a) a pigment derivative represented by the following general formula (1), (b) a resin, (c) a solvent, and (d) a pigment. It can be constructed using components.
[Pig]-(ABC) _n General formula (1)

In the general formula (1), [Pig] represents a pigment mother nucleus structure. A represents one linking group selected from the group consisting of CH ₂ , CH ₂ O, CH ₂ S, O, CO, and COO. B represents a chain organic linking group. C represents one or more functional groups selected from the group consisting of an acidic functional group, a basic functional group, and a hydrogen bonding functional group. n represents an integer of 1 to 10.

In the pigment derivatives contained in the pigment dispersion compositions that have been developed in the past, in order to introduce a substituent (adsorptive group) into the pigment itself, the linking groups that can be introduced such as a sulfonamide structure and a phthalimide structure are limited. Therefore, the flexibility of the adsorbing group that interacts with the dispersion resin is lowered, and it is difficult to efficiently disperse the pigment.
On the other hand, as described above, the pigment derivative contained in the pigment dispersion composition of the present invention has a pigment core structure Pig ([Pig] in the above general formula (1)) and a functional group C (the above general formula (1)). C) is connected by a linking group A (A in the above general formula (1)) and a linking group B (B in the above general formula (1)), so that the flexibility of the adsorbing group is high. , Can interact with the dispersing resin efficiently. Therefore, the dispersion stability of the pigment in the pigment dispersion composition can be obtained, and a higher contrast can be obtained in a film using the pigment dispersion composition.
Further, by increasing the length of the connecting chain between the pigment core structure Pig and various functional groups, that is, by increasing the number of atoms constituting the main chain of B in the general formula (1), the pigment derivative And the dispersion resin become more efficient, and the contrast and dispersion stability are further improved.
In addition, since these linking groups (linking group A and linking group B) have relatively high thermal stability, (a) the heat resistance of the pigment derivative is increased, and various problems such as discoloration due to heat are avoided. Can do.

-(A) Pigment derivative-
The (a) pigment derivative used in the present invention is a pigment derivative represented by the general formula (1). As described above, from the pigment mother core structure Pig, the linking group A, the linking group B, and the functional group C. Composed.

<Pigment core structure Pig>
“Pigment mother nucleus structure” refers to a partial chemical structure of an organic pigment typified by a chromophoric atomic group. In the present invention, the pigment has a chemical structure similar to such a partial chemical structure. Similar chemical structures capable of forming an interaction are also included in the “pigment mother core structure”.
Examples of the pigment core structure Pig include, for example, Hansa yellow, disazo yellow, benzimidazolone, lake red, toluidine red, naphthol AS, isoindoline, isoindolinone, quinacridone, perylene, Various pigment mother nuclei such as anthraquinone, diketopyrrolopyrrole, dioxazine violet, phthalocyanine, azomethine, pteridine, naphthol, pyrazolone, indigo, thioindigo, xanthene, indazine, carbon black A structure can be used.
The pigment core structure Pig may be the same as or different from the structure of the (d) pigment contained in the pigment dispersion composition, but (d) a structure close to the structure of the pigment is preferable. .

As a specific example of the pigment mother nucleus structure Pig, for example, the following structure can be used, but it is not limited to the following structure.
In the structure shown below, X is (ABC) in the general formula (1). When two or more Xs are contained in one molecule, different Xs may be used as each X.

<Functional group C>
The functional group C of the pigment derivative (a) in the present invention is one or more functional groups selected from the group consisting of an acidic functional group, a basic functional group, and a hydrogen bonding functional group. You may contain 2 or more types of functional groups C in 1 molecule. For example, the combination of an acidic functional group and a hydrogen bondable functional group, or the combination of a basic functional group and a hydrogen bondable functional group is mentioned.

(Acid functional group)
Examples of the acidic functional group of the pigment derivative (a) in the pigment dispersion composition of the present invention include sulfonic acid groups, sulfonic acid salts, carboxylic acid groups, phosphoric acid groups, hydroxyl groups, and boric acid groups. Examples of the counter ion include metal ions, monoalkylammonium ions having 1 to 12 carbon atoms, dialkylammonium ions having 1 to 24 carbon atoms, and trialkylammonium ions having 1 to 36 carbon atoms.
The acidic functional group is preferably a sulfonic acid group, a sulfonate having a metal ion as a counter ion, or a carboxylic acid group, and more preferably a sulfonate having a sulfonic acid group or a metal ion as a counter ion. .

  As a metal ion which is a counter ion of the sulfonate, a metal ion selected from Groups 1 to 13 of the periodic table can be used, and preferably a metal ion selected from Groups 1 to 2 of the periodic table is used. More preferably, potassium ions and sodium ions can be used.

  The acidic functional group of the pigment derivative (a) in the pigment dispersion composition of the present invention can be used in combination of a plurality of types of acidic functional groups. For example, a sulfonate having a sulfonic acid group and a carboxylic acid group, a sulfonic acid group and a metal ion as a counter ion, and a sulfonic acid having a sulfonic acid group, a carboxylic acid group, and a trialkylammonium ion having 1 to 36 carbon atoms as a counter ion. Examples thereof include a salt, a sulfonate group having a sulfonic acid group, a carboxylic acid group, and a trialkylammonium ion having 1 to 72 carbon atoms as a counter ion and a hydroxyl group. The combination of acidic functional groups is not limited to these.

(Basic functional group)
The basic functional group of the pigment derivative (a) in the pigment dispersion composition of the present invention can be used as long as it has a basic structure, but preferably -NR ¹ R ² and heterocyclic ring containing a nitrogen atom and the like, more preferably ^-NR 1 ^{R 2.}

R ¹ and R ² each independently represents a hydrogen atom, a carboxyl group, or a monovalent organic group. Specific examples of R ¹ and R ² include a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, and a substituent. Examples thereof may include a heteroaryl group which may have a hydrogen atom, a carboxyl group, an alkoxycarbonyl group, an alkyl group which may have a substituent, and an aryl group which may have a substituent. R ¹ and R ² may form a bond and form a ring.

  The heterocycle containing a nitrogen atom is preferably a heterocycle having 1 to 36 carbon atoms, more preferably a heterocycle having 2 to 24 carbon atoms. Specifically, for example, a pyrrolyl group, a benzopyrrolyl group, a pyrazolyl group, Indazolyl group, imidazolyl group, benzimidazolyl group, quinolinyl group, isoquinolinyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, quinazolinyl group, quinoxalinyl group, acridinyl group, phenanthridinyl group, phthalazinyl group, carbazolyl group, carbolinyl group, purinyl group Triazolyl group is preferable, among which 3-pyrazolyl group, 4-pyrazolyl group, 2-imidazolyl group, 4-imidazolyl group, 5-imidazolyl group, 2-benzoimidazolyl group, 2-pyridyl group, 3-pyridyl group, 4- Pyridyl group, 2-quinolinyl group, 4- Noriniru group, 1-isoquinolinyl group, 3-isoquinolinyl group, 3-pyridazinyl group, 4-pyridazinyl group, 2-pyrimidinyl group, 4-pyrimidinyl group, 5-pyrimidinyl group, 2-pyrazinyl group are more preferred.

  The basic functional group of the pigment derivative (a) in the pigment dispersion composition of the present invention can be used by combining a plurality of types of basic functional groups. Examples thereof include a dimethylamino group and an imidazolyl group, a dicyclohexylamino group and a 3-quinolinyl group, a methylamino group, a diphenylamino group, and a 5-pyridyl group. The combination of basic functional groups is not limited to these.

(Hydrogen bondable functional group)
The hydrogen bondable functional group of the pigment derivative (a) in the pigment dispersion composition of the present invention may be a functional group that exhibits one or more pairs of hydrogen bonds with other low molecular compounds or polymer compounds. The hydrogen-bonding functional group is preferably a functional group that exhibits two pairs of hydrogen bonds with other low-molecular compounds or polymer compounds, and more preferably a dispersion resin ((b) resin in the present invention) It is a functional group that forms two pairs of hydrogen bonds. More specifically, a functional group having a hydrogen atom such as a hydroxyl group, a primary amino group, or an ammonium group, or a functional group containing an atom having an unshared electron pair such as an oxygen atom, a nitrogen atom, a fluorine atom, or a sulfur atom. Represents. Examples of the form of hydrogen bonding formed by the hydrogen bonding functional group of the present invention and other low molecular compounds or high molecular compounds include those shown in Table 1 below. However, the form of hydrogen bonding is not limited to the form shown in Table 1 below. In Table 1 below, R, R ′, and R ″ represent portions other than the hydrogen bonding functional group.

Moreover, as a specific example of a hydrogen bondable functional group, the functional group shown by following Table 2 and Table 3 is mentioned, for example. Here, in Table 2 and Table 3 below, P is a hydrogen-bonding functional group (C in the above general formula (1)) contained in (a) the pigment derivative, and Q is another group that forms a hydrogen bond with P. It is a hydrogen bonding functional group of a low molecular compound or a high molecular compound.
In Tables 2 and 3 below, Q is a hydrogen-bonding functional group contained in the pigment derivative (a), and P is a hydrogen bond property of another low molecular compound or polymer compound that forms a hydrogen bond with Q. It may be a functional group.
In Tables 2 and 3 below, Y and Z are (a) a residue other than the hydrogen-bonding functional group contained in the pigment derivative, or (a) another low-molecular compound or high molecular weight that interacts with the pigment derivative. It is a substituent other than the hydrogen bonding functional group of the molecular compound.
In addition, the hydrogen bonding functional group of the pigment derivative (a) of the present invention is not limited to the specific examples shown in Tables 2 and 3 below.

<Linking group A>
The linking group A of the pigment derivative (a) in the pigment dispersion composition of the present invention is one linking group selected from the group consisting of CH ₂ , CH ₂ O, CH ₂ S, O, CO, and COO. The linking group A is preferably CH ₂ O, CH ₂ S, or O, more preferably CH ₂ O or O, from the viewpoint of flexibility.

<Linking group B>
The linking group B of the pigment derivative (a) in the pigment dispersion composition of the present invention is a chain organic linking group that links the linking group A and the functional group C.
Here, in the present invention, the “chain organic linking group” is linear or branched, and two or more selected from the group consisting of a carbon atom, an oxygen atom, a sulfur atom, a nitrogen atom, and a hydrogen atom. A linking group formed using the atoms of

  In the linking group B, the number of atoms constituting the main chain (number of atoms used for linking the linking group A and the functional group C) is preferably 3 to 30, more preferably 5 to 5. 30, more preferably 7-30.

Specific examples of the linking group B include a linear or branched alkylene group, a linear poly (alkyleneoxy) group, and a linear or branched unsaturated hydrocarbon group. A linear or branched alkylene group, a linear poly (alkyleneoxy) group, or a linear or branched unsaturated hydrocarbon group may have a substituent introduced on the main chain. The linking group may be introduced.
Preferred linking group B is an unsubstituted linear or branched alkylene group, a linear or branched alkylene group having a substituent introduced on the main chain, a linear having a linking group introduced into the main chain, or A branched alkylene group, more preferably an unsubstituted linear or branched alkylene group, or a linear or branched alkylene group having a substituent introduced on the main chain.

  In the linear or branched alkylene group, the linear poly (alkyleneoxy) group, the linear or branched unsaturated hydrocarbon group, the substituent introduced onto the main chain includes a hydrogen atom, a fluorine atom, carbon An alkyl group having 1 to 24 carbon atoms, a fluoroalkyl group having 1 to 24 carbon atoms, an allyl group, an aralkyl group having 1 to 24 carbon atoms, an aryl group having 1 to 24 carbon atoms, a heteroaryl group having 1 to 24 carbon atoms, carbon An amino group which may have a substituent having 1 to 24 carbon atoms, an alkoxycarbonyl group having 1 to 24 carbon atoms, an aryloxycarbonyl group having 1 to 24 carbon atoms, an alkylaminocarbonyl having 1 to 24 carbon atoms Group, an arylaminocarbonyl group having 1 to 24 carbon atoms, an alkylcarbamoyl group having 1 to 24 carbon atoms, an arylcarbamoyl group having 1 to 24 carbon atoms, or a carbamoyloxy group. It is.

  In the linear or branched alkylene group, linear poly (alkyleneoxy) group, linear or branched unsaturated hydrocarbon group, other linking groups introduced into the main chain include an oxygen atom and a sulfur atom. , Nitrogen atom, ester group, amide group, urea group, carbamoyl group and the like.

  Specific examples of the (a) pigment derivative in the present invention are listed below, but are not limited thereto.

As content in the pigment dispersion composition of (a) pigment derivative in this invention, 0.1-50 mass% is preferable with respect to the total mass of a pigment dispersion composition, More preferably, it is 0.5-30 mass. %, And more preferably 1 to 20% by mass. When the content is within the above range, it is preferable because the dispersion stability is high and the hue is not impaired.
The pigment derivative of this invention may be used individually by 1 type, and may use 2 or more types together.

-(B) Resin-
Examples of the structure of the resin (b) used in the present invention include linear polymers, graft polymers, block polymers, and terminal-modified polymers. Moreover, as (b) resin, polyurethane, polyester, polyimide, or the like can be suitably used.

(Linear polymer)
As a linear polymer, the radical polymer which has a carboxylic acid group in a side chain is mentioned, for example. Specifically, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-54-92723, JP-A-59-53836. Disclosed in JP-A-59-71048, ie, a resin having a monomer having a carboxyl group alone or copolymerized, a monomer having an acid anhydride being alone or copolymerized, and an acid anhydride Examples thereof include resins obtained by hydrolyzing, half-esterifying or half-amidating units, and epoxy acrylates obtained by modifying epoxy resins with unsaturated monocarboxylic acids and acid anhydrides.
Examples of the monomer having a carboxyl group include acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxylstyrene, and the monomer having an acid anhydride includes maleic anhydride. It is done.
Examples of the linear polymer include acidic cellulose derivatives having a carboxylic acid group in the side chain. In addition, a polymer obtained by adding a cyclic acid anhydride to a polymer having a hydroxyl group is also useful.

  (B) When a copolymerized copolymer is used as the resin, a monomer other than the above-described monomers can be used as the compound to be copolymerized. Examples of other monomers include the following compounds (1) to (12).

  (1) 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate Acrylic acid esters and methacrylic acid esters having an aliphatic hydroxyl group such as

  (2) Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, isobutyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, benzyl acrylate, acrylic acid-2- Alkyl acrylates such as chloroethyl, glycidyl acrylate, 3,4-epoxycyclohexylmethyl acrylate, vinyl acrylate, 2-phenylvinyl acrylate, 1-propenyl acrylate, allyl acrylate, 2-allyloxyethyl acrylate, propargyl acrylate;

  (3) Methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, isobutyl methacrylate, amyl methacrylate, hexyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid-2- Alkyl methacrylates such as chloroethyl, glycidyl methacrylate, 3,4-epoxycyclohexylmethyl methacrylate, vinyl methacrylate, 2-phenylvinyl methacrylate, 1-propenyl methacrylate, allyl methacrylate, 2-allyloxyethyl methacrylate, and propargyl methacrylate.

  (4) Acrylamide, methacrylamide, N-methylolacrylamide, N-ethylacrylamide, N-hexylmethacrylamide, N-cyclohexylacrylamide, N-hydroxyethylacrylamide, N-phenylacrylamide, N-nitrophenylacrylamide, N-ethyl- Acrylamide or methacrylamide such as N-phenylacrylamide, vinylacrylamide, vinylmethacrylamide, N, N-diallylacrylamide, N, N-diallylmethacrylamide, allylacrylamide, allylmethacrylamide.

(5) Vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl vinyl ether, and phenyl vinyl ether.
(6) Vinyl esters such as vinyl acetate, vinyl chloroacetate, vinyl butyrate and vinyl benzoate.

  (7) Styrenes such as styrene, α-methylstyrene, methylstyrene, chloromethylstyrene, and p-acetoxystyrene.

(8) Vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
(9) Olefins such as ethylene, propylene, isobutylene, butadiene, and isoprene.
(10) N-vinylpyrrolidone, acrylonitrile, methacrylonitrile and the like.
(11) Unsaturated imides such as maleimide, N-acryloylacrylamide, N-acetylmethacrylamide, N-propionylmethacrylamide, N- (p-chlorobenzoyl) methacrylamide.

(12) A methacrylic acid monomer having a hetero atom bonded to the α-position. For example, compounds described in Japanese Patent Application No. 2001-115595, Japanese Patent Application No. 2001-115598 and the like can be mentioned.
Among these, (meth) acrylic resins having an allyl group, a vinyl ester group, and a carboxyl group in the side chain, and double in the side chain described in JP-A Nos. 2000-187322 and 2002-62698 are disclosed. An alkali-soluble resin having a bond and an alkali-soluble resin having an amide group in the side chain described in JP-A No. 2001-242612 are preferable because of excellent balance of film strength, sensitivity, and developability.

  Moreover, it is preferable that (b) resin is comprised including the monomer which has a functional group which can adsorb | suck to a pigment. A monomer having a functional group that can be adsorbed to the pigment is preferably used because it can increase the dispersion stability of the pigment by adsorbing to the pigment and suppressing reaggregation of the pigment. Specific examples of the monomer having a functional group that can be adsorbed on the pigment 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 include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, and flavan. Examples include monomers having a dye structure of throne, perinone, perylene, and thioindigo.
Examples of the monomer having a heterocyclic structure include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, Piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, anthraquinone And monomers having a heterocyclic structure such as
More specifically, examples of the monomer having a functional group that can be adsorbed to the pigment include monomers having the following structure. However, the monomer is not particularly limited to the following structure.

Examples of the monomer having an acidic group include a vinyl monomer having a carboxyl group, a vinyl monomer having a sulfonic acid group, and a vinyl monomer having 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 mono (1-methyl-2-acryloyloxyethyl ester) and the like.

Examples of the monomer having a basic nitrogen atom include monomers having a heterocyclic ring, (meth) acrylic acid esters, (meth) acrylamides, styrenes and the like.
Specific examples of the monomer having a heterocyclic ring include vinyl pyridine, vinyl imidazole, and vinyl triazole.
Specific examples of (meth) acrylic acid esters include N, N-dimethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, and (meth) acrylic acid 1- (N, N-dimethylamino) -1,1-dimethylmethyl, (meth) acrylic acid N, N-dimethylaminohexyl, (meth) acrylic acid N, N-diethylaminoethyl, (meth) acrylic acid N, N- Diisopropylaminoethyl, N, N-di-n-butylaminoethyl (meth) acrylate, N, N-di-i-butylaminoethyl (meth) acrylate, morpholinoethyl (meth) acrylate, (meth) acryl Piperidinoethyl acid, 1-pyrrolidinoethyl (meth) acrylate, N, N-methyl-2-pyrrolidylaminoethyl (meth) acrylate and Meth) acrylic acid and N, N- methylphenylamino ethyl.

Specific examples of (meth) acrylamides include N- (N ′, N′-dimethylaminoethyl) acrylamide, N- (N ′, N′-dimethylaminoethyl) methacrylamide, and N- (N ', N'-diethylaminoethyl) acrylamide, N- (N', N'-diethylaminoethyl) methacrylamide, N- (N ', N'-dimethylaminopropyl) acrylamide, N- (N', N'-dimethyl) Aminopropyl) methacrylamide, N- (N ′, N′-diethylaminopropyl) acrylamide, N- (N ′, N′-diethylaminopropyl) methacrylamide, 2- (N, N-dimethylamino) ethyl (meth) acrylamide 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylic Rilamide, 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 and the like can be mentioned.
Specific examples of styrenes include N, N-dimethylaminostyrene and N, N-dimethylaminomethylstyrene.

  Further, (b) the resin may be a monomer having a urea group, a urethane group, a hydrocarbon group having 4 or more carbon atoms having a coordinating oxygen atom, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group, or the like. is there. Specific examples include monomers having the following structure.

Moreover, the monomer (ionic vinyl monomer) which contains an ionic functional group further can be utilized for (b) resin. Examples of the ionic vinyl monomer include an anionic vinyl monomer and a cationic vinyl monomer.
Examples of the anionic vinyl monomer include alkali metal salts of vinyl monomers having the acidic group, salts of vinyl monomers having the acidic group and organic amines (for example, tertiary amines such as triethylamine and dimethylaminoethanol). It is done.
As the cationic vinyl monomer, the nitrogen-containing vinyl monomer is an alkyl halide (the alkyl group has 1 to 18 carbon atoms, the halogen atom is a chlorine atom, bromine atom or iodine atom); benzyl chloride, benzyl bromide, etc. Benzyl halide; alkyl sulfonic acid ester such as methane sulfonic acid (alkyl group has 1 to 18 carbon atoms); aryl sulfonic acid alkyl ester such as benzene sulfonic acid and toluene sulfonic acid (alkyl group has 1 to 1 carbon atoms) 18); those quaternized with dialkyl sulfate (the alkyl group has 1 to 4 carbon atoms), and dialkyl diallylammonium 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.

(Block polymer)
The type of monomer constituting the block polymer is not particularly limited, but various block polymers can be synthesized using the monomers used for the linear polymer synthesis and used. Preferably, a block polymer comprising a pigment adsorbing block, a block having an alkali-soluble group and a block not adsorbing to the pigment, a block polymer comprising a block not adsorbing to the pigment and a block having an alkali-soluble group, and the like can be mentioned.

  As a method for obtaining the block polymer, a conventionally known method can be used. For example, living polymerization, iniferter method and the like are known, and as another method, when radical polymerization of a monomer having a pigment adsorbing group or a monomer not having a pigment adsorbing group, thiolcarboxylic acid or molecule A polymer obtained by polymerizing a compound containing a thioester and a thiol group (for example, 2-acetylthioethyl ether, 10-acetylthiodecanethiol, etc.) in the interior is added with an alkali such as sodium hydroxide or ammonia. There is also known a method of radical polymerization of the monomer component of the other block in the presence of a polymer having a thiol group at one end obtained in the presence of a polymer having a thiol group at one end. Yes. Among these, living polymerization is preferable.

  Commercially available products can be used as the block polymer. Specific examples include “Disperbyk-2000, 2001” manufactured by BYK Chemie, “EFKA 4330, 4340” manufactured by EFKA, and the like.

(Graft polymer)
The graft polymer is not particularly limited, but is a compound obtained by reacting a polyalkyleneimine and a polyester compound described in JP-A No. 54-37082, JP-A No. 61-174939, etc., JP-A No. 9-169821. Preferred examples include compounds obtained by modifying the side chain amino group of polyallylamine with polyester with a polyester polyol-added polyurethane described in JP-A-60-166318, and further, JP-A-9-171253 and Further, as described in Macromonomer Chemistry and Industry (IPC Publishing Co., Ltd., 1989), a graft polymer having a polymerizable oligomer (hereinafter referred to as a macromonomer) as a copolymerization component can also be suitably exemplified. .

  As the branch part of the graft polymer, polystyrene, polyethylene oxide, polypropylene oxide, poly (meth) acrylic acid ester, polycaprolactone and the like are preferably mentioned. At least the structural unit represented by the following general formula (5) is included in the branch part. The graft type polymer is more preferable.

In the general formula (5), R ⁷⁴ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, Q is a cyano group, an aryl group having 6 to 30 carbon atoms, —COOR ⁷⁵ (where R ⁷⁵ represents a hydrogen atom, an alkyl group having 1 to 22 carbon atoms, or an aryl group having 6 to 30 carbon atoms) or a group having an alkali-soluble group in a cyclic structure.

In the general formula (5), the alkyl group represented by R ⁷⁴ may have a substituent, preferably an alkyl group having 1 to 6 carbon atoms, and particularly preferably a methyl group. Examples of the substituent for the alkyl group include a halogen atom, a carboxyl group, an alkoxycarbonyl group, and an alkoxy group.
Specific examples of such an alkyl group include a methyl group, an ethyl group, a hexyl group, an octyl group, a trifluoromethyl group, a carboxymethyl group, and a methoxycarbonylmethyl group.
Of such R ⁷⁴ , a hydrogen atom and a methyl group are preferable.

In the general formula (5), the aryl group represented by Q may have a substituent, preferably an aryl group having 6 to 20 carbon atoms, and particularly preferably an aryl group having 6 to 12 carbon atoms. . Examples of the substituent for the aryl group include a halogen atom, an alkyl group, an alkoxy group, and an alkoxycarbonyl group.
Specific examples of such aryl groups include phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxy. Examples thereof include a phenyl group, a decyloxyphenyl group, a chlorophenyl group, a dichlorophenyl group, a bromophenyl group, a methoxycarbonylphenyl group, an ethoxycarbonylphenyl group, and a butoxycarbonylphenyl group.
Among such aryl groups, an unsubstituted aryl group, or an aryl group substituted with a halogen atom, an alkyl group, or an alkoxy group is preferred, and an unsubstituted aryl group or an aryl group substituted with an alkyl group is particularly preferred. preferable.

In -COOR ⁷⁵ represented by Q in the above general formula (5), the alkyl group represented by R ⁷⁵ may have a substituent, and is preferably an alkyl group having 1 to 12 carbon atoms. An alkyl group having 1 to 8 carbon atoms is preferred. Examples of the substituent for the alkyl group include a halogen atom, an alkenyl group, an aryl group, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, an amino group, an acylamino group, and a carbamoyl group.
Specific examples of such alkyl groups include methyl, ethyl, propyl, butyl, heptyl, hexyl, octyl, decyl, dodecyl, tridecyl, tetradecyl, hexadecyl, octadecyl. Group, 2-chloroethyl group, 2-bromoethyl group, 2-methoxycarbonylethyl group, 2-methoxyethyl group, 2-bromopropyl group, 2-butenyl group, 2-pentenyl group, 3-methyl-2-pentenyl group, 2-hexenyl group, 4-methyl-2-hexenyl group, benzyl group, phenethyl group, 3-phenylpropyl group, naphthylmethyl group, 2-naphthylethyl group, chlorobenzyl group, bromobenzyl group, methylbenzyl group, ethylbenzyl Group, methoxybenzyl group, dimethylbenzyl group, dimethoxybenzyl group, cyclohexyl Group, 2-cyclohexylethyl group, 2-cyclopentylethyl group, bicyclo [3.2.1] oct-2-yl group, 1-adamantyl group, dimethylaminopropyl group, acetylaminoethyl group, N, N-dibutyl An aminocarbamoylmethyl group etc. are mentioned.
Among such alkyl groups, an unsubstituted alkyl group, or an alkyl group substituted with a halogen atom, an aryl group, or a hydroxyl group is preferable, and an unsubstituted alkyl group is particularly preferable.

The aryl group represented by R ⁷⁵ in —COOR ⁷⁵ represented by Q in the general formula (5) may have a substituent, and is preferably an aryl group having 6 to 20 carbon atoms. An aryl group having 6 to 12 carbon atoms is preferred. Examples of the substituent for the aryl group include a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, and an acylamino group.
Specific examples of such aryl groups include phenyl, naphthyl, tolyl, xylyl, propylphenyl, butylphenyl, octylphenyl, dodecylphenyl, methoxyphenyl, ethoxyphenyl, butoxy. Phenyl group, decyloxyphenyl group, chlorophenyl group, dichlorophenyl group, bromophenyl group, methoxycarbonylphenyl group, ethoxycarbonylphenyl group, butoxycarbonylphenyl group, acetamidophenyl group, propioamidophenyl group, dodeciloylamidophenyl group, Etc.
Among such aryl groups, an unsubstituted aryl group or an aryl group substituted with a halogen atom, an alkyl group, or an alkoxy group is preferable, and an aryl group substituted with an alkyl group is particularly preferable.

Of such R ⁷⁵ , a hydrogen atom and an alkyl group having 1 to 22 carbon atoms are preferable, and a hydrogen atom and an alkyl group having 1 to 12 carbon atoms are particularly preferable.

  Specific examples of the branch part of the graft polymer having at least the structural unit represented by the general formula (5) in the branch part include polymethyl (meth) acrylate and poly-n-butyl (meth). Acrylate, poly-i-butyl (meth) acrylate, poly (methyl (meth) acrylate-co-benzyl (meth) acrylate), poly (methyl (meth) acrylate-co-styrene), poly (methyl (meth) acrylate- co- (meth) acrylic acid), poly (methyl (meth) acrylate-co-acrylonitrile), and the like.

Any known method may be used for synthesizing the graft polymer having at least the structural unit represented by the general formula (5) in the branch.
Specific examples include copolymerization of a macromonomer having at least the structural unit represented by the general formula (5) and an ethylenically unsaturated monomer copolymerizable with the macromonomer.

  Among the macromonomers having at least the structural unit represented by the general formula (5), preferred are those represented by the following general formula (6).

In the general formula (6), R ⁷⁶ represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and W is a single bond or

(Z ₁ and Z ₂ represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 6 carbon atoms, a cyano group, and a hydroxyl group, and Z ₃ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, and the number of carbon atoms. Represents an aryl group of 6 to 20.)

A single linking group selected from the atomic groups such as the above or a linking group composed of any combination is represented. A represents a group having at least the structural unit represented by the general formula (5).
Specific examples of the macromonomer represented by the general formula (6) include the following structures.

In said structural formula, A is synonymous with A in the said General formula (6).
Examples of such commercially available macromonomers include one-end methacryloylated polymethyl methacrylate oligomer (Mn = 6000, trade name: AA-6, manufactured by Toa Gosei Chemical Co., Ltd.) and one-end methacryloylated poly-n. -Butyl acrylate oligomer (Mn = 6000, trade name: AB-6, manufactured by Toa Gosei Chemical Co., Ltd.), single-end methacryloylated polystyrene oligomer (Mn = 6000, trade name: AS-6, Toa Gosei Chemical Co., Ltd.) ) Made).

  The molecular weight of the macromonomer is preferably a polystyrene-equivalent number average molecular weight (Mn) of 1000 to 20000, and more preferably 2000 to 15000. When the number average molecular weight is within the above range, the steric repulsion effect as a pigment dispersant can be more effectively obtained.

  Examples of the ethylenically unsaturated monomer copolymerizable with the macromonomer described above include various monomers used during the synthesis of the linear polymer.

  Examples of commercially available graft polymers include “Solsperse 24000, 28000, 32000, 38500, 39000, 55000” manufactured by Lubrizol, “Disperbyk-161, 171, 174” manufactured by BYK Chemie, and the like.

(Terminal modified polymer)
Examples of the terminal-modified polymer include polymers having a functional group at the end of the polymer described in JP-A-9-77994, JP-A-2002-273191, and the like.

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. A method of synthesizing by polymerization (for example, radical polymerization, anionic polymerization, cationic polymerization, etc.) using a functional group-containing polymerization initiator.
2. A method of synthesis by radical polymerization using a functional group-containing chain transfer agent.

  Here, the functional group introduced into the terminal of the polymer is an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or a carbon number of 4 The site | part selected from the above hydrocarbon group, an alkoxy silyl group, an epoxy group, an isocyanate group, a hydroxyl group, and an ionic functional group etc. are mentioned. Moreover, you may be a functional group which can be induced | guided | derived to these adsorption sites.

  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.

  As a monomer used for polymerization, a monomer used in the synthesis of the linear polymer can be used.

  Examples of commercially available terminal-modified polymers include “Solsperse 3000, 17000, 27000” manufactured by Lubrizol.

  As the dispersant, a polymer compound having a weight average molecular weight of 1,000 or more, a graft polymer, or a terminal-modified polymer having a heterocyclic ring in the side chain of the present invention is preferable, and among them, it has an organic dye structure or a heterocyclic structure. Graft-type polymer containing copolymerized units derived from monomers, terminal-modified type having an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, or a urethane group as a terminal group Polymers are particularly preferred.

In addition, Japanese Patent Publication No. 7-2004, Japanese Patent Publication No. 7-120041, Japanese Patent Publication No. 7-120042, Japanese Patent Publication No. 8-12424, Japanese Patent Laid-Open No. 63-287944, Japanese Patent Laid-Open No. 63-287947, Japanese Patent Laid-Open No. No. 271741 and Japanese Patent Application No. 10-116232, a urethane-based binder polymer containing an acid group, and a urethane having an acid group and a double bond in the side chain described in JP-A No. 2002-107918. Binder polymers and the like are also useful.
In addition, the acetal-modified polyvinyl alcohol-based binder polymer having an acid group described in EP999666, EP1204000, JP-A-2001-318463, etc. is excellent in balance between film strength and developability, and is suitable. It is.
Furthermore, polyvinyl pyrrolidone, polyethylene oxide and the like are useful as the water-soluble linear organic polymer. In order to increase the strength of the cured film, alcohol-soluble nylon, polyether of 2,2-bis- (4-hydroxyphenyl) -propane and epichlorohydrin, and the like are also useful.

(B) The weight average molecular weight of the resin is preferably 5,000 or more, more preferably in order to realize a viscosity range that is easy to use in the process of applying a color resist, and to ensure film strength. The range is from 10,000 to 300,000, and the number average molecular weight is preferably 1,000 or more, and more preferably from 2,000 to 250,000.
The polydispersity (weight average molecular weight / number average molecular weight) is preferably 1 or more, and more preferably 1.1 to 10.

  As the resin (b) used in the present invention, a polymer having a large acid value is desirable from the viewpoint of developability. On the other hand, if the acid value is too large, the solubility in alkali becomes too large and the appropriate development range (development latitude) becomes narrow. Therefore, the polymer acid value is preferably in the range of 20 to 300 (mg KOH / g polymer), more preferably in the range of 30 to 150 (mg KOH / g polymer), and still more preferably 35 to 120 (mg KOH / g polymer). Range.

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

The (b) resin used in the present invention can also be used as a polymer compound for coating a pigment described in the column of the pigment used in the present invention.

As content in the pigment dispersion composition of (b) resin in this invention, 0.1-50 mass% is preferable with respect to the total mass of a pigment dispersion composition, More preferably, it is 0.5-40 mass%. Yes, more preferably 1 to 30% by mass. When the content is within the above range, it is preferable because the dispersion stability is high and the hue is not impaired.
(B) resin in this invention may be used individually by 1 type, and may use 2 or more types together.

-(C) Solvent-
The solvent (c) used is not particularly limited as long as it satisfies the solubility of each component of the pigment dispersion composition and the coating property of the curable composition, but is selected in consideration of safety. Is preferred.
(C) Specific examples of the solvent are preferably esters, ethers, ketones, aromatic hydrocarbons and the like.

  Specific examples of esters include ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, and 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 (for example, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate), methyl 2-oxypropionate, 2-oxypropion Acid 2-oxypropionic acid alkyl esters such as propyl 2-oxypropionate (for example, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, 2 -Ethyl ethoxypropionate, methyl 2-oxy-2-methylpropionate, 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.

  Specific examples of ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, and propylene. Examples include glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, and propylene glycol propyl ether acetate.

Specific examples of the ketones include methyl ethyl ketone, cyclohexanone, 2-heptanone, and 3-heptanone.
Specific examples of aromatic hydrocarbons include toluene and xylene.

  Among 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, propylene glycol monomethyl ether acetate (PGMEA) and the like are more preferable.

  (C) As a ratio to the pigment dispersion composition of a solvent, 20-95 mass% is preferable and 25-90 mass% is more preferable. (C) When the content of the solvent is within the above range, the pigment can be dispersed uniformly, which is advantageous in terms of dispersion stability after dispersion.

-(D) Pigment-
As the (d) pigment that can be used in the pigment dispersion composition in the present invention, conventionally known various inorganic pigments or organic pigments can be used. (D) The pigment preferably has a volume average particle size as small as possible from the viewpoint of preferably high transmittance. Further, when handling properties are also taken into consideration, the volume average particle diameter of the (d) pigment is preferably 0.005 μm to 0.1 μm, and more preferably 0.005 μm to 0.05 μm.

  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-mentioned metal oxides.

As an organic pigment that can be used in the pigment dispersion composition of the present invention, for example,
CI Pigment Yellow 1, 1, 1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35: 1, 36, 36 : 1, 37, 37: 1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62: 1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127: 1, 128, 129, 133, 134, 136, 138, 139 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 1 73, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191: 1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208

CI Pigment Orange 1, 2, 5, 13, 16, 17, 19, 20, 21, 22, 23, 24, 34, 36, 38, 39, 43, 46, 48, 49, 61, 62, 64, 65 67, 68, 69, 70, 71, 72, 73, 74, 75, 77, 78, 79
CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53 : 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81 : 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 1 9, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276

CI Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32 , 37, 39, 42, 44, 47, 49, 50
CI Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33 , 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79
CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55
CI Pigment Brown 23, 25, 26
CI pigment black 1,7 Carbon black, acetylene black, lamp black, bone black, graphite, iron black, aniline black, cyanine black, titanium black and the like can be mentioned.

  The pigment (d) used in the present invention is preferably a pigment having a hydrogen atom with a low pKa in consideration of ease of penetration into the developer (d) pigment, specifically, a diketopyrrolopyrrole pigment, Quinacridone pigments, isoindolinone pigments, isoindolinone pigments, and indigo pigments are preferably used, more preferably diketopyrrolopyrrole pigments and quinacridone pigments.

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 it can be used such as a mixture of.
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 in terms of color reproducibility, these red pigments and C.I. I. Mixing with Pigment Yellow 139 (yellow pigment) is preferred. The mass ratio of the red pigment to the yellow pigment is preferably 100: 5 to 100: 50. 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. When the ratio is 100: 51 or more, the dominant wavelength is shorter than the short wavelength, and the deviation from the NTSC target hue may be large. In particular, the mass ratio is optimally in the range of 100: 10 to 100: 30. In the case of a combination of red pigments, it can be adjusted in accordance with the chromaticity.

  As the green pigment, a 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 (green pigment) 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 (yellow pigment) is preferred. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. The mass ratio is particularly preferably in the range of 100: 30 to 100: 120.

  As the blue pigment, a phthalocyanine pigment can be used alone, or a mixture thereof with a dioxazine purple pigment can be used. For example, C.I. I. Pigment blue 15: 6 (blue pigment) and C.I. I. Mixing with pigment violet 23 (purple pigment) is preferred. The mass ratio of the blue pigment to the violet pigment is preferably 100: 0 to 100: 30, more preferably 100: 10 or less.

  Further, as the pigment for the black matrix, carbon, titanium carbon, iron oxide, titanium oxide alone or a mixture thereof is used, and a combination of carbon and titanium carbon is preferable. The mass ratio of carbon to titanium carbon is preferably in the range of 100: 0 to 100: 60.

  As the pigment (d) used in the present invention, it is preferable to use a pigment that has been subjected to a refinement treatment in advance. As for the refinement of primary pigment particles, a method of mechanically kneading i) pigment, ii) water-soluble inorganic salt, and iii) water-soluble organic solvent with a kneader or the like is well known (a salt milling method). In this step, if necessary, iv) a polymer compound for pigment coating may be used at the same time.

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

ii) Water-soluble inorganic salt 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. Alternatively, it is preferable to use sodium sulfate. The amount of the inorganic salt used for salt milling is preferably 1 to 30 times by weight, particularly 5 to 25 times by weight of the organic pigment, from the viewpoint of both processing efficiency and production efficiency. The larger the ratio of the inorganic salt to the organic pigment is, the higher the refinement efficiency is.

iii) Water-soluble organic solvent The water-soluble organic solvent is a small amount of water-soluble organic solvent that does not substantially dissolve the water-soluble inorganic salt. The water-soluble organic solvent functions to wet the organic pigment and the inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. 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.

  The addition amount of the water-soluble organic solvent is preferably 5% by weight to 50% by weight with respect to the water-soluble inorganic salt. More preferably, it is 10 to 40% by weight with respect to the inorganic salt, and optimally 15 to 35% by weight with respect to the inorganic salt. If the addition amount is less than 5% by weight, uniform kneading becomes difficult and the particle sizes may become uneven. When the addition amount is 50% 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 cannot 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.

iv) Polymer compound for pigment coating The pigment coating polymer compound that may be added is preferably a solid at room temperature, insoluble in water, and at least partially soluble in a water-soluble organic solvent used as a wetting agent during salt milling. It is necessary to use a natural resin, a modified natural resin, a synthetic resin, or a synthetic resin modified with a natural resin. 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 an epoxy resin, an acrylic resin, a maleic acid resin, a butyral resin, a polyester resin, a melamine resin, a phenol resin, and a polyurethane resin. 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 condensation A thing etc. are also mentioned.
As for the timing of adding these resins, all of them may be added at the beginning of salt milling, or they may be added separately.

  When the pigment dispersion composition of the present invention is used for a color filter, from the viewpoint of color unevenness and contrast, the primary particle size (volume average particle size) of (d) pigment is preferably 5 to 100 nm, and preferably 5 to 70 nm. More preferably, 5 to 50 nm is more preferable, and 5 to 40 nm is most preferable.

≪Photosensitive resin composition≫
The photosensitive resin composition of the present invention comprises the above-described pigment dispersion composition of the present invention, (e) a photopolymerizable compound, and (f) a photopolymerization initiator. g) It may contain other components such as a sensitizer.

The content of the pigment dispersion composition in the photosensitive resin composition of the present invention is such that (d) the pigment content is in the range of 30 to 80% by mass with respect to the total solid content (mass) of the photosensitive resin composition. The amount of (d) the pigment content is more preferably in the range of 40 to 70% by mass.
When the content of the pigment dispersion composition is within this range, the color density is sufficient and effective in securing excellent color characteristics.

-(E) Photopolymerizable compound-
(E) As the photopolymerizable compound, a compound widely known as a compound having an ethylenically unsaturated double bond in the color filter-related industrial field can be used without particular limitation. For example, the compound which has chemical forms, such as a monomer, a prepolymer, ie, a dimer, a trimer, an oligomer, or mixtures thereof, and those copolymers is mentioned.

Examples of monomers and copolymers thereof include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.), esters thereof, and amides. Preferably, an ester of an unsaturated carboxylic acid and an aliphatic polyhydric alcohol compound, or an amide of an unsaturated carboxylic acid and an aliphatic polyvalent amine compound is used.
In addition, an addition reaction product of an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, amino group or mercapto group with a monofunctional or polyfunctional isocyanate or epoxy, and a monofunctional or polyfunctional compound. A dehydration condensation reaction product with a functional carboxylic acid is also preferably used.
Further, an addition reaction product of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an epoxy group or an epoxy group with a monofunctional or polyfunctional alcohol, amine or thiol, a halogen group or In addition, a substitution reaction product of an unsaturated carboxylic acid ester or amide having a leaving substituent such as a tosyloxy group and a monofunctional or polyfunctional alcohol, amine or thiol is also suitable.
As another example, it is also possible to use a group of compounds substituted with unsaturated phosphonic acid, styrene, vinyl ether or the like instead of the unsaturated carboxylic acid.

Examples of the monomer of the ester of the aliphatic polyhydric alcohol compound and the unsaturated carboxylic acid include acrylic acid ester, methacrylic acid ester, and itaconic acid ester.
Specific examples of acrylic esters include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, trimethylolpropane tri Acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, hexanediol diacrylate, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, penta Erythritol tetraacrylate, dipentaerythritol diacryl Over DOO, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, polyester acrylate oligomers, and the like. Moreover, the EO modified body of these compounds, or PO modified body is also mentioned.

  Specific examples of the methacrylic acid ester include, for example, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, ethylene glycol dimethacrylate, 1,3- Butanediol dimethacrylate, hexanediol dimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, dipentaerythritol dimethacrylate, dipentaerythritol hexamethacrylate, sorbitol trimethacrylate, sorbitol tetramethacrylate, bis [p- ( 3-methacryloxy-2 Hydroxypropoxy) phenyl] dimethyl methane, bis - [p- (methacryloxyethoxy) phenyl] dimethyl methane, and their EO-modified product, PO-modified products thereof.

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

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

  Specific examples of amide monomers of aliphatic polyvalent amine compounds and unsaturated carboxylic acids include methylene bis-acrylamide, methylene bis-methacrylamide, 1,6-hexamethylene bis-acrylamide, 1,6-hexamethylene bis. -Methacrylamide, diethylenetriamine trisacrylamide, xylylene bisacrylamide, xylylene bismethacrylamide and the like. Examples of other preferable amide monomers include those having a cyclohexylene structure described in JP-B-54-21726.

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

CH ₂ = C (R ⁴ ) COOCH ₂ CH (R ⁵ ) OH (E)
(However, R ⁴ and R ⁵ each independently represent a hydrogen atom or a methyl group.)

  Further, urethane acrylates described in JP-A-51-37193, JP-B-2-32293, and JP-B-2-16765, JP-B 58-49860, JP-B 56-17654, JP-B Urethane compounds having an ethylene oxide skeleton described in 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. Can obtain a curable composition having a very high photosensitive speed.

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

  (E) From the viewpoint of curing sensitivity, the photopolymerizable compound preferably contains two or more ethylenically unsaturated bonds, and more preferably contains three or more. Especially, it is preferable to contain 2 or more (meth) acrylic acid ester structures, it is more preferable to contain 3 or more, and it is most preferable to contain 4 or more. Furthermore, it is preferable to contain an EO modified body from the viewpoint of curing sensitivity and developability of the unexposed area. Moreover, it is preferable to contain a urethane bond from a viewpoint of hardening sensitivity and exposure part intensity | strength.

  From the above viewpoints, bisphenol A diacrylate, modified bisphenol A diacrylate EO, trimethylolpropane triacrylate, trimethylolpropane tri (acryloyloxypropyl) ether, trimethylolethane triacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate Acrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, sorbitol triacrylate, sorbitol tetraacrylate, sorbitol pentaacrylate, sorbitol hexaacrylate, tri (acryloyloxy D (I) Isocyanurate, pentaerythritol tetraacrylate EO modified product, dipentaerythritol hexaacrylate EO modified product and the like are preferable, and as a commercial product, urethane oligomer UAS-10, UAB-140 (manufactured by Sanyo Kokusaku Pulp Co., Ltd.) ), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, and AI-600 (manufactured by Kyoeisha Chemical Co., Ltd.) are preferred.

  Among them, bisphenol A diacrylate EO modified, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tri (acryloyloxyethyl) isocyanurate, pentaerythritol tetraacrylate EO modified, di Examples of commercially available modified products such as pentaerythritol hexaacrylate EO include DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 ( Kyoeisha Chemical Co., Ltd.) is more preferable.

  (E) As for the photopolymerizable compound, an appropriate structure, blending, and addition amount can be arbitrarily selected from the viewpoints of polymerization inhibition with respect to oxygen, resolution, fogging, refractive index change, surface adhesiveness, and the like.

  (E) Photopolymerizable compounds can be used in combination of two or more, in addition to being used alone.

-(F) Photopolymerization initiator-
(F) As the photopolymerization initiator, for example, halomethyl oxadiazole described in JP-A-57-6096, JP-A 59-1281, JP-A 53-133428, and the like. Active halogen compounds such as s-triazine, aromatic carbonyl compounds such as ketals, acetals, or benzoin alkyl ethers described in US Pat. No. 4,318,871 and European Patent Publication EP-88050A, US Pat. No. US Pat. No. 4,1994,420 Aromatic ketone compounds such as benzophenones described in the document, (thio) xanthone compounds or acridine compounds described in the specification of Fr-2456541, coumarin compounds or biimidazole compounds described in JP-A-10-62986, Sulphonium organoboron as disclosed in JP-A-8-015521 Complex, and the like, and the like can be given.

  (F) As photopolymerization initiators, 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, oxime ester series and the like are 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.

  Preferable examples of the benzophenone photopolymerization initiator include benzophenone, 4,4 ′-(bisdimethylamino) benzophenone, 4,4 ′-(bisdiethylamino) benzophenone, and 4,4′-dichlorobenzophenone. 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 oxime ester compounds described in JP-A No. 2000-66385.
Moreover, these photoinitiators can also be used together.

  (F) As content in the photocurable composition of a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of this composition, More preferably, 0.5- 5.0% by mass. 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.

-(G) Sensitizer-
The photosensitive resin composition of the present invention may contain (g) a sensitizer for the purpose of improving the radical generation efficiency of the (f) photopolymerizable initiator.

(G) As the sensitizer, those belonging to the following compounds and having an absorption wavelength in the range of 330 nm to 450 nm are preferably used.
For example, polynuclear aromatics (for example, phenanthrene, anthracene, pyrene, perylene, triphenylene, 9,10-dialkoxyanthracene), xanthenes (for example, fluorescein, eosin, erythrosine, rhodamine B, rose bengal), thioxanthones (Isopropylthioxanthone, diethylthioxanthone, chlorothioxanthone), cyanines (eg thiacarbocyanine, oxacarbocyanine), merocyanines (eg merocyanine, carbomerocyanine), phthalocyanines, thiazines (eg thionine, methylene blue, toluidine blue) , Acridines (eg, acridine orange, chloroflavin, acriflavine), anthraquinones (eg, anthraquinone), squariums (eg Squalium), acridine orange, coumarins (eg 7-diethylamino-4-methylcoumarin), ketocoumarin, phenothiazines, phenazines, styrylbenzenes, azo compounds, diphenylmethane, triphenylmethane, distyrylbenzenes, carbazole , Porphyrins, spiro compounds, quinacridone, indigo, styryl, pyrylium compounds, pyromethene compounds, pyrazolotriazole compounds, benzothiazole compounds, barbituric acid derivatives, thiobarbituric acid derivatives, acetophenone, benzophenone, thioxanthone, Michler's ketone, and other aromatics Examples include ketone compounds and heterocyclic compounds such as N-aryloxazolidinones.

(G) A sensitizer may be used individually by 1 type and may use 2 or more types together.
The content of the (g) sensitizer in the photosensitive resin composition of the present invention is 0.1 to 20% by mass in terms of solid content from the viewpoint of light absorption efficiency to the deep part and initiation decomposition efficiency. Is preferable, and 0.5-15 mass% is more preferable.

-Other ingredients-
If necessary, the photosensitive resin composition of the present invention includes a surfactant, a polymerization inhibitor, a substrate adhesion agent, a co-sensitizer, a chain transfer agent, a thermal polymerization initiator, a thermal polymerization component, and an ultraviolet absorber. Various additives such as an agent, a filler, a polymer compound other than the (b) resin, a colorant, an adhesion promoter, an antioxidant, and an anti-aggregation agent can be contained.

<Surfactant>
The photosensitive resin composition of the present invention is preferably composed of various surfactants from the viewpoint of improving coatability. In addition to the fluorosurfactant, nonionic, cationic, and anionic Various surfactants can be used. Of these, fluorine-based surfactants and nonionic surfactants are preferable.

  By including a fluorosurfactant in the photosensitive resin composition, the liquid properties (particularly fluidity) of the coating solution can be improved, and the coating film (curable layer) can be made uniform in film thickness and liquid-saving. Can improve sex. That is, the interfacial tension between the substrate and the coating liquid is reduced to improve the wettability to the substrate and the coating property to the substrate is improved, so that a thin film of about several μm is formed with a small amount of liquid. This is also effective in that a film having a uniform thickness with small thickness unevenness can be formed.

  The fluorine content of the fluorosurfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. 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, F475, 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 Co., Ltd.) ), 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, 01, the same 802 (manufactured by JEMCO (Ltd.)), and the like.

The fluorine-based surfactant 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 the photosensitive resin composition, and, as for the addition amount of a fluorine-type surfactant, More preferably, it is 0.005-1.0 mass%.

  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., etc. It can be used as appropriate.

<Polymerization inhibitor>
In the present invention, a small amount of a thermal polymerization inhibitor (in order to prevent unnecessary thermal polymerization of a compound having an ethylenically unsaturated double bond that can be polymerized during the production or storage of the photosensitive resin composition, It is desirable to add a polymerization inhibitor). Suitable polymerization inhibitors 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-tert-butylphenol),
N-nitrosophenylhydroxyamine primary cerium salt and the like. The addition amount of the polymerization inhibitor is preferably about 0.01% by mass to about 5% by mass with respect to the mass of the total photosensitive resin composition.
If necessary, a higher fatty acid derivative such as behenic acid or behenic acid amide may be added to prevent polymerization inhibition due to oxygen, and it may be unevenly distributed on the surface of the photosensitive layer in the course of drying after coating. . The amount of the higher fatty acid derivative added is preferably about 0.1% by mass to about 10% by mass of the total photosensitive resin composition.

<Board adhesive>
In the present invention, in the color filter, it is desirable to add a substrate adhesive to the photosensitive resin composition in order to improve the adhesion to the substrate. Examples of the substrate adhesion agent include various silane coupling agents. Examples of the silane coupling agent include γ- (2-aminoethyl) aminopropyltrimethoxysilane and γ- (2-aminoethyl) aminopropyl. Dimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropyltriethoxy Silane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ -A Nopropyltrimethoxysilane / hydrochloride, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, aminosilane, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, methyltrimethoxy Silane, methyltriethoxysilane, vinyltriacetoxysilane, γ-chloropropyltrimethoxysilane, hexamethyldisilazane, γ-anilinopropyltrimethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (β-methoxyethoxy) ) Silane, octadecyldimethyl [3- (trimethoxysilyl) propyl] ammonium chloride, γ-chloropropylmethyldimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, Methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, bisallyltrimethoxysilane, tetraethoxysilane, bis (trimethoxysilyl) hexane, phenyltrimethoxysilane, N -(3-acryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, N- (3-methacryloxy-2-hydroxypropyl) -3-aminopropyltriethoxysilane, (methacryloxymethyl) methyldiethoxysilane , (Acryloxymethyl) methyldimethoxysilane, and the like. The amount of the substrate adhesion agent added is preferably about 0.1% by mass to about 10% by mass of the total photosensitive resin composition.

<Co-sensitizer>
The photosensitive resin composition of the present invention preferably contains a co-sensitizer. In the present invention, the co-sensitizer has functions such as further improving the sensitivity of the sensitizing dye and the initiator to actinic radiation or suppressing inhibition of polymerization of the polymerizable compound by oxygen.
Examples of such cosensitizers include amines such as M.I. R. Sander et al., “Journal of Polymer Society”, Vol. 10, 3173 (1972), Japanese Patent Publication No. 44-20189, Japanese Patent Publication No. 51-82102, Japanese Patent Publication No. 52-134692, Japanese Patent Publication No. 59-138205. , JP-A-60-84305, JP-A-62-18537, JP-A-64-33104, Research Disclosure 33825, and the like. Specific examples include triethanolamine. P-dimethylaminobenzoic acid ethyl ester, p-formyldimethylaniline, p-methylthiodimethylaniline and the like.

  Other examples of co-sensitizers include thiols and sulfides, for example, thiol compounds described in JP-A-53-702, JP-B-55-500806, JP-A-5-142773, and JP-A-56. And the like. Specific examples include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2-mercapto-4 (3H) -quinazoline, β-mercaptonaphthalene. Etc.

  Other examples include amino acid compounds (eg, N-phenylglycine), organometallic compounds described in Japanese Patent Publication No. 48-42965 (eg, tributyltin acetate), and hydrogen described in Japanese Patent Publication No. 55-34414. Examples thereof include donors and sulfur compounds described in JP-A-6-308727 (eg, trithian etc.).

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

<Chain transfer agent>
Examples of the chain transfer agent that can be added to the photosensitive resin 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.

<Thermal polymerization initiator>
It is also effective to contain a thermal polymerization initiator in the photosensitive resin 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 contain a thermal polymerization component in the photosensitive resin 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.

  In addition to the above, various additives can be added to the photosensitive resin 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 photosensitive resin composition is further improved, the photosensitive resin composition has an organic carboxylic acid, preferably a low molecular weight organic compound having a molecular weight of 1000 or less. Carboxylic acid 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.

  The photosensitive resin composition of the present invention has high sensitivity, is cured well at a low exposure amount, and has good storage stability. Moreover, when it is applied (for example, applied) to the surface of a hard material such as a substrate, it exhibits high adhesion with the substrate or the like, and a fine and well-shaped pattern can be formed. Therefore, the photosensitive resin composition of the present invention can be preferably used in the fields of image forming materials such as three-dimensional stereolithography, holography, and color filters, and inks, paints, adhesives, and coating agents.

≪Color filter and its manufacturing method≫
Next, the color filter of the present invention and the manufacturing method thereof will be described.
The color filter of the present invention is configured by providing a color pattern formed using the above-described photosensitive resin composition of the present invention (preferably on a support).
Hereinafter, the color filter of the present invention will be described in detail through its manufacturing method (color filter manufacturing method of the present invention).

  The method for producing a color filter of the present invention is a process for forming a curable layer by applying a photosensitive resin composition directly or via another layer (hereinafter referred to as a “curable layer forming process”). And a step of exposing the coated curable layer in a pattern-like manner through a mask (hereinafter sometimes referred to as “exposure step”), and developing and coloring the curable layer after exposure. A pattern forming process (hereinafter, also referred to as “development process”), and if necessary, the formed colored pattern is cured by heating and / or exposure, or is heated at a high temperature. You may further have other processes, such as a post-baking process.

Hereinafter, each process in the manufacturing method of the color filter of this invention is demonstrated.
(Curable layer forming step)
In the curable layer forming step, the photosensitive resin composition of the present invention is applied on the support to form a curable layer.

As the support, for example, soda glass used for liquid crystal display elements, Pyrex (registered trademark) glass, quartz glass, and those obtained by attaching a transparent conductive film to these, photoelectric conversion element substrates used for imaging elements, For example, a silicon substrate, a complementary metal oxide semiconductor (CMOS), or the like can be given. These substrates may have black stripes that separate pixels.
If necessary, an undercoat layer may be provided on the support for improving adhesion between the formed layers, preventing diffusion of substances, or flattening the substrate surface.

  As the coating method, various coating methods such as slit coating, ink jet method, spin coating, cast coating, roll coating, and screen printing can be applied.

  As coating thickness of the photosensitive resin composition, 0.1-10 micrometers is preferable, 0.2-5 micrometers is more preferable, 0.2-3 micrometers is further more preferable.

  The photosensitive resin composition coated on the support is usually dried at 70 to 110 ° C. for about 2 to 4 minutes to form a curable layer.

(Exposure process)
In the exposure step, the curable layer formed in the curable layer forming step is exposed in a pattern manner through a mask.
In the exposure, light is irradiated through a predetermined mask pattern, and only the irradiated portion is cured. A colored film composed of colored pixels (preferably having three colors or four colors or more) remains in a pattern shape after being cured by development processing described later.

  As radiation used for exposure, ultraviolet rays such as g-line and i-line are preferable, and a high-pressure mercury lamp is more preferable. The irradiation intensity is preferably 5 mJ to 1500 mJ, more preferably 10 mJ to 1000 mJ, and most preferably 10 mJ to 800 mJ.

(Development process)
In the development step, the exposed curable layer is developed to elute the unexposed portion (uncured portion) into the developer (for example, an alkaline aqueous solution), leaving only the exposed portion (cured portion).
As the developer, an organic alkali developer that does not cause damage to a circuit or the like provided on the support is desirable. The development temperature is usually 20 ° C. to 30 ° C., and the development time is 20 to 90 seconds.

  Examples of the alkali include ammonia water, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7. An alkaline aqueous solution obtained by diluting an organic alkaline compound such as undecene with pure water so as to have a concentration of 0.001 to 10% by mass, preferably 0.01 to 1% by mass is suitably used. When a developer composed of an alkaline aqueous solution is used, it is generally washed (rinsed) with pure water after development.

  After the development, the excess developer is washed away and dried, followed by further heat treatment (post-bake).

  By repeating the above-described curable layer forming step, exposing step, and developing step (further, if necessary, a curing step and a post-bake step) for the desired number of hues, a color filter having a desired hue can be produced.

≪Liquid crystal display element, solid-state image sensor≫
Since the color filter of the present invention has high contrast and excellent heat resistance, it can be suitably used for a liquid crystal display element.
The color filter of the present invention can be suitably used for a solid-state imaging device such as a CCD, and is particularly suitable for a high-resolution CCD device, CMOS, or the like exceeding 1 million pixels. The color filter of the present invention can be used as, for example, a color filter disposed between a light receiving portion of each pixel constituting a CCD and a microlens for condensing light.

  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.

[Synthesis Example 1]
<Synthesis of Compound (I)>
N, N-diethylaminopropanol (24 mmol, 1.2 eq) and tetrahydrofuran (THF) (200 ml) were added to a 500 ml three-necked flask and stirred on an ice bath. Sodium hydride (24 mmol, 1.2 eq) / THF (20 ml) was added thereto, and after the addition was completed, the mixture was stirred on an ice bath for 15 minutes, and then 3-cyanobenzyl bromide (20 mmol, 1.0 eq) was added thereto. Stir for 1 hour at room temperature. Then, it is poured into ice water, the mixed solution is extracted (extraction solvent: ethyl acetate), the organic solution is concentrated under reduced pressure, and further subjected to column chromatography (developing solvent: ethyl acetate / hexane), as shown below. Compound (I) having a structure was obtained. The yield was 95%.

<Synthesis of Pigment Derivative (G1)>
To a 1 L three-necked flask, 300 ml of t-amyl alcohol and 0.2 mol of potassium t-butoxy were charged. After cooling to 5 ° C., 0.2 mol of the above compound (I) was added and stirred at room temperature for 30 minutes. This reaction solution was heated to 100 ° C., and 0.1 mol of diisopropyl succinate was added dropwise over 2 hours. After the dropwise addition, the mixture was further heated and stirred for 2 hours, and then the reaction solution was returned to room temperature. This was added dropwise to 1 L of acetone, and the resulting red solid was collected by filtration and further washed with 500 mL of distilled water. The following desired pigment derivative (G1) was obtained in a yield of 20% by drying under reduced pressure at 50 ° C. for 5 hours.

<Synthesis of Compounds (II) to (VII) and Pigment Derivatives (G2) to (G7)>
The pigment derivative (G7) was converted from the pigment derivative (G2) in the same manner as the synthesis of the pigment derivative (G1) except that the compound (VII) was used instead of the following compound (II) instead of the compound (I). Synthesized. The pigment derivative (G8) was synthesized with reference to Japanese Patent Application Laid-Open No. 2001-51112.

[Example 1]
[A1. Preparation of photosensitive resin composition]
Here, an example in which a photosensitive resin composition containing a pigment is prepared for forming a color filter for use in a liquid crystal display element will be described.

A1-1. Preparation of pigment dispersion (P1) C.I. I. Pigment Red 254 (primary particle size 25 nm) and C.I. I. 40 parts by mass of 70/30 (mass ratio) mixture with Pigment Red 177 (primary particle size 20 nm), 50 parts by mass of Disperbyk-170 (manufactured by BYK Corporation, 30% solution) as a dispersion resin, the pigment in the present invention A mixed liquid consisting of 5 parts by mass of the derivative (G1) and 110 parts by mass of ethyl 3-ethoxypropionate as a solvent was mixed and dispersed by a bead mill for 15 hours to prepare a pigment dispersion (P1).

A1-2. Preparation of photosensitive resin composition (1) (coating liquid) Using the pigment dispersion liquid (P1) subjected to the dispersion treatment, the photosensitive resin composition (1) was prepared by stirring and mixing so that the following composition ratio was obtained.
Colorant (Pigment dispersion (P1)) 600 parts by weight Photopolymerization initiator (2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 ′ -Biimidazole) 30 parts by mass-pentaerythritol tetraacrylate 50 parts by mass-alkali-soluble resin (benzyl methacrylate / methacrylic acid / hydroxyethyl methacrylate copolymer, molar ratio: 80/10/10, Mw: 10,000) 5 parts by mass Solvent: 900 parts by mass of PGMEA / substrate adhesion agent (3-methacryloxypropyltrimethoxysilane) 1 part by mass / sensitizer (the following chemical formula α) 15 parts by mass / co-sensitizer (2-mercaptobenzimidazole) 15 parts by mass

[A2. Production of color filter (1)]
A2-1. Curable layer forming step The photosensitive resin composition (1) as a resist solution was slit-coated on a 550 mm × 650 mm glass substrate under the following conditions, and then allowed to stand for 10 minutes, followed by vacuum drying and prebaking (prebake). (100 degreeC, 80 second) was given, and the photosensitive resin composition coating film (curable layer) was formed. The slit application conditions are as follows.

(Slit application conditions)
・ Gap between the openings at the tip of the coating head: 50 μm ・ Coating speed: 100 mm / second ・ Clearance between substrate and coating head: 150 μm ・ Dry film thickness 1.75 μm ・ Coating temperature: 23 ° C.

A2-2. Exposure Step and Development Step After that, the curable film is exposed in a pattern using a test photomask with a line width of 20 μm using a 2.5 kW ultra-high pressure mercury lamp. After the exposure, the entire surface of the coating film is organically developed. The sample was covered with a 10% aqueous solution (trade name: CD, manufactured by FUJIFILM Electronics Materials Co., Ltd.) and left still for 60 seconds.

A2-3. After the heat treatment is stopped, pure water is sprayed in a shower to wash away the developer, and the coating film (curable film) that has been subjected to the photocuring process and the developing process in the exposure process and the developing process is heated in a 220 ° C. oven. Heated for hours (post bake). Thereby, the color filter (1) formed by forming a colored resin film (colored pattern) on the glass substrate was obtained.

[Examples 2-6, Comparative Examples 1-2]
Pigment dispersions (P2) to (P8) were obtained in the same manner as in Example 1, except that the pigment derivatives (G2) to (G8) were used instead of the pigment derivative (G1). Further, photosensitive resin compositions (2) to (8) were respectively obtained in the same manner as in Example 1 except that the pigment dispersions (P2) to (P8) were used instead of the pigment dispersion (P1). Obtained. Further, color filters (2) to (8) were respectively obtained in the same manner as in Example 1 except that the photosensitive resin compositions (2) to (8) were used instead of the photosensitive resin composition (1). Got.

[Performance evaluation]
The performances of the obtained pigment dispersions (P1) to (P8), photosensitive resin compositions (1) to (8), and color filters (1) to (8) were measured according to the following methods. The results are shown in Table 4.

(1. Viscosity)
After adjusting the respective dispersions (pigment dispersions (P1) to (P8)) for 3 hours, the viscosity at 25 ° C. was measured with an E-type viscometer (trade name RE-810, manufactured by Toki Sangyo Co., Ltd.) The results are shown in Table 4 with the following distinction.
<Criteria>
◎: Less than 50 mPa · s ○: 100 mPa · s or more, less than 50 mPa · s Δ: 100 mPa · s or more, less than 200 mPa · s ×: 200 mPa · s or more

(2. Contrast)
<Measurement of contrast>
A polarizing plate is placed on the colored pattern of the obtained color filter, and a colored resin film is sandwiched between the deflecting plate and the glass substrate. The luminance when the polarizing plate is parallel and the luminance when the polarizing plate is orthogonal are BM-5 manufactured by Topcon Corporation. The value obtained by dividing the parallel brightness by the orthogonal brightness (= the parallel brightness / the orthogonal brightness) was used as an index for evaluating the contrast. Larger values indicate higher contrast.
<Criteria>
◎: 5000 or more ○: 4000 to 5000
Δ: 3000 to 4000
×: 3000 or more

(3. Heat resistance)
In the substrate coated with the obtained photosensitive resin composition, color evaluation (trade name: MCPD-1000, manufactured by Otsuka Electronics Co., Ltd.) was performed before and after heating for 1 hour at 200 ° C. with a hot plate. The color difference (ΔEab value) before and after the heating was determined and evaluated according to the following criteria. A smaller ΔEab value indicates better heat resistance.
<Criteria>
○: ΔEab value <5
Δ: 5 ≦ Eab value ≦ 10
×: 10 <ΔEab value

  From the results of Table 4, it can be seen that the pigment dispersion compositions in the examples have a low dispersion viscosity and excellent dispersion stability even after 3 hours from the preparation. Moreover, it turns out that the color filter excellent in contrast and heat resistance is obtained by using those pigment dispersion compositions.

  Hereinafter, an example in which a photosensitive resin composition containing a colorant (pigment) is prepared for forming a color filter for use in a solid-state imaging device will be described.

[Example 7]
[B1. Preparation of resist solution (photosensitive resin composition (9))]
Components of the following composition were mixed and dissolved to prepare a resist solution (photosensitive resin composition (9)).
<Composition of resist solution (photosensitive resin composition (9))>
Propylene glycol monomethyl ether acetate 19.20 parts by mass (PGMEA: solvent)
-Ethyl lactate 36.67 parts by mass-Resin (40% PGMEA solution of benzyl methacrylate / methacrylic acid / methacrylic acid-2-hydroxyethyl copolymer (molar ratio = 60/22/18)) 30.51 parts by mass Ethylenically unsaturated double bond-containing compound (dipentaerythritol hexaacrylate) 12.20 parts by mass Polymerization inhibitor (p-methoxyphenol) 0.0061 parts by mass Fluorosurfactant (F-475, Dainippon Ink) 0.83 parts by mass / photopolymerization initiator (trihalomethyltriazine photopolymerization initiator) 0.586 parts by mass (TAZ-107, manufactured by Midori Chemical Co., Ltd.)

[B2. Production of silicon substrate 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.

[B3. Preparation of pigment dispersion (P9)]
As a pigment, C.I. I. Pigment Red 254 (primary particle size 32 nm) and C.I. I. 40 parts by mass of 70/30 (mass ratio) mixture with Pigment Red 177 (primary particle size 30 nm), 50 parts by mass of Disperbyk-170 (manufactured by BYK Corporation (30% solution)) as a dispersant, pigment derivative in the present invention (G1) A pigment dispersion (P9) was prepared by mixing and dispersing a mixture of 10 parts by mass and 110 parts by mass of propylene glycol monomethyl ether as a solvent using a bead mill for 15 hours.
With respect to the pigment dispersion (P9), the average particle diameter (volume average particle diameter) of the pigment was measured by the dynamic light scattering method in the same manner as in Example 1. As a result, it was 65 nm.

[B4. Preparation of photosensitive resin composition (9) (coating solution)]
A photosensitive resin composition (9) was prepared by stirring and mixing the pigment dispersion liquid (P9) subjected to the dispersion treatment so as to have the following composition ratio.
-Colorant (Pigment dispersion (P9)) 600 parts by mass-Photopolymerization initiator (oxime photopolymerization initiator)
(CGI-124, manufactured by Ciba Specialty Chemicals Co., Ltd.) 30 parts by mass, TO-1382 (manufactured by Toagosei Co., Ltd.) 25 parts by mass, 30 parts by mass of dipentaerythritol hexaacrylate, 900 parts by mass of solvent (PGMEA), substrate Adhesive (3-methacryloxypropyltrimethoxysilane) 1 part by mass

[B5. Production and Evaluation of Color Filter (9) Using Photosensitive Resin Composition (9)]
<Evaluation of pattern formation and sensitivity>
The photosensitive resin composition (9) prepared as described above was added to the B2. The colored layer (coating film) was formed by coating on the undercoat layer of the silicon wafer with the undercoat layer obtained in (1). Then, heat treatment (pre-baking) was performed for 120 seconds using a hot plate at 100 ° C. so that the dry film thickness of the coating film became 0.7 μm.
Next, using an i-line stepper exposure apparatus FPA-3000i5 + (manufactured by Canon Inc.), exposure was performed at various exposure doses of 50 to 1200 mJ / cm ² through an Island pattern mask having a pattern of 2 μm square at a wavelength of 365 nm.
Thereafter, the silicon wafer substrate on which the irradiated coating film 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 (FUJIFILM Corporation). Paddle development was performed at 23 ° C. for 60 seconds using Electronics Materials Co., Ltd. to form a colored pattern on the silicon wafer substrate.

  A silicon wafer on which a colored pattern is formed is fixed to the horizontal rotary table by a vacuum chuck method, and the silicon wafer substrate is rotated at a rotation speed of 50 r. p. m. While being rotated, pure water was supplied from the upper part of the rotation center in the form of a shower through a spray nozzle, followed by rinsing treatment, and then spray drying. A color filter (9) was obtained as described above.

[Examples 8 to 12, Comparative Examples 3 to 4]
Pigment dispersions (P10) to (P16) were obtained in the same manner as in Example 7, except that the pigment derivatives (G2) to (G8) were used instead of the pigment derivative (G1). Further, photosensitive resin compositions (10) to (16) were respectively obtained in the same manner as in Example 7 except that the pigment dispersions (P10) to (P16) were used instead of the pigment dispersion (P9). Obtained. Further, color filters (10) to (16) were respectively obtained in the same manner as in Example 7 except that the photosensitive resin compositions (10) to (16) were used instead of the photosensitive resin composition (9). Got.

  The performance evaluation of Examples 7 to 12 and Comparative Examples 3 to 4 was performed by the same evaluation method as in Example 1. The results are shown in Table 5.

  From the results of Table 5, it can be seen that the pigment dispersion compositions in Examples used for forming color filters for solid-state imaging devices have a low dispersion viscosity and excellent dispersion stability even after 3 hours from the preparation. . Moreover, it turns out that the color filter excellent in contrast and heat resistance is obtained by using those pigment dispersion compositions.

From the above results, the pigment dispersion composition of the present invention has excellent dispersion stability, and the photosensitive resin composition containing the pigment dispersion composition of the present invention is used for color filters for liquid crystal display devices and for solid-state imaging devices. It has been found that excellent contrast and heat resistance can be realized when producing the color filter.

Claims (10)

A pigment dispersion composition comprising at least a pigment derivative represented by the following general formula (1), a resin, a solvent, and a pigment.
[Pig]-(ABC) _n General formula (1)
[In the above general formula (1), [Pig] represents a pigment mother nucleus structure. A represents one linking group selected from the group consisting of CH ₂ , CH ₂ O, CH ₂ S, O, CO, and COO. B represents a chain organic linking group. C represents one or more functional groups selected from the group consisting of an acidic functional group, a basic functional group, and a hydrogen bonding functional group. n represents an integer of 1 to 10. ]   The pigment dispersion composition according to claim 1, wherein B in the general formula (1) has 3 to 30 atoms constituting the main chain.   The pigment dispersion composition according to claim 1, wherein B in the general formula (1) has 5 to 30 atoms constituting the main chain.   The pigment dispersion composition according to claim 1, wherein B in the general formula (1) has 7 to 30 atoms constituting the main chain.   The pigment dispersion composition according to any one of claims 1 to 4, which is used for forming a colored region in a color filter.   A photosensitive resin composition comprising the pigment dispersion composition according to any one of claims 1 to 5, a photopolymerizable compound, and a photopolymerization initiator.   A color filter comprising a colored region formed of the photosensitive resin composition according to claim 6 on a substrate. A curable layer forming step of forming the curable layer by applying the photosensitive resin composition according to claim 6 directly or via another layer onto a support;
An exposure step of exposing the curable layer formed by coating in a pattern manner through a mask;
And a developing step of developing the curable layer after exposure to form a colored pattern.   A liquid crystal display element comprising the color filter according to claim 7.   A solid-state imaging device comprising the color filter according to claim 7.