JP2008083594A - Colored photosensitive composition, color filter and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a colored photosensitive composition that is superior in slit coating property and stability, having high contrast and suitably usable for a color filter, a color filter obtained by using the colored photosensitive composition, and to provide a method for producing the color filter. <P>SOLUTION: The colored photosensitive composition comprises a high molecular compound, having 2-100 pigment adsorbing functional groups at one terminal, a pigment, an organic solvent, a photopolymerizable compound and a photopolymerization initiator. The colored photosensitive composition has its viscosity measured at 25°C with an E-type viscosimeter, where the number of revolutions of a rotor is 5 rpm is 50 mP×s or smaller and value calculated by the following expression (I) is 0.95-1.15; (I): (viscosity measured at 25°C with the E-type viscosimeter where the number of revolutions of the rotor is 5 rpm)/(viscosity measured at 25°C with the E-type viscosimeter in which the number of revolutions of the rotor is 50 rpm). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The demand for liquid crystal displays is rapidly expanding from conventional monitor applications to television applications. Along with the rapid increase in demand for TV applications, there has been a demand for further improvements in image quality represented by contrast, color reproduction, video display performance, etc., and the demand for higher contrast for color filters has increased. (For example, refer nonpatent literature 1).

  Panel manufacturers are also working to improve productivity by increasing board size in order to win fierce cost competition. As the substrate size increases, the color filter creation method is changing from the conventional spin method to the slit-spin method (for example, see Non-Patent Document 2) and further to the slit method (for example, Patent Document 1). reference).

  By the way, light scattering by pigment particles in the color filter can be cited as a major factor in reducing the contrast. From this, it is known that finer pigment particles are effective in achieving high contrast (see, for example, Patent Document 2). Since such fine pigment particles have a large surface area, they tend to aggregate and thicken and are difficult to stabilize. For this problem, it is known to use a known polymer dispersant (see, for example, Patent Document 3).

  However, in order to stabilize the finer particles, it is necessary to use a larger amount of the polymer dispersant because of the increase in the total surface area accompanying the finer particles. Even if a large amount of a known polymer dispersant is used to stabilize finer particles, sufficient stability cannot be obtained, and viscosity depends on shear rate (so-called thixotropy). The present situation is that it has a defect that a streak-like defect occurs when coating is performed by the slit method.

As means for improving coating properties, use of a fluorosurfactant (for example, see Patent Document 4), improvement of a resin component (for example, see Patent Document 5), and the like have been disclosed. The effect was insufficient for a high contrast colored photosensitive composition using particles.
Japanese Patent Laid-Open No. 2003-2222997 JP-A-9-197118 JP 2001-335717 A JP 2001-269564 A JP-A-2005-70152 2003 FPD Technology Encyclopedia, Electronic Journal Color filter deposition technology and chemicals, 1998, CMC

  An object of this invention is to provide the coloring photosensitive composition excellent in slit coating property. Also provided are a colored photosensitive composition that is excellent in stability and has a high contrast and can be suitably used for a color filter, a color filter using the colored photosensitive composition, and a method for producing the color filter. For the purpose.

Means for solving the above problems are as follows.
<1> Contains a polymer compound having 2 to 100 pigment-adsorptive functional groups at one end, a pigment, an organic solvent, a photopolymerizable compound, and a photopolymerization initiator, at 25 ° C. The viscosity of the E-type viscometer measured at 5 rpm is 50 mP · s or less, and the value obtained by the following formula (I) is 0.95 to 1.15. Sex composition.
Formula (I)
(Viscosity measured at 25 ° C. with a rotor speed of 5 rpm in an E-type viscometer) /
(Viscosity measured at 25 ° C. with a rotor speed of E-type viscometer at 50 rpm)
<2> The colored photosensitive composition according to <1>, wherein the polymer compound has an acid value of 20 to 200 mgKOH / g.
<3> The colored photosensitive composition according to <1> or <2>, wherein an average particle size of the pigment is 0.01 μm to 0.05 μm.

<4> The colored photosensitive composition according to any one of <1> to <3>, wherein a value obtained by the formula (I) is 0.98 to 1.10.
<5> The colored photosensitive composition according to any one of <1> to <4>, wherein an average particle size of the pigment is 0.01 μm to 0.035 μm.

<6> The colored photosensitive composition according to any one of <1> to <5>, wherein the polymer compound is a compound represented by the following general formula (1).

[In General Formula (1), R ¹ represents an (m + n) -valent organic linking group, and R ² represents a single bond or a divalent organic linking group. A ¹ is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a substituent. Represents a monovalent organic group having a group selected from the group consisting of an organic dye structure or a heterocyclic ring and a hydroxyl group, and n A ^{1 s} may be the same or different . m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer skeleton. ]

<7> The colored photosensitive composition according to any one of <1> to <6>, wherein the polymer compound is contained in an amount of 20 to 100 parts by mass with respect to 100 parts by mass of the pigment.
<8> The coloring according to any one of claims 1 to 7, wherein the proportion of the pigment in the components other than the solvent in the colored photosensitive composition is 30% by mass to 50% by mass. Photosensitive composition.

<9> A color filter comprising the colored photosensitive composition according to any one of <1> to <8>.

<10> A coating film of the colored photosensitive composition according to any one of <1> to <8> is formed by slit coating on a substrate directly or via another layer, and then prebaked and patterned exposure And a method for producing a color filter, wherein alkali development is sequentially performed.

  The present invention can provide a colored photosensitive composition excellent in slit coatability. Also provided are a colored photosensitive composition that is excellent in stability and has a high contrast and can be suitably used for a color filter, a color filter using the colored photosensitive composition, and a method for producing the color filter. be able to.

  Hereinafter, the colored photosensitive composition of the present invention, a color filter using the same, and a method for producing the color filter will be described in detail.

<Colored photosensitive composition>
The colored photosensitive composition of the present invention comprises a polymer compound having 2 to 100 pigment-adsorptive functional groups at one end (hereinafter sometimes referred to as “specific polymer compound”), a pigment, and an organic compound. It contains a solvent, a photopolymerizable compound, and a photopolymerization initiator, and has a viscosity of 50 mP · s or less measured at 25 ° C. with a rotor rotation speed of 5 rpm in an E-type viscometer represented by the following formula (I) The value calculated | required by 0.95 is 1.5-1.15, Furthermore, it can comprise using another component as needed.
Formula (I)
(Viscosity measured at 25 ° C. with a rotor speed of 5 rpm in an E-type viscometer) /
(Viscosity measured at 25 ° C. with a rotor speed of E-type viscometer at 50 rpm)

  The colored photosensitive composition of the present invention has a viscosity of 50 mP · s or less, more preferably a viscosity of 30 mP · s or less, and a viscosity measured at 25 ° C. with an E-type viscometer at 5 rpm. Is 20 mP · s or less. When the viscosity exceeds 50 mP · s, the stability and flow characteristics deteriorate, and the contrast further decreases.

Moreover, the value calculated | required by the following formula (I) is 0.95-1.15 in the colored photosensitive composition of this invention.
Formula (I)
(Viscosity measured at 25 ° C. with a rotor speed of 5 rpm in an E-type viscometer) /
(Viscosity measured at 25 ° C. with a rotor speed of E-type viscometer at 50 rpm)
As a value calculated | required by said Formula (I), a more preferable value is 0.98-1.10, and it is 1.00-1.10 optimally. If this value exceeds 1.15, the stability and flow characteristics deteriorate. On the other hand, if this value is less than 0.95, the flow characteristics deteriorate, which is not preferable.

  A colored photosensitive composition having a viscosity of 50 mP · s or less measured at 25 ° C. and a rotor rotation number of 5 rpm in an E-type viscometer, and a value obtained by the formula (I) of 0.95 to 1.15. A thing is obtained by using the specific high molecular compound mentioned later.

(Specific polymer compound)
Examples of the pigment adsorbing group in the polymer compound having 2 to 100 pigment adsorbing groups at one end of the present invention and having a weight average molecular weight of 3000 to 50000 include, for example, an acidic group and a basic nitrogen atom. An organic dye structure which may have a group having a hydrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a substituent Examples thereof include a heterocyclic ring and a hydroxyl group, and an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, and an organic dye structure or a heterocyclic ring which may have a substituent are preferable.

In addition, 2 to 100 pigment adsorbing groups exist at one end of the specific polymer compound,
Preferably 3 to 50 are present, more preferably 4 to 20 are present. If the number of pigment adsorbing groups present at one end of the specific polymer compound is less than 2, the adsorptive power with respect to the pigment is insufficient, and sufficient stability cannot be obtained. The interaction between the groups increases, the adsorption efficiency to the pigment decreases, and sufficient stability cannot be obtained.

  On the other hand, the weight average molecular weight of the specific polymer compound is preferably from 3,000 to 50,000, more preferably from 5,000 to 40,000, and from 10,000 to 35,000 in terms of stability, flow characteristics, and developability. Further preferred.

  It is preferable to add 20-100 mass parts of specific polymer compounds with respect to 100 mass parts of pigments mentioned later. A more preferable addition amount is 20 to 85 parts by mass, and most preferably 25 to 75 parts by mass with respect to 100 parts by mass of the pigment. When the polymer compound is added in an amount of 20 to 100 parts by mass with respect to 100 parts by mass of the pigment to be described later, there are few excess polymer compounds that cannot be adsorbed on the pigment particle surface, and the flow characteristics are improved. Moreover, sufficient dispersion stability is obtained, stability and flow characteristics are improved, and contrast is further improved.

  The specific polymer compound preferably has an acid value of 20 to 200 mgKOH / g, preferably 30 to 180, and more preferably 50 to 150 in terms of stability, flow characteristics, and developability. . In the present invention, the acid value of the specific polymer compound was determined by calculation from the structure.

  Specific examples of the specific polymer compound include a polymer compound in which a sulfonic acid group or a monosulfate group is introduced only at one end of a polymer portion described in JP-A-2002-273191, and JP-A-2004-54213. A pigment adsorption block containing a basic group as a pigment adsorption group, or a pigment adsorption block containing an acid group as a pigment adsorption group in addition to a pigment adsorption block containing a basic group as a pigment adsorption group, and a block not containing a pigment adsorption group A block copolymer resin comprising: Coat. Technol. 58 (736), 71 (1986), and a polyurethane having a carboxyl group at the terminal.

  Moreover, as a specific high molecular compound, the high molecular compound represented by following General formula (1) is mentioned preferably.

In General Formula (1), R ¹ represents an (m + n) -valent organic linking group, and R ² represents a single bond or a divalent organic linking group. A ¹ is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, a substituted group An organic dye structure or a heterocyclic ring which may have a group, and a monovalent organic group having a group selected from a hydroxyl group, and n A ¹ may be the same or different. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer skeleton.

  The polymer compound represented by the general formula (1) is an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or a group having 4 or more carbon atoms at the end of the polymer. Since it has a plurality of functional groups selected from hydrocarbon groups, alkoxysilyl groups, epoxy groups, isocyanate groups, organic dye structures or heterocyclic rings which may have substituents, hydroxyl groups, etc. It has excellent characteristics, excellent micelle formation ability, surface activity, and various characteristics.

In the general formula (1), A ¹ is not particularly limited, but examples of the “monovalent organic group having an acidic group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, Examples thereof include monovalent organic groups having a phosphoric acid group, a monophosphate ester group, a boric acid group, and the like.

Examples of the “monovalent organic group having a group having a basic nitrogen atom” include, for example, a monovalent organic group having an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R). ¹⁰ ) having a monovalent organic group (wherein R ⁸ , R ⁹ and R ¹⁰ are each independently an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or 7 or more carbon atoms). An aralkyl group.), A monovalent organic group having a guanidyl group represented by the following formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl having 1 to 20 carbon atoms. Group, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms. A monovalent organic group having an amidinyl group represented by the following formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ are each independently an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms The above aryl group and an aralkyl group having 7 or more carbon atoms are represented. And the like.

Examples of the “monovalent organic group having a urea group” include, for example, —NHCONHR ¹⁵ (wherein R ¹⁵ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, carbon Represents an aralkyl group of 7 or more).

As the “monovalent organic group having a urethane group”, for example, —NHCOOR ¹⁶ , —OCONHR ¹⁷ (wherein R ¹⁶ and R ¹⁷ are each independently an alkyl group having 1 to 20 carbon atoms, 6 carbon atoms, The above aryl group, and an aralkyl group having 7 or more carbon atoms).
Examples of the “monovalent organic group having a“ group having a coordinating oxygen atom ”” include a group having an acetylacetonato group and a group having a crown ether.

  Examples of the “monovalent organic group having a hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms (for example, octyl group, dodecyl group, etc.) and an aryl group having 6 or more carbon atoms (for example, phenyl Group, a naphthyl group, etc.), an aralkyl group having 7 or more carbon atoms (for example, a benzyl group) and the like.

Examples of the “monovalent organic group having an alkoxysilyl group” include groups having a trimethoxysilyl group, a triethoxysilyl group, and the like.
Examples of the “monovalent organic group having an epoxy group” include a group having a glycidyl group.
Examples of the “monovalent organic group having an isocyanate group” include a 3-isocyanatopropyl group.

  The “monovalent organic group having an organic dye structure or a heterocyclic ring” is not particularly limited. More specifically, examples of the organic dye structure include phthalocyanine-based, insoluble azo-based, azo lake-based, and anthraquinone-based compounds. Quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, ansanthrone, indanthrone, flavanthrone, perinone, perylene, thioindigo and the like. Examples of the heterocyclic ring include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine, piperidine, dioxane, Examples include morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, and anthraquinone.

The organic dye structure or the heterocyclic ring may have a substituent. Examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. C1-C6 acyloxy groups such as aryl groups having 6 to 16 carbon atoms, such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, and acetoxy groups, methoxy groups, and ethoxy groups Alkoxy groups having 1 to 6 carbon atoms such as halogen atoms such as chlorine and bromine, methoxycarbonyl groups, ethoxycarbonyl groups, cyclohexyloxycarbonyl groups, etc., alkoxycarbonyl groups having 2 to 7 carbon atoms, cyano groups, t- And carbonic acid ester groups such as butyl carbonate.
Examples of the “group having a hydroxyl group” include a 3-hydroxypropyl group.

Among the above, A ¹ is preferably a monovalent organic group having a group selected from an acidic group, a group having a basic nitrogen atom, a urea group, and a hydrocarbon group having 4 or more carbon atoms. . Further, as the A ^1, it is preferably a monovalent organic group represented by the following general formula (4).

A ¹ is preferably a monovalent organic group represented by the following general formula (4).

In the general formula (4), B ¹ is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, or an alkoxysilyl group. , An epoxy group, an isocyanate group, an organic dye structure which may have a substituent, or a group selected from a heterocyclic ring and a hydroxyl group, and R ¹⁸ represents a single bond or an a-valent organic linking group. a represents 1 to 5, and a B ¹ may be the same or different.

B ¹ has the same meaning as A ¹ in formula (4), and the preferred embodiment is also the same.
R ⁸ represents a single bond or an a-valent organic linking group, and a represents 1 to 5. The a-valent organic linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 Groups comprising from 20 to 20 sulfur atoms are included and may be unsubstituted or further substituted.

  Specific examples of the a-valent organic linking group include the following structural units or groups constituted by combining the structural units.

  Among the above, when the a-valent organic linking group has a substituent, examples of the substituent include carbon having 1 to 20 carbon atoms such as methyl and ethyl, carbon such as phenyl and naphthyl. Carbon number such as acyloxy group having 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc., methoxy group, ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate, etc. And carbonate ester groups.

In the general formula (1), R ¹ represents an (m + n) -valent organic linking group. m + n satisfies 3-10.
Examples of the (m + n) -valent organic linking group represented by R ¹ include 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups consisting of up to 200 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.

Specific examples of the (m + n) -valent organic linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure). .

  Among the above, when the polyvalent organic linking group has a substituent, examples of the substituent include carbon such as an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Carbon number such as acyloxy group having 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc., methoxy group, ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate, etc. And carbonate ester groups.

R ² represents a single bond or a divalent organic linking group. The divalent organic linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 Groups comprising from 20 to 20 sulfur atoms are included and may be unsubstituted or further substituted.

  Specific examples of the divalent organic linking group include the following structural units or groups formed by combining the structural units.

  Among the above, when the divalent organic linking group has a substituent, examples of the substituent include carbon having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a carbon such as a phenyl group and a naphthyl group. Carbon number such as acyloxy group having 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc., methoxy group, ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate, etc. And carbonate ester groups.

In said general formula (1), m represents 1-8. As m, 1-5 are preferable, 1-3 are more preferable, and 1-2 are especially preferable.
N represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In the general formula (1), P ¹ represents a polymer skeleton and can be selected from known polymers according to the purpose and the like.
Among polymers, in order to constitute a polymer skeleton, a vinyl monomer polymer or copolymer, ester polymer, ether polymer, urethane polymer, amide polymer, epoxy polymer, silicone polymer, and these Modified product or copolymer [for example, polyether / polyurethane copolymer, copolymer of polyether / vinyl monomer, etc. (any of random copolymer, block copolymer, graft copolymer) May be included). Is preferably selected from the group consisting of vinyl monomer polymers or copolymers, ester polymers, ether polymers, urethane polymers, and modified products or copolymers thereof. At least one kind is more preferred, and a polymer or copolymer of vinyl monomers is particularly preferred.
Furthermore, the polymer is preferably soluble in an organic solvent. If the affinity with the organic solvent is low, for example, when used as a pigment dispersant, the affinity with the dispersion medium is weakened, and it may not be possible to secure a sufficient adsorption layer for stabilizing the dispersion.

  Among the polymer compounds represented by the general formula (1), the polymer compound represented by the following general formula (2) is more preferable.

In the general formula (2), A ² represents an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, or an alkoxysilyl group. Represents a monovalent organic group having a group selected from an epoxy group, an isocyanate group, an organic dye structure or a heterocyclic ring which may have a substituent, and a hydroxyl group, and A ² represents A in the general formula (1) ^It is synonymous with ¹ , and its specific preferable embodiment is also the same.

In the general formula (2), R ³ represents an (m + n) -valent organic linking group. m + n satisfies 3-10. The (m + n) -valent organic linking group represented by R ³ includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups comprising up to 100 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.

The (m + n) -valent organic linking group represented by R ³ has the same meaning as the (m + n) -valent organic linking group in R ¹ , and the preferred embodiments thereof are also the same. Further, specific examples include the same structural unit as described above or a group formed by combining the structural units.

Among these, preferred specific examples [specific examples (1) to (17)] of the organic linking group represented by R ³ are shown below. However, the present invention is not limited to these.

  Among the above, from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents, particularly preferred organic linking groups are the following groups.

  In addition, when the polyvalent organic linking group has a substituent, examples of the substituent include carbon having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a carbon such as a phenyl group and a naphthyl group. Carbon number such as acyloxy group having 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc., methoxy group, ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate, etc. And carbonate ester groups.

In the general formula (2), R ⁴ and R ⁵ each independently represents a single bond or a divalent organic linking group.
The “divalent organic linking group” represented by R ⁴ and R ⁵ may be unsubstituted or substituted, and may be a linear, branched, or cyclic alkylene group, arylene group, aralkylene group. and, -O -, - S -, - C (= O) -, - N (R 19) -, - SO -, - SO 2 -, - CO 2 -, - N (R 20) SO 2 - Or a divalent group in which two or more of these groups are combined can be cited as a preferred example (the above R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms). .)

Examples of R ⁴ include linear and branched alkylene groups, aralkylene groups, and —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO ₂ —, — N (R ²⁰ ) SO ₂ — (wherein R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), or a divalent group obtained by combining two or more of these groups Are more preferable, a linear or branched alkylene group, an aralkylene group, and —O—, —C (═O) —, —N (R ¹⁹ ) — (wherein R ¹⁹ represents a hydrogen atom or a carbon number of 1 to 4). Represents an alkyl group), —CO ₂ — or a divalent group in which two or more of these groups are combined is particularly preferred.

R ⁵ includes a single bond or a linear or branched alkylene group, an aralkylene group, —O—, —C (═O) —, —N (R ¹⁹ ) —, —SO ₂ —, —CO _2. —, —N (R ²⁰ ) SO ₂ — (wherein R ¹⁹ and R ²⁰ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms), or a combination of two or more of these groups And a linear or branched alkylene group, an aralkylene group, and —O—, —C (═O) —, —N (R ¹⁹ ) — (wherein R ¹⁹ represents a hydrogen atom or a carbon number). Represents 1 to 4 alkyl groups), —CO ₂ — or a divalent group in which two or more of these groups are combined is particularly preferable.

When R ⁴ and R ⁵ have a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon number of 6 such as a phenyl group and a naphthyl group. From 1 to 16 carbon atoms such as aryl groups, hydroxyl groups, amino groups, carboxyl groups, sulfonamido groups, N-sulfonylamido groups, acetoxy groups and the like, acyloxy groups having 1 to 6 carbon atoms, methoxy groups, ethoxy groups and the like. Carbonate esters such as alkoxy groups of up to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups of 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, cyano groups and t-butyl carbonate Group, and the like.

In said general formula (2), m represents 1-8. As m, 1-5 are preferable, 1-3 are more preferable, and 1-2 are especially preferable.
N represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

P ² in the general formula (2) represents a polymer skeleton and can be selected from known polymers according to the purpose and the like. The preferred embodiment of the polymer, has the same meaning as P ¹ in Formula (1), the same applies to its preferred embodiment.

Among the polymer compounds represented by the general formula (2), in particular, R ³ is the specific example (1), (2), (10), (11), (16), or (17). R ⁴ represents a single bond or a linear or branched alkylene group, aralkylene group, and —O—, —C (═O) —, —N (R ¹⁹ ) — (wherein R ¹⁹ represents a hydrogen atom) Or an alkyl group having 1 to 4 carbon atoms), —CO ₂ — or a divalent organic group obtained by combining two or more of these groups, wherein R ⁵ is a single bond, an ethylene group, a propylene group, Or the following group (a) or (b), wherein P ² is a polymer or copolymer of a vinyl monomer, an ester-based polymer, an ether-based polymer, a urethane-based polymer, or a modified product thereof, and m is 1 A polymer compound in which n is 2 and n is 3 to 6 is most preferable. In the following groups, R ²¹ represents a hydrogen atom or a methyl group, and l represents 1 or 2.

  As a molecular weight in case a specific high molecular compound is represented by the said General formula (1), 3000-50000 are preferable at a weight average molecular weight, 5000-40000 are more preferable, and 7000-35000 are especially preferable. When the weight average molecular weight is within the above range, the effects of the multiple functional groups introduced at the polymer ends are fully exhibited, and the performance of adsorbing to the solid surface, micelle forming ability, and surface activity is excellent. To do. In particular, when the polymer compound according to the present invention is used as a pigment dispersant, good dispersibility and dispersion stability can be achieved.

The polymer compound represented by the general formula (1) (including those represented by the general formula (2)) is not particularly limited, but can be synthesized by the following method. Of the following synthesis methods, the following synthesis methods such as 2, 3, 4, 5 and the like are more preferable, and the following synthesis methods such as 3, 4, 5, and the like are particularly preferable because of ease of synthesis.
1. A polymer in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group, or the like is introduced at the terminal; an acid halide having a plurality of functional groups (A ¹ or A ² in the general formula); or a plurality of functional groups ( A method of polymerizing an alkyl halide having A ¹ or A ² ) in the general formula or an isocyanate having a plurality of functional groups (A ¹ or A ² in the general formula).
2. A method in which a polymer having a carbon-carbon double bond introduced at the terminal and a mercaptan having a plurality of functional groups (A ¹ or A ² in the above general formula) are subjected to a Michael addition reaction.
3. A method in which a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having a plurality of functional groups (A ¹ or A ² in the above general formula) are reacted in the presence of a radical generator.
4). A method in which a polymer having a plurality of mercaptans introduced at its terminal and a functional group having a carbon-carbon double bond introduced (A ¹ or A ² in the above general formula) are reacted in the presence of a radical generator.
5. A method of radical polymerization of a vinyl monomer using a mercaptan compound having a plurality of functional groups (A ¹ or A ² in the above general formula) as a chain transfer agent.

  Among the above, the polymer compound of the present invention (particularly the polymer compound represented by the general formula (2)) can be synthesized, for example, by any of the above methods 2, 3, 4, and 5. From the viewpoint of ease of synthesis, it is most preferable to synthesize by the above method 5.

  More specifically, radical polymerization is preferably performed using a compound represented by the following general formula (3) as a chain transfer agent.

In the general formula (3), R ⁶ , R ⁷ , A ³ , m and n have the same meanings as R ³ , R ⁴ , A ² , m and n in the general formula (2), respectively. The preferred embodiment is also the same.

  Although it does not restrict | limit especially as said vinyl monomer, For example, (meth) acrylic acid, (meth) acrylic acid esters, crotonic acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters (Meth) acrylamides, vinyl ethers, esters of vinyl alcohol, styrenes, (meth) acrylonitrile and the like are preferable. Examples of such include the following compounds.

  Examples of the (meth) acrylate esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n- (meth) acrylate. Butyl, isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2 -Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate , 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate , 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) Acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether , Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, disi (meth) acrylate Clopentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromo (meth) acrylate Examples thereof include phenyl and tribromophenyloxyethyl (meth) acrylate.

  Examples of the crotonic acid esters include butyl crotonic acid and hexyl crotonic acid.

  Examples of the vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.

  Examples of the maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

  Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.

  Examples of the itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  Examples of the (meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N- n-butylacryl (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, Examples thereof include N, N-diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide and the like.

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

  Examples of the vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, and methoxyethyl vinyl ether.

In addition to the above compounds, (meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (eg, vinylpyridine, vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole Vinyl caprolactone can also be used.
In addition to the above compounds, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used. Such a monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group containing It can be appropriately synthesized by an addition reaction between a monomer and monoisocyanate.

The above vinyl monomers may be polymerized by only one kind, or may be copolymerized by using two or more kinds together. Such a radical polymer is prepared by a known method in accordance with a conventional method for each corresponding vinyl monomer. It is obtained by polymerizing.
For example, a method (solution polymerization method) in which these vinyl monomers and a chain transfer agent are dissolved in a suitable solvent, a radical polymerization initiator is added thereto and polymerized in a solution at about 50 ° C. to 220 ° C. It is obtained by using.

  Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  Examples of radical polymerization initiators include azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile), benzoyl par Peroxides such as oxides, and persulfates such as potassium persulfate and ammonium persulfate can be used.

Although the compound represented by the general formula (3) can be synthesized by the following method or the like, the following method 7 is more preferable because of ease of synthesis.
6). A method of converting a halide compound having a plurality of functional groups (A ¹ or A ² in the above general formula) into a mercaptan compound (a method of reacting with thiourea and hydrolyzing, a method of reacting directly with NaSH, CH ₃ COSNa and (For example, a method of reacting and hydrolyzing)
7). Addition of a compound having 3 to 10 mercapto groups in one molecule and a compound having a functional group (A ¹ or A ² in the above general formula) and a functional group capable of reacting with a mercapto group How to react

Suitable examples of the “functional group capable of reacting with a mercapto group” in Method 7 include acid halides, alkyl halides, isocyanates, and carbon-carbon double bonds.
It is particularly preferable that the “functional group capable of reacting with a mercapto group” is a carbon-carbon double bond, and the addition reaction is synthesized by a radical addition reaction. The carbon-carbon double bond is more preferably a mono- or di-substituted vinyl group in terms of reactivity with the mercapto group.

  Specific examples of the "compound having 3 to 10 mercapto groups in one molecule" [specific examples (18) to (34)] include the following compounds.

  Among the above, the following compounds are particularly preferable from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents.

A functional group (A ¹ or A ² in the formula), and carbon - The compound having a carbon double bond is not particularly limited, include the following.

  In addition, the compound having an organic dye structure or a heterocyclic ring and having a carbon-carbon double bond is not particularly limited, and examples thereof include the following.

  For example, “the compound having 3 to 10 mercapto groups in one molecule” and the above “the acid group, the group having a basic nitrogen atom, the urea group, the urethane group, the group having a coordinating oxygen atom, carbon It has at least one functional group selected from a hydrocarbon group of 4 or more, an alkoxysilyl group, an epoxy group, an isocyanate group, an organic dye structure or a heterocyclic ring, and a hydroxyl group, and a carbon-carbon double bond The radical addition reaction product with “compound having” includes, for example, the above “compound having 3 to 10 mercapto groups in one molecule” and “acid group, group having basic nitrogen atom, urea group, urethane group” , A group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, an organic dye structure or a heterocyclic ring, and a hydroxyl group The compound having at least one functional group and having a carbon-carbon double bond ”is dissolved in a suitable solvent, and a radical generator is added thereto, followed by addition at about 50 ° C. to 100 ° C. It is obtained using a method (thiol-ene reaction method).

  Examples of suitable solvents used in the above method include “compounds having 3 to 10 mercapto groups in one molecule”, “acid groups, groups having basic nitrogen atoms, urea groups, urethane groups, A group having a coordinated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, an organic dye structure or a heterocyclic ring, and at least one functional group selected from a hydroxyl group; The compound having a functional group capable of reacting with a mercapto group (for example, a carbon-carbon double bond) and the solubility of the resulting radical addition reaction product can be arbitrarily selected. For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  As the radical generator, azo compounds such as 2,2′-azobis (isobutyronitrile) (AIBN) and 2,2′-azobis- (2,4′-dimethylvaleronitrile), benzoyl peroxide And persulfates such as potassium persulfate and ammonium persulfate can be used.

-Pigment-
The colored photosensitive composition of the present invention contains at least one pigment as a colorant. By containing the pigment, a visible image having a desired color can be formed.
The average particle size of the pigment used in the present invention is preferably 0.01 μm to 0.05 μm. A more preferable average particle size is 0.01 μm to 0.04 μm, and most preferably 0.01 μm to 0.035 μm. When the average particle size of the pigment is 0.05 μm to 0.01 μm, the influence of light scattering by the pigment particles is reduced, and the contrast is improved. Further, the dispersion stability is improved.

  In the pigment used in the present invention, the proportion of particles exceeding 0.05 μm is preferably less than 20%. The proportion of particles greater than 0.05 μm is more preferably less than 15% and optimally less than 10%. When the proportion of particles exceeding 0.05 μm is less than 20%, the contrast is improved.

  Further, in the pigment used in the present invention, the proportion of particles smaller than 0.01 μm is preferably less than 30%. The proportion of particles smaller than 0.01 μm is more preferably less than 20% and optimally less than 10%. When the proportion of particles smaller than 0.01 μm is less than 30%, the dispersion stability is improved. The particle size was measured from an image obtained by photographing the pigment with a transmission electron microscope at a magnification of 100,000 times. For non-spherical particles, the average value of the long and short diameters was taken as the particle size. Moreover, about average particle size, 100 particle | grains were measured and the average value was made into average particle size.

The proportion of the pigment in the colored photosensitive composition other than the solvent is preferably 30% by mass to 50% by mass.
Moreover, as content in the total mass of the non-volatile component in the coloring photosensitive composition of a pigment, when a pigment is black (BM) with respect to the total mass of the non-volatile component in a coloring photosensitive composition, it is 40 mass%. The above is preferable, 45 mass% or more is more preferable, and 50 mass% or more and 75 mass% or less is still more preferable. In the case of red (R), 25 mass% or more is preferable, 30 mass% or more is more preferable, and 35 mass% or more and 50 mass% or less is still more preferable. In the case of green (G), 35 mass% or more is preferable, 38 mass% or more is more preferable, and 40 mass% or more and 50 mass% or less is still more preferable. Moreover, in the case of blue (B), 25 mass% or more is preferable, 28 mass% or more is more preferable, and 30 mass% or more and 50 mass% or less are still more preferable. The “nonvolatile component” is a component other than the solvent in the colored photosensitive composition, that is, a solid component remaining as a coating film on the substrate after forming a photocurable coating film on the substrate and drying and solidifying it. Say.

  The pigment is not particularly limited, and any of chromatic pigments such as R, G, and B that form color pixels of a color filter and black pigments generally used for forming a black matrix Can also be used.

  Examples of the black pigment include carbon black, titanium black, graphite, iron oxide, titanium oxide, and other pigments / dyes, and are not particularly limited. Among these, carbon black, titanium black, and graphite are preferable, and carbon black is more preferable. These may be used in combination of two or more in addition to being used alone.

  The mass ratio (mass of carbon black: mass of pigment to be used) when two or more are used in combination is preferably in the range of 95: 5 to 60:40, more preferably 95: 5 to 70:30, and 90: 10-80: 20 is still more preferable. When there are a plurality of black pigments, the total mass is a plurality. When the mass ratio is within the above range, there is no aggregation of the dispersion, and a stable coating film without unevenness can be formed.

  Examples of the carbon black include carbon black # 2400, # 2350, # 2300, # 2200, # 1000, # 980, # 970, # 960, # 950, # 900, # 850, MCF88, #M manufactured by Mitsubishi Chemical Corporation. 650, MA600, MA7, MA8, MA11, MA100, MA220, IL30B, IL31B, IL7B, IL11B, IL52B, # 4000, # 4010, # 55, # 52, # 50, # 47, # 45, # 44, # 40 , # 33, # 32, # 30, # 20, # 10, # 5, CF9, # 3050, # 3150, # 3250, # 3750, # 3950, Diamond Black A, Diamond Black N220M, Diamond Black N234, Diamond Black I, Diamond Black LI, Diamond Black II, Diamond Black N33 Diamond Diamond SH, Diamond Black SHA, Diamond Black LH, Diamond Black H, Diamond Black HA, Diamond Black SF, Diamond Black N550M, Diamond Black E, Diamond Black G, Diamond Black R, Diamond Black N760M, Diamond Black LP; Carbon Black Thermax N990, N991, N907, N908, N990, N991, N908 manufactured by Curve Corporation; carbon black Asahi # 80, Asahi # 70, Asahi # 70L, Asahi F-200, Asahi # 66, manufactured by Asahi Carbon Asahi # 66HN, Asahi # 60H, Asahi # 60U, Asahi # 60, Asahi # 55, Asahi # 50H, Asahi # 51, Asahi # 50U, Asahi # 50, Asahi # 35, Asahi # 15, Asahi Thermal; Carbon black of Color Black Fw200, Color lack Fw2, Color Black Fw2V, Color Black Fw1, Color Black Fw18, Color Black S170, Color Black S160, Special Black6, Special Black5, Special Black4, Special Black4A, Printex U, be mentioned PrintexV, Printex 140U, Printex 140V, etc. Can do.

  Carbon black preferably has insulating properties. Insulating carbon black refers to carbon black that exhibits insulating properties when the volume resistance as a powder is measured by the following method. For example, an organic substance is adsorbed, coated or chemically bonded to the surface of carbon black particles ( It has an organic compound on the surface of carbon black particles, such as grafted).

In the above, propylene glycol monomethyl carbon black and a copolymer obtained by copolymerizing benzyl methacrylate and methacrylic acid at a molar ratio of 70:30 (weight average molecular weight 30,000) so as to have a 20:80 mass ratio. A coating solution is prepared by dispersing in ether, and coated on a chromium substrate having a thickness of 1.1 mm, 10 cm × 10 cm to produce a coating film having a dry film thickness of 3 μm. After heat treatment for 1 hour in JIS
When applied with a high resistivity meter Hi-Lester UP (MCP-HT450, manufactured by Mitsubishi Chemical Corporation) in accordance with K 6911 and the volume resistance value was measured under environmental conditions of a temperature of 23 ° C. and a relative humidity of 65%, Carbon black having a volume resistance value of 10 ⁶ Ω · cm or more, more preferably 10 ⁸ Ω · cm or more, and particularly 10 ⁹ Ω · cm or more is preferable.

Examples of inorganic pigments other than carbon black used in the present invention include metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, cobalt, aluminum, cadmium, lead, copper, titanium, Mention may be made of metal oxides such as magnesium, chromium, zinc and antimony, and composite oxides of metals.
As an organic pigment used in the present invention,
C. I. Pigment Yellow 11, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;
C. I. Pigment Orange 36, 38, 43, 71;
C. I. Pigment Red 81, 105, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224, 242, 254, 255, 264, 270;
C. I. Pigment Violet 19, 23, 32, 39;
C. I. Pigment Blue 1, 2, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment Green 7, 36, 37;
C. I. Pigment Brown 25, 28;
C. I. Pigment Black 1, 7;
Etc.

Among the pigments, more preferable pigments include the following. However, it is not limited to these.
C. I. Pigment Yellow 11, 24, 108, 109, 110, 138, 139, 150, 151, 154, 167, 180, 185
C. I. Pigment Orange 36, 71,
C. I. Pigment Red 122, 150, 171, 175, 177, 209, 224, 242, 254, 255, 264
C. I. Pigment Violet 19, 23, 32,
C. I. Pigment Blue 15: 1, 15: 3, 15: 6, 16, 22, 60, 66,
C. I. Pigment Green 7, 36, 37;
C. I. Pigment Black 1, 7
Organic pigments can be used in various combinations in order to increase color purity, in addition to being used alone. Specific examples are shown below.

  Examples of red pigments include anthraquinone pigments, perylene pigments, diketopyrrolopyrrole pigments alone or at least one of them, and disazo yellow pigments, isoindoline yellow pigments, quinophthalone yellow pigments or perylene red pigments. Mixing or the like is used. For example, as an anthraquinone pigment, C.I. I. Pigment Red 177 is C.I. as a perylene pigment. I. Pigment red 155, C.I. I. Pigment Red 224 is C.I. as a diketopyrrolopyrrole pigment. I. Pigment Red 254, and C.I. I. Pigment yellow 83 or C.I. I. Mixing with Pigment Yellow 139 was good.

  The mass ratio of the red pigment to the yellow pigment was preferably 100: 5 to 100: 50. If it is less than 100: 5, the light transmittance of 400 to 500 nm cannot be suppressed, and the color purity may not be improved. On the other hand, if the ratio exceeds 100: 50, the dominant wavelength becomes shorter and the deviation from the NTSC target hue increases. In particular, the range of 100: 10 to 100: 30 is optimal. In the case of a combination of red pigments, it is adjusted according to the chromaticity.

  Examples of the green pigment include a halogenated phthalocyanine pigment alone or a mixture thereof with a disazo yellow pigment, a quinophthalone yellow pigment, an azomethine yellow pigment, or an isoindoline yellow pigment. I. Pigment Green 7, 36, or 37; 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. Good mixing with Pigment Yellow 185. The mass ratio of the green pigment to the yellow pigment is preferably 100: 5 to 100: 150. If it is less than 100: 5, the light transmittance of 400 to 450 nm cannot be suppressed, and the color purity cannot be increased. On the other hand, when the ratio exceeds 100: 150, the dominant wavelength becomes longer and the deviation from the NTSC target hue increases. A more preferable mass ratio is in the range of 100: 30 to 100: 120.

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

  Furthermore, by using a powdered processed pigment in which the above pigment is finely dispersed in acrylic resin, maleic acid resin, vinyl chloride-vinyl acetate copolymer, ethyl cellulose resin, etc., good dispersibility and dispersion stability are achieved. A pigment-containing photocurable resin composition can be obtained. The pigment of the present invention is not limited to the pigment types exemplified above.

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

  The chemical structure includes pyrazole azo, anilino azo, triphenyl methane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, Xanthene-based, phthalocyanine-based, benzopyran-based and indigo-based dyes can be used.

  In the present invention, carbon black and the pigment are dispersed by a specific polymer compound. These specific polymer compounds can be used alone or in combination.

Further, a dispersant may be added as long as the effects of the present invention are not impaired. Examples of the dispersant include a carboxyl group, an OH group, a sulfonic acid group, a phosphoric acid group, an amino group, a carbonyl group, and a polyoxyalkylene moiety. A hydrophilic part such as a phenyl group (including a naphthalene ring), an alicyclic ring, an alkyl group and a compound having a lipophilic part such as a substituted group thereof, a pigment-like structure having a hydrophilic part and / or a lipophilic part. Although the compound which has it is common as a dispersing agent, the compound illustrated below can be used. However, it is not limited to these compounds.
EFKA-1101, 1120, 1125, 4008, 4009, 4046, 4047, 4520, 4010, 4015, 4020, 4050, 4055, 4060, 4080, 4300, 4330, 4400, 4401, 4402, 4403, 4406, 4800, 5010, 5044, 5244, 5054, 5055, 5063, 5064, 5065, 5066, 5070, 5207 (manufactured by EFKA ADDITIVES), Anti-Terra-U, Anti-Terra-U100, Anti-Terra-204, Anti-Terra-205 Anti-Terra-P, Disperbyk-101, 102, 103, 106, 108, 109, 110, 111, 112, 151, P-104, P-104S, P105 220S, 203, 204, 205, 9075, 9076, 9077 (by BYK), Disparlon 7301, 325, 374, 234, 1220, 2100, 2200, KS260, KS273N, 1210, 2150, KS860, KS873N, 7004, 1813 , 1860, 1401, 1200, 550, EDAPLAN 470, 472, 480, 482, K-SPERSE 131, 152, 152MS (manufactured by Enomoto Kasei), Solsperse 3000, 5000, 9000, 12000, 13240, 13940, 17000, 22000, 24000 26000, 28000, etc. (manufactured by AVECIA), Carribbon B, L-400, Eleminol MBN-1, Sunspear PS-2, PS-8, Ionette S 20 (manufactured by Sanyo Chemical Industries, Ltd.) Disperse Aid 6, Disperse Aid 8, Disperse Aid 15, Disperse Aid 9100 (manufactured by San Nopco), etc. can be used. These may be used alone or in combination of two or more.

  Moreover, a dispersion resin can be used if necessary. Dispersion stability and storage stability are improved by using a dispersion resin. As a specific example of the dispersion resin, a resin having a carboxyl group, a sulfonic acid group, a phosphoric acid group, an amino group, or the like is preferable. Examples of the polymer having a carboxylic acid in the side chain include, for example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12777, JP-B-54-25957, JP-A-59- A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partial, as described in Japanese Patent No. 53836 and JP-A-59-71048 There are esterified maleic acid copolymers and the like, and similarly there are acidic cellulose derivatives having a carboxylic acid in the side chain. These include, for example, monomers having a carboxyl group such as (meth) acrylic acid, (anhydrous) maleic acid, crotonic acid, itaconic acid, fumaric acid, styrene, α-methylstyrene, methyl (meth) acrylate, (meth) Ethyl acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, vinyl acetate, acrylonitrile, (meth) acrylamide, glycidyl (meth) acrylate, allyl glycidyl Ether, glycidyl ethyl acrylate, glycidyl crotonic acid ether, (meth) acrylic acid chloride, benzyl (meth) acrylate, phenyl (meth) acrylate, hydroxyethyl (meth) acrylate, N-methylolacrylamide, N, N dimethyl Acrylamide, N- methacryloyl morpholine, N, N- dimethylaminoethyl (meth) acrylate, N, N- dimethylaminoethyl acrylamide, polymers obtained by copolymerizing one or more copolymerizable components such. Among them, preferred is a (meth) acrylic resin containing at least (meth) acrylic acid or (meth) acrylic acid alkyl ester as a constituent monomer, and a (meth) acrylic resin containing (meth) acrylic acid and styrene is also suitable. . These acrylic copolymer components are not limited to the above.

Moreover, these resins can also add an ethylenic double bond to a side chain. By imparting a double bond to the side chain, photocurability is increased, and resolution and adhesion can be further improved.
Examples of the synthesis means for introducing an ethylenic double bond include the methods described in JP-B-50-34443 and JP-B-50-34444. Specific examples include a method of reacting a compound having both a glycidyl group, an epoxycyclohexyl group and a (meth) acryloyl group with a carboxyl group or a hydroxyl group, or acrylic acid chloride. For example, glycidyl (meth) acrylate, allyl glycidyl ether, glycidyl α-ethyl acrylate, crotonyl glycidyl ether, (iso) crotonic acid glycidyl ether, (3,4-epoxycyclohexyl) methyl (meth) acrylate, (meth) By using a compound such as acrylic acid chloride or (meth) allyl chloride and reacting with a resin having a carboxyl group or a hydroxyl group, a resin having a polymer group in the side chain can be obtained.

  In particular, a resin obtained by reacting (3,4-epoxycyclohexyl) methyl (meth) acrylate is preferable. Specific examples of these compounds include a dial NR series (manufactured by Mitsubishi Rayon Co., Ltd.), Photomer 6173 (COOH-containing Polyurethane acrylic oligomer, manufactured by Diamond Shamrock Co. Ltd.,), Biscoat R-264, and KS resist 106 (all Osaka Organic Chemical Industry Co., Ltd.), Cyclomer P Series, Plaxel CF200 Series (all manufactured by Daicel Chemical Industries, Ltd.), Ebecryl 3800 (manufactured by Daicel UCB Co., Ltd.), and the like.

Further, it is also possible to use a polymer obtained by a copolymerization reaction of at least a monomer represented by the following general formula [II] and at least an acid group-containing monomer (the above-mentioned copolymerization component can be mentioned). it can.
Formula [II]
_{H 2 C = CRC (= O} ) OCR 4 R 5 C (= R 3) = CR 2 R 1
In the general formula [II], R represents a hydrogen atom or a methyl group, and R _{1 to} R ₅ each independently represents a group selected from a hydrogen atom, a halogen atom, a cyano group, an alkyl group, and an aryl group.

Specific examples of the halogen atom include Cl, Br, and I. The alkyl group may be linear, branched, or cyclic, and examples thereof include a methyl group, an n-propyl group, an iso-propyl group, and a tert-butyl group, and those having 1 to 7 carbon atoms. preferable.
Examples of the aryl group include a phenyl group, a furyl group, and a naphthyl group. Among the above, as the dispersion resin, a copolymer of (meth) acrylic acid and (meth) acrylic acid ester is preferable because various monomers can be selected and solubility and acid value can be controlled. The preferred range of the weight average molecular weight of these dispersed resins measured by gel permeation chromatography (GPC) is 1,000 to 80,000, more preferably 3,000 to 50,000, most preferably 3, 000-20.000. By setting it to 80,000 or less, good dispersibility and fluidity of the liquid can be obtained, and good developability can be obtained.

These resins can be used not only at the time of dispersion but also at the time of preparing a resist. It is preferable to add the following epoxy resin in addition to the above resin when preparing the resist.
Furthermore, the resins mentioned in the previous section and / or the following epoxy resins can be added and used. The epoxy resin 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, etc. (more from Nagase Kasei), Plaxel GL-61, GL-62, G101, G102 (more from Daicel Chemical) and their similarities The bisphenol F type and bisphenol S type can also be mentioned. Epoxy acrylates such as Ebecryl 3700, 3701, 600 (manufactured by Daicel UC) may also be used. Examples of the cresol novolak type include Epototo YDPN-638, YDPN-701, YDPN-702, YDPN-703, YDPN-704, etc. (manufactured by Tohto Kasei), Denacol EM-125, etc. (manufactured by Nagase Kasei), and biphenyl type Examples of alicyclic 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, etc. (manufactured by Toto Kasei), Epilon 430, 673, 695, 850S, 4032 (Dainippon Ink) It can be mentioned.
1,1,2,2-tetrakis (p-glycidyloxyphenyl) ethane, tris (p-glycidyloxyphenyl) methane, triglycidyltris (hydroxyethyl) isocyanurate, o-phthalic acid diglycidyl ester, terephthalic acid Diglycidyl ester, amine type epoxy resins such as Epototo YH-434 and YH-434L, and glycidyl ester obtained by modifying dimer acid in the skeleton of bisphenol A type epoxy resin can also be used.

  Among these, “molecular weight / number of epoxy rings” is preferably 100 or more, and more preferably 130 to 500. If the “molecular weight / number of epoxy rings” is small, the curability is high, the shrinkage at the time of curing is large, and if it is too large, the curability is insufficient and the reliability is poor or the flatness is poor. Specific preferred compounds include Epototo YD-115, 118T, 127, YDF-170, YDPN-638, YDPN-701, Plaxel GL-61, GL-62, 3,5,3 ', 5'-tetramethyl. -4,4 'diglycidyl biphenyl, celoxide 2021, 2081, epolide GT-302, GT-403, EHPE-3150, etc. are mentioned.

-Polymerizable compound-
The colored photosensitive composition of the present invention contains at least one polymerizable compound. The polymerizable compound is polymerized and cured under the action of an active species from a photopolymerization initiator described later to form an image.
As the polymerizable compound, a compound having at least one ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure is preferable, and a tetrafunctional or higher acrylate compound is more preferable.

  Examples of the compound having at least one ethylenically unsaturated group having a boiling point of 100 ° C. or higher under normal pressure include polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. Monofunctional acrylates and methacrylates; polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, Dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (a (Liloyloxyethyl) Isocyanurate, polyfunctional alcohols such as glycerin and trimethylolethane, after addition of ethylene oxide or propylene oxide and (meth) acrylate, poly (meth) acrylate of pentaerythritol or dipentaerythritol Urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193, JP-A-48-64183, JP-B-49-43191, Examples thereof include polyfunctional acrylates and methacrylates such as polyester acrylates described in Japanese Patent Publication No. 52-30490, and epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid.

Furthermore, the Japan Adhesion Association Vol. 20, no. 7, what is introduced as a photocurable monomer and oligomer on pages 300 to 308 can also be used.
Further, compounds which are described in JP-A-10-62986 as general formulas (1) and (2) together with specific examples thereof and (meth) acrylated after addition of ethylene oxide or propylene oxide to the polyfunctional alcohol are also included. Can be used.
Among these, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and a structure in which these acryloyl groups are via ethylene glycol or propylene glycol residues are preferable. These oligomer types are also used.

A polymeric compound can be used individually by 1 type or in combination of 2 or more types.
The content of the polymerizable compound in the colored photosensitive composition is preferably 20 to 200 parts by mass, more preferably 50 to 120 parts by mass with respect to 100 parts by mass of the colored photosensitive composition (total solid content). Part. When the content is within the above range, curing can be performed satisfactorily.

-Photopolymerization initiator-
The colored photosensitive composition of the present invention contains at least one photopolymerization initiator. By using a photopolymerizable initiator, a higher degree of curing can be obtained, and the curability can be controlled as desired.
Examples of the photopolymerization initiator include active halogen compounds such as halomethyloxadiazole compounds and halomethyl-s-triazine compounds, 3-aryl substituted coumarin compounds, and at least one lophine dimer.

Among the active halogen compounds, examples of the halomethyloxadiazole compound include 2-halomethyl-5-vinyl-1,3,4-oxax represented by the general formula IV described in JP-B-57-6096. And diazole compounds.
Specific examples of the 2-halomethyl-5-vinyl-1,3,4-oxadiazole compound include 2-trichloromethyl-5-styryl-1,3,4-oxadiazole and 2-trichloromethyl-5. -(P-cyanostyryl) -1,3,4-oxadiazole, 2-trichloromethyl-5- (p-methoxystyryl) -1,3,4-oxadiazole and the like.

Examples of the halomethyl-s-triazine compound include a vinyl-halomethyl-s-triazine compound represented by the general formula V described in JP-B-59-1281, and JP-A-53-133428. 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound represented by general formula VI and 4- (p-aminophenyl) -2,6 represented by general formula VII -Di-halomethyl-s-triazine compounds and the like.
Specific examples of the vinyl-halomethyl-s-triazine compound include 2,4-bis (trichloromethyl) -6-p-methoxystyryl-s-triazine, 2,4-bis (trichloromethyl) -6- (1-p-dimethylaminophenyl-1,3-butadienyl) -s-triazine, 2-trichloromethyl-4-amino-6-p-methoxystyryl-s-triazine and the like.
Specific examples of the 2- (naphth-1-yl) -4,6-bis-halomethyl-s-triazine compound include 2- (naphth-1-yl) -4,6-bis-trichloromethyl- s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4-ethoxy-naphth-1-yl) -4,6-bis -Trichloromethyl-s-triazine, 2- (4-butoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-methoxyethyl) -naphth-1 -Yl] -4,6-bis-trichloromethyl-s-triazine, 2- [4- (2-ethoxyethyl) -naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2 -[4- (2-Butoxye ) -Naphth-1-yl] -4,6-bis-trichloromethyl-s-triazine, 2- (2-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-Methoxy-5-methyl-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-methoxy-naphth-2-yl) -4,6-bis -Trichloromethyl-s-triazine, 2- (5-methoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,7-dimethoxy-naphth-1-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (6-ethoxy-naphth-2-yl) -4,6-bis-trichloromethyl-s-triazine, 2- (4,5-dimethoxy- Naphth-1-yl) 4,6-bis - trichloromethyl -s- triazine.

  Specific examples of the 4- (p-aminophenyl) -2,6-di-halomethyl-s-triazine compound include 4- [p-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2. , 6-Di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-methyl-pN, N-di (chloroethyl) aminophenyl ] -2,6-di (trichloromethyl) -s-triazine, 4- (pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (pN- Etoki Carbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN, N-di (phenyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine 4- (pN-chloroethylcarbonylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- [pN- (p-methoxyphenyl) carbonylaminophenyl] 2,6- Di (trichloromethyl) -s-triazine, 4- [m-N, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine,

4- [m-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N- Di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-fluoro-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6 -Di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (ethoxycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [O-chloro-pN, N-di (ethoxycarbonylmethyl) aminophenyl-2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-pN, N-di (eth Cycarbonylmethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-bromo-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloro Methyl) -s-triazine, 4- [o-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [o-fluoro-p -N, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [m-bromo-pN, N-di (chloroethyl) aminophenyl] -2, 6-di (trichloromethyl) -s-triazine, 4- [m-chloro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- [ m Fluoro-pN, N-di (chloroethyl) aminophenyl] -2,6-di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-ethoxycarbonylmethylaminophenyl) -2, 6-di (trichloromethyl) -s-triazine,

4- (m-chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-ethoxycarbonylmethylaminophenyl)- 2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o -Chloro-pN-ethoxycarbonylmethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-ethoxycarbonylmethylaminophenyl) -2,6- Di (trichloromethyl) -s-triazine, 4- (m-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) s-triazine, 4- (m-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (m-fluoro-pN-chloroethylaminophenyl) ) -2,6-di (trichloromethyl) -s-triazine, 4- (o-bromo-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- ( o-chloro-pN-chloroethylaminophenyl) -2,6-di (trichloromethyl) -s-triazine, 4- (o-fluoro-pN-chloroethylaminophenyl) -2,6-di (Trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6- [3-bromo-4- [N, N-bis (ethoxycarbonylmethyl) amino] phenyl] -1,3,5 Triazine, and the like.

Particularly preferred among the 3-aryl substituted coumarin compounds are {(s-triazin-2-yl) amino} -3-arylcoumarin compounds.
The lophine dimer refers to a 2,4,5-triphenylimidazolyl dimer composed of two lophine residues. Specific examples include 2- (o-chlorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-fluorophenyl) -4,5-diphenylimidazolyl dimer, 2- (o-methoxyphenyl). ) -4,5-diphenylimidazolyl dimer, 2- (p-methoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, Examples include 2- (2,4-dimethoxyphenyl) -4,5-diphenylimidazolyl dimer, 2- (p-methylmercaptophenyl) -4,5-diphenylimidazolyl dimer, and the like.

In addition to the above photopolymerization initiator, other known initiators can also be used.
For example, a vicinal polykettle aldonyl compound described in US Pat. No. 2,367,660 and an α-carbonyl compound 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, a triallylimidazole dimer / p-aminophenylketone combination described in US Pat. No. 3,549,367, And benzothiazole compounds / trihalomethyl-s-triazine compounds described in JP-A-51-48516.

  Also, Adeka optomer SP-150, 151, 170, 171, N-1717, N1414, etc. (above Asahi Denka Co., Ltd.), OXE-01, OXE-02, CGI113, IR369, IR907, IR184, IR819 (manufactured by Ciba Specialties Chemicals Co. Ltd.) can also be used as a photopolymerization initiator.

  As content in the coloring photosensitive composition in the case of containing a photoinitiator, 0.1-10.0 mass% is preferable with respect to the total solid of this composition, More preferably, it is 0.5. It is -5.0 mass%. When the content of the photopolymerization initiator is in the above range, the polymerization and curing can be performed satisfactorily and a high film strength can be obtained.

  The following sensitizers can be used in combination with the photopolymerization initiator. Specific examples include benzoin, benzoin methyl ether, 9-fluorenone, 2-chloro-9-fluorenone, 2-methyl-9-fluorenone, 9-anthrone, 2-bromo-9-anthrone, 2-ethyl-9-anthrone. 9,10-anthraquinone, 2-ethyl-9,10-anthraquinone, 2-t-butyl-9,10-anthraquinone, 2,6-dichloro-9,10-anthraquinone, xanthone, 2-methylxanthone, 2- Methoxyxanthone, 2-ethoxyxanthone, thioxanthone, benzyl, dibenzalacetone, p- (dimethylamino) phenylstyryl ketone, p- (dimethylamino) phenyl-p-methylstyrylketone, benzophenone, p- (dimethylamino) benzophenone (Or Michler's ketone), p (Diethylamino) benzophenone, benzoanthrone, 7- {L-4-chloro-6- (diethylamino) -S-triazinyl (2), 1-amino} -3-phenylcoumarin, and the like, and Japanese Patent Publication No. 51-48516 And the described benzothiazole compounds.

  In addition, when the pigment concentration is increased to create high color purity, the thixotropy of the coating solution generally increases, which tends to cause film thickness unevenness after coating. It is important to form a uniform thickness coating by beveling. For this reason, it is preferable to contain an appropriate surfactant in the colored photosensitive resin composition.

Preferred examples of the surfactant include surfactants disclosed in JP-A Nos. 2003-337424 and 11-133600.
Nonionic surfactants, fluorine-based surfactants, silicon-based surfactants, and the like are added as surfactants for improving coating properties. Nonionic surfactants include, for example, polyoxyethylene glycols, polyoxypropylene glycols, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, polyoxyethylene alkyl esters, polyoxypropylene alkyl ethers. Nonionic surfactants such as polyoxypropylene alkyl aryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters and monoglyceride alkyl esters are preferred. Specifically, polyoxyalkylene glycols such as polyoxyethylene glycol and polyoxypropylene glycol; polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether and polyoxyethylene oleyl ether; polyoxy Polyoxyethylene aryl ethers such as ethylene octyl phenyl ether, polyoxyethylene polystyryl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene-propylene polystyryl ether, polyoxyethylene nonylphenyl ether; polyoxyethylene dilaurate , Polyoxyalkylene dialkyl esters such as polyoxyethylene distearate, sorbitan fatty acids Ester, there is nonionic surfactants such as polyoxyalkylene sorbitan fatty acid esters.

  Specific examples of these include, for example, the Adeka Pluronic series, Adecanol series i, Tetronic series (above ADEKA), Emulgen series, Leodol series (above Kao), Eleminol series, Nonipole series, Octopole Series, Dodecapol Series, New Pole Series (above Sanyo Kasei Co., Ltd.), Pionein Series (above Takemoto Yushi Co., Ltd.), Nissan Nonion Series (above Nihon Yushi Co., Ltd.), etc. These commercially available products can be used as appropriate. A preferable HLB value is 8 to 20, more preferably 10 to 17.

  As the fluorosurfactant, a compound having a fluoroalkyl or fluoroalkylene group in at least one of the terminal, main chain and side chain can be suitably used. Specific commercial products include, for example, MegaFuck F142D, F172, F173, F176, F176, F177, F183, 780, 781, R30, R08 (Dainippon Ink Co., Ltd.), Florard FC -135, FC-170C, FC-430, FC-431 (manufactured by Sumitomo 3M), Surflon S-112, S-113, S-131, S-141, S-145 S-382, SC-101, SC-102, SC-103, SC-104, SC-105, SC-105, SC-106 (manufactured by Asahi Glass Co., Ltd.), Ftop EF351, 352, 801 and 802 (manufactured by JEMCO).

  Examples of the silicone-based surfactant include Torre Silicone DC3PA, DC7PA, SH11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH-190, SH-193, SZ-6032, and SF-8428. DC-57, DC-190 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4442 (above GE Toshiba Silicone Co., Ltd.).

  These surfactants are preferably used in an amount of 5 parts by mass or less, more preferably 2 parts by mass or less, with respect to 100 parts by mass of the resist solution. When the amount of the surfactant exceeds 5 parts by mass, surface roughness is likely to occur during coating and drying, and the smoothness tends to deteriorate.

-Alkali-soluble resin-
The pigment dispersion composition of the present invention can contain an alkali-soluble resin having an acidic group. The alkali-soluble resin having an acidic group contained in the pigment dispersion composition of the present invention is preferably a polymer having a polar group such as a carboxylic acid group or a carboxylic acid group in the side chain. Examples thereof include JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, and JP-A-57-36. A methacrylic acid copolymer, an acrylic acid copolymer, an itaconic acid copolymer, a crotonic acid copolymer, a maleic acid copolymer, a partially esterified maleic acid copolymer as described in JP-A-59-71048 Etc.

  Moreover, the cellulose derivative which has a carboxylic acid group in a side chain can also be mentioned, In addition to this, what added the cyclic acid anhydride to the polymer which has a hydroxyl group can also be used preferably. As particularly preferred examples, copolymers of benzyl (meth) acrylate and (meth) acrylic acid described in US Pat. No. 4,139,391, benzyl (meth) acrylate and (meth) acrylic acid are used. And multi-component copolymers with other monomers. These alkali-soluble resins having polar groups may be used singly or in a composition used in combination with a normal film-forming polymer, and the amount added per 100 parts by weight of the organic pigment is 1. -100 mass parts is common, and 5-50 mass parts is preferable.

  When the alkali-soluble resin having an acidic group is a polymer compound, the number of acidic groups in the polymer compound is not particularly limited, but when the number of repeating units contained in one molecule is 100, the acidic group It is preferable that the repeating unit which has is 5-100, and it is more preferable that it is 10-100. Further, the polymerization ratio of the repeating unit derived from the compound having (1) carboxyl group and the repeating unit derived from the compound having (2) carboxylic acid ester group is the mole of repeating unit (1). % Is preferably 5 to 40, the repeating unit (2) is preferably 40 to 90, and the repeating unit other than the repeating unit (1) or (2) is preferably 25 or less. Moreover, 3000-100000 are preferable, as for the molecular weight of alkali-soluble resin which has an acidic group, 3000-500000 are more preferable, 5000-30000 are especially preferable.

-Solvent-
In general, the colored photosensitive composition of the present invention can be suitably prepared using a solvent. Examples of the solvent include esters such as ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, alkyl esters, methyl lactate, Such as ethyl lactate, methyl oxyacetate, ethyl oxyacetate, butyl oxyacetate, methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate; methyl 3-oxypropionate, ethyl 3-oxypropionate, etc. 3-oxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate; methyl 2-oxypropionate, 2-oxyp 2-oxypropionic acid alkyl esters such as ethyl pionate, propyl 2-oxypropionate, such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, Ethyl 2-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,

Dipropylene glycol monomethyl ether acetate, propylene glycol n-butyl ether acetate, diethylene glycol monoethyl ether acetate, tripropylene glycol methyl ether acetate, 1,3-butylene glycol diacetate, dipropylene glycol n-propyl ether acetate, propylene carbonate, diethylene glycol Monobutyl ether acetate, dipropylene glycol n-butyl ether acetate, propylene glycol phenyl ether acetate, triacetin, tripropylene glycol n-butyl ether acetate, triacetin monoacetate, triacetin diacetate and the like; and ethers such as diethylene glycol monoethyl ether, Jeechile Glycol dimethyl ether, dipropylene glycol mono n-butyl ether, diethylene glycol monobutyl ether, tripropylene glycol mono n-butyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, diethylene glycol monobutyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, etc .; ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, etc .; Aromatic hydrocarbons such as toluene, Kishireshi, and the like.

  Among the above, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, ethyl carbitol acetate Butyl carbitol acetate, propylene glycol methyl ether acetate, butylene glycol diacetate and the like are preferable. You may use a solvent in combination of 2 or more types besides using individually by 1 type.

-Other ingredients-
In addition to the above components, the colored photosensitive composition of the present invention includes various additives as necessary, for example, a filler, a polymer compound other than the specific polymer compound, a surfactant other than the above, an adhesion promoter, an antioxidant. An agent, an ultraviolet absorber, an anti-aggregation agent, etc. can be blended.
Specific examples of various additives include fillers such as glass and alumina; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyl Dimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, (meth) acryloylpropyltrimethoxysilane, (meth) acryloylpropyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-glycid Xylpropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryl Adhesion promoters such as xylpropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane; antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol And ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone.

  Further, in order to promote alkali solubility of the uncured part and further improve the developability of the colored photosensitive composition, an organic carboxylic acid, preferably a low molecular weight organic carboxylic acid having a molecular weight of 1000 or less is added. be able to. 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, and camphoric acid; aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelitic acid, and mesitylene acid; phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, Aromatic polycarboxylic acids such as trimesic acid, melophanoic acid, pyromellitic acid; phenylacetic acid Others such as phenoxyacetic acid, methoxyphenoxyacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, methyl cinnamate, benzyl cinnamate, cinnamylidene acetic acid, coumaric acid, umberic acid Carboxylic acid is mentioned.

  In addition to the above, it is preferable to add a thermal polymerization inhibitor to the colored photosensitive composition of the present invention. Examples of the thermal polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, p-methoxyphenol, di-t-butyl-p-cresol, pyrogallol, t-butylcatechol, benzoquinone, 4,4′-thiobis (3-methyl- 6-t-butylphenol), 2,2′-methylenebis (4-methyl-6-t-butylphenol), 2-mercaptobenzimidazole, and the like are useful.

-Preparation of colored photosensitive composition-
The colored photosensitive composition of the present invention comprises a specific polymer compound, a pigment, a polymerizable compound, a photopolymerization initiator, and, if necessary, other components mixed with an organic solvent, and various mixers and dispersers. It can be prepared by mixing and dispersing.
The step of mixing and dispersing (mixing and dispersing step) is preferably composed of kneading and dispersing followed by fine dispersion treatment, but kneading and dispersing can be omitted. In addition, it is preferable that the pigment type used in the kneading and dispersing steps is previously refined in particle size by a salt milling method or the like. A method of salt milling is known from Japanese Patent No. 3130217, Japanese translations of PCT publication No. 2003-504480 and the like. Also, fine pigments formed by the build-up method can be used.

  In the kneading and dispersing step, wetting the surface of the pigment particles of the raw material with the constituents mainly composed of the resin component of the vehicle is promoted, and the solid / gas interface between the pigment particles and the air is changed to the solid / solution interface between the pigment particles and the vehicle solution. Convert. In the fine dispersion step, the pigment particles are dispersed to a fine state close to the primary particles by mixing and stirring together with a dispersion medium for fine particles of glass, zirconia or ceramic. Therefore, in the kneading and dispersing step, it is necessary to convert the interface formed by the pigment particle surface from air to a solution. Therefore, a strong shear force compression force is required, and a kneading machine and a material to be kneaded that are suitable for the kneading material preferably have a high viscosity. On the other hand, in the fine dispersion process, it is necessary to distribute the particles uniformly and stably to a fine state, and a disperser that does not require impact force and shear force on the aggregated pigment particles, and a relatively low dispersion It is desirable that the product has a relatively low viscosity.

  Using the colored photosensitive composition of the present invention, for example, a kneading and dispersing step for producing a color filter is performed first by using a pigment such as an organic pigment or carbon black, a part of a specific polymer compound, and, if necessary, alkali-soluble. A resin, a dispersion resin, a dispersant or a surface treatment agent is kneaded together with a part of the solvent. Examples of the machine used for kneading include two rolls, three rolls, a ball mill, a tron mill, a disper, a kneader, a kneader, a homogenizer, a blender, a single screw or a twin screw extruder, and the like. Subsequently, the remaining solvent and the specific polymer compound (the remainder not used for the kneading) are added, and a vertical or horizontal sand grinder, pin mill, slit mill, ultrasonic disperser, etc. are used, and 0.01-1 mm Disperse with beads made of glass, zirconia, etc. It is possible to omit the kneading step. In that case, a bead dispersion of a pigment such as a pigment, a specific polymer compound and, if necessary, an alkali-soluble resin, a dispersion resin, a dispersant or a surface treatment agent together with a solvent.

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

<Black matrix and color filter>
The black matrix using the colored photosensitive composition of the present invention is formed by, for example, applying a colored photosensitive composition prepared in a liquid form on a desired substrate to form a photosensitive layer, and forming the photocurable It can be formed by exposing the layer in a pattern and developing it. Since the black matrix using the colored photosensitive composition of the present invention is composed of the above-described colored photosensitive composition, the black matrix has a high optical density of black and is composed of a good sharp pattern with a rectangular cross section. It is.

The color filter of the present invention uses the above-described colored photosensitive composition of the present invention.
In addition, a preferable method for producing the color filter of the present invention is formed by slit-coating a coating film of the above-described colored photosensitive composition of the present invention on a substrate directly or through another layer, and then prebaking. Further, pattern exposure and alkali development are sequentially performed.

  The color filter of the present invention is generally configured by providing a plurality of colored pixels having different hues and a black matrix separating the colored pixels. These are formed by applying the above-described colored photosensitive composition of the present invention on a substrate to form a photocurable layer, drying (prebaking), exposing to a desired pattern, and performing development processing. Can be produced.

  For example, a colored photosensitive composition is applied on a substrate directly or via another layer by a coating method such as spin coating, slit coating, cast coating, roll coating (preferably slit coating), and a photocurable layer. After drying (pre-baking), pattern exposure through a predetermined photomask, curing only the exposed area, and developing and removing the unexposed area with a developer are repeated for the desired number of hues. Thus, a color filter provided with a colored image (including pixels and a black matrix) of a desired hue (for example, three colors or four colors such as R, G, B, and black) can be manufactured.

  As ultraviolet rays used for exposure, a high-pressure mercury lamp is preferably used as a light source. In particular, ultraviolet rays such as g-line, h-line, i-line, and j-line are preferable, and ultraviolet rays including i-line and h-line as main components and including j-line are preferable. The exposure machine can be a proximity type exposure machine, a mirror projection system or a stepper system.

  The thickness (after drying) of the photocurable layer formed using the colored photosensitive composition is generally preferably from 0.3 to 5.0 μm, more preferably from 0.5 to 3.5 μm, and particularly preferably 1 0.0 to 2.5 μm.

  Drying (prebaking) of the photocurable layer can be performed by heating for 10 to 300 seconds in a temperature range of 50 to 140 ° C. with a hot plate, an oven, or the like. Especially, it is preferable to heat for 60 to 180 seconds in a 70-130 degreeC temperature range, and it is more preferable to heat for 90 to 120 seconds in a 90-120 degreeC temperature range.

The development treatment is preferably an alkali development treatment, and an uncured portion is eluted in an alkaline aqueous solution by exposure to leave only a photocured cured portion.
Any developer can be used as long as it dissolves the uncured portion and does not dissolve the cured portion forming the filter portion. Specifically, a combination of various organic solvents or an alkaline aqueous solution can be used, and an alkaline developer is particularly preferable.

  Examples of the alkaline aqueous solution include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogencarbonate, sodium oxalate, sodium metasuccinate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, Concentration of an alkaline compound such as tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo- [5,4,0] -7-undecene, in a concentration of 0.001 to 10% by mass, preferably 0.01 to An alkaline aqueous solution dissolved so as to be 1% by mass is preferably used.

  The development temperature is usually 20 ° C. to 30 ° C., and the development time is preferably in the range of 20 to 90 seconds. In the case where a developer composed of such an alkaline aqueous solution is used, it is generally washed (rinsed) with water after development.

  After the development processing, post-baking processing can be performed as necessary. The post-baking is a heat treatment after development for complete curing, and can be usually performed at a temperature of about 200 to 220 ° C. (hard baking). The post-baking treatment can be performed continuously or batchwise using a heating means such as a hot plate, a convection oven (hot air circulation dryer) or a high-frequency heater so that the layer after development is in the above-mentioned condition.

  Examples of the substrate include alkali-free glass, soda glass, Pyrex (registered trademark) glass, quartz glass used for liquid crystal display elements and the like, and those having a transparent conductive film attached thereto, and photoelectric elements used for solid-state imaging elements. Examples include a conversion element substrate, such as a silicon substrate. Furthermore, a plastic substrate is also possible. When producing a color filter, a plurality of colored pixels and a black matrix for isolating each pixel are usually formed on these substrates.

  Raw materials for the plastic substrate include amorphous polyolefin, polyethersulfone, polyglutarimide, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, norbornene polymer, bisaniline fluorene and diamine from the viewpoint of optical properties, heat resistance, mechanical strength, etc. Examples include polyimide as a component, polyester composed of bisphenolfluorene and dibasic acid, and the like. Among these, polyethersulfone, polycarbonate, polyethylene terephthalate, and norbornene polymer are preferable. Said raw materials are particularly preferred in LCD applications.

The properties required for plastic substrates include low thermal expansion (preventing deterioration of display accuracy associated with the curing process during color filter creation), gas barrier properties (ensuring liquid crystal stability), optical transmittance and optical isotropy, etc. Characteristics, surface smoothness, etc. Regarding thermal expansion, the thermal expansion coefficient is preferably 10 ⁻⁴ or less. The plastic substrate preferably has a gas barrier layer and / or a solvent resistant layer on the surface thereof.

  The colored photosensitive composition of the present invention is suitable for forming a black matrix separating colored pixels constituting a color filter and chromatic colored pixels such as RGB.

An overcoat layer (flattening layer) can be provided on the color filter obtained using the colored photosensitive composition of the present invention. Examples of the resin (OC agent) forming the overcoat layer include an acrylic resin composition, an epoxy resin composition, and a polyimide resin composition.
The black matrix of the present invention is suitable for a liquid crystal display element (LCD), and is particularly suitable for applications such as televisions, personal computers, liquid crystal projectors, game machines, mobile terminals such as mobile phones, digital cameras, car navigation systems, and the like. Applicable to.

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.
[Example 1]
≪Preparation of red colored photosensitive composition≫
The following RED composition A was stirred for 1 hour using a homogenizer under the condition of 3000 rpm. The obtained mixed solution was finely dispersed for 4 hours with a bead disperser (trade name: Dispermat, manufactured by GETZMANN) using 0.1 mm zirconia beads to obtain a dispersion.
-RED composition A-dispersion-Pigment Red 254 (average particle size 20 nm in SEM observation) 11 parts-Pigment Red 177 (average particle size 18 nm in SEM observation) 4 parts-Disperbyk-2001 (Big Chemie) 9 parts / solvent B: 76 parts of propylene glycol monomethyl ether acetate

-RED composition B-Coating solution-100 parts of dispersion of RED composition A-Resin solution: benzyl methacrylate / methacrylic acid copolymer (75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol Monomethyl ether acetate solution (solid content: 50% by mass) 8 parts / epoxy resin: (trade name EHPE3150 manufactured by Daicel Chemical) 2 parts / polymerizable compound: dipentaerythritol penta / hexaacrylate 8 parts / polymerization initiator: 4- (O-bromo-pN, N-di (ethoxycarbonylmethyl) amino-phenyl) -2,6-di (trichloromethyl) -s-triazine 1 part polymerization initiator: 2-benzyl-2-dimethylamino -1- (4-morpholinophenyl)
-Butanone 1 part-Polymerization initiator: Diethylthioxanthone 0.5 part-Polymerization inhibitor: p-methoxyphenol 0.001 part-Fluorosurfactant (trade name: Megafac R30, manufactured by Dainippon Ink) 0.01 Part / nonionic surfactant (trade name: manufactured by Tetronic R150 ADEKA) 0.2 part / solvent: 130 parts of propylene glycol monomethyl ether acetate The above RED composition B is mixed and stirred to obtain a coating solution for a colored photosensitive composition. It was.

[Example 2]
≪Preparation of green colored photosensitive composition≫
A RED composition A of Example 1 was changed to the following GREEN composition A to obtain a dispersion.
-GREEN composition A-Dispersion-Pigment Green 36 (average particle size 19 nm in SEM observation) 11 parts-Pigment Yellow 150 (average particle size 22 nm in SEM observation) 7 parts-9 parts of the following compound (C-4)-Solvent B: 73 parts of 3-ethoxypropionic acid methyl ether acetate

-GREEN composition B-Coating solution-GREEN composition A dispersion 100 parts-Resin solution: benzyl methacrylate / methacrylic acid copolymer (75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene glycol Monomethyl ether acetate solution (solid content: 50% by mass) 8 parts ・ Epoxy resin: (trade name EHPE3150, manufactured by Daicel Chemical) 2 parts ・ Polymerizable compound: dipentaerythritol pentahexaacrylate 8 parts ・ Polymerization initiator: 1, 3-bistrihalomethyl-5-benzooxolantolyazine 2 parts, polymerization initiator: 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl)
-Butanone 1 part-Polymerization initiator: Diethylthioxanthone 0.5 part-Polymerization inhibitor: p-methoxyphenol 0.001 part-Fluorosurfactant (trade name: Megafac R08, manufactured by Dainippon Ink)
0.02 part nonionic surfactant (trade name: Emulgen A-60 manufactured by Kao) 0.5 part solvent: 150 parts propylene glycol monomethyl ether acetate The above GREEN composition B was mixed and stirred to obtain a colored photosensitive composition. A coating solution was obtained.

[Example 3]
≪Preparation of blue colored photosensitive composition≫
The RED composition A of Example 1 was changed to the following BLUE composition A to obtain a dispersion.
-BLUE composition A-dispersion-Pigment Blue 15: 6 (average particle size 15 nm in SEM observation) 14 parts-Pigment Violet 23 (average particle size 23 nm in SEM observation) 1 part- Compound (C-5) below 9 Part / alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (= 75/25
[Mass ratio] copolymer, propylene glycol monomethyl ether acetate solution (solid content: 50% by mass) of weight average molecular weight Mw: 5000 1 part / solvent: 75 parts of propylene glycol monomethyl ether acetate

-BLUE composition B-Coating liquid-BLUE composition A dispersion 100 parts-Alkali-soluble resin: benzyl methacrylate / methacrylic acid copolymer (75/25 [mass ratio] copolymer, weight average molecular weight Mw: 5000) propylene Glycol monomethyl ether acetate solution (solid content: 50% by mass) 6 parts / epoxy resin: (trade name EHPE3150 manufactured by Daicel Chemical Industries) 2 parts / UV curable resin: (trade name Cyclomer P ACA-250 manufactured by Daicel Chemical Industries, Ltd., Propylene glycol monomethyl ether acetate solution of an acrylic copolymer having alicyclic, COOH and acryloyl groups in the side chain (solid content: 50% by mass) 4 parts Polymerizable compound: 12 parts of dipentaerythritol pentaacrylate Polymerization initiator: 1- (9-ethyl-6- (2-methylben Yl) -9H-carbazol-3-yl) -1- (O-acetyloxime) ethanone 3 parts Polymerization inhibitor: p-methoxyphenol 0.001 part Fluorosurfactant (trade name: Megafac R08 Dainippon Ink) 0.02 part ・ Nonionic surfactant (trade name: Emulgen A-60, Kao) 1.0 part ・ Solvent: Propylene glycol monomethyl ether acetate 170 parts A coating solution of the composition was obtained.

[Example 4]
≪Preparation of blue colored photosensitive composition≫
In Example 3, except that the compound (C-5) was changed to the following compound (weight average molecular weight 24000, acid value 85 mgKOH / g), BLUE composition C (dispersion), BLUE composition was the same as in Example 3. D (coating solution) was obtained.

[Comparative Example 1]
In Example 1, except that Disperbyk-2001 (manufactured by Big Chemie Japan) was changed to the compound of Synthesis Example 4 of JP-A-2003-26950, the RED composition C ( Dispersion) and RED composition D (coating solution) were obtained.

[Comparative Example 2]
In Example 2, GREEN composition C (dispersion liquid) and GREEN composition D (coating liquid) were the same as in Example 3 except that the compound C-4 was changed to the compound of Synthesis Example 9 of JP-A-2003-26950. Got.

[Comparative Example 3]
In Example 3, BLUE composition E (dispersion liquid) and BLUE composition F (coating liquid) were the same as in Example 3, except that the compound C-5 was changed to the compound of Synthesis Example 1 of JP-A-2001-335717. Got.

<Evaluation>
(1) TI value:
Using a rotary viscometer (E-type viscometer, manufactured by Toki Sangyo Co., Ltd.), the viscosity at 25 ° C. when the rotational speed of the rotor is 5 rpm and the viscosity when the rotational speed of the rotor is 50 rpm are measured. The TI value was calculated according to the formula: The respective viscosities and TI values are shown in Table 1.
TI value =
(Viscosity measured at 25 ° C. with a rotor speed of 5 rpm in an E-type viscometer) /
(Viscosity measured at 25 ° C. with a rotor speed of E-type viscometer at 50 rpm)

(2) Application unevenness:
Using a slit coater equipped with a slit head with a slit gap of 50 μm and an effective coating width of 200 mm, the gap between the slit and the substrate is adjusted to 50 μm so that the coating thickness after drying is 2.0 μm. The coating solution of the colored photosensitive composition of each example and comparative example was applied onto a rectangular glass substrate having a width of 230 mm, a length of 300 mm, and a thickness of 0.7 mm at a coating speed of / sec. Got. After coating, prebaking was performed at 90 ° C. for 60 seconds on a hot plate, and then the coated surface was visually observed to count the number of streaky irregularities and evaluated according to the following criteria. The results are shown in Table 1.
・ With no streak-like unevenness on the coated surface: “○”
・ 1-5 items: “△”
・ Six or more: “×”

(3) Contrast The obtained colored photosensitive composition was apply | coated on the glass substrate, and the sample was produced so that the thickness of the coating film after drying might be set to 1 micrometer. This sample is placed between two polarizing plates, and the amount of transmitted light is measured when the polarization axis is parallel and vertical ("1990 Seventh Color Optical Conference, 512-color display 10.4" size TFT-LCD Color filter, garden plant, Koseki, Fukunaga, Yamanaka "), and the ratio was evaluated as a contrast according to the following criteria. The results are shown in Table 1.
-Contrast of 2000 or more: “○”
-1000 or more and less than 2000: "△"
-Less than 1000: “×”

(4) Viscosity measurement with time After the colored photosensitive composition was stored at 25 ° C. for 1 week, the viscosity was measured at a rotation speed of 50 rpm and evaluated according to the following criteria. The results are shown in Table 1.
・ Viscosity change before storage is within 0.5 mP · s: “○”
· 0.5 mP · s to 1.0 mP · s: “△”
・ Thickness greater than 1.0 mP · s: “×”

Claims (10)

Contains a polymer compound having 2 to 100 pigment-adsorptive functional groups at one end, a pigment, an organic solvent, a photopolymerizable compound, and a photopolymerization initiator, and is E-type at 25 ° C. A colored photosensitive composition characterized in that a viscosity measured by a rotor in a viscometer at a rotation speed of 5 rpm is 50 mP · s or less, and a value obtained by the following formula (I) is 0.95 to 1.15. .
Formula (I)
(Viscosity measured at 25 ° C. with a rotor speed of 5 rpm in an E-type viscometer) /
(Viscosity measured at 25 ° C. with a rotor speed of E-type viscometer at 50 rpm)   The colored photosensitive composition according to claim 1, wherein the polymer compound has an acid value of 20 to 200 mg KOH / g.   3. The colored photosensitive composition according to claim 1, wherein an average particle size of the pigment is 0.01 μm to 0.05 μm.   The colored photosensitive composition according to any one of claims 1 to 3, wherein a value obtained by the formula (I) is 0.98 to 1.10.   5. The colored photosensitive composition according to claim 1, wherein an average particle size of the pigment is 0.01 μm to 0.035 μm. The colored photosensitive composition according to claim 1, wherein the polymer compound is a compound represented by the following general formula (1).

[In General Formula (1), R ¹ represents an (m + n) -valent organic linking group, and R ² represents a single bond or a divalent organic linking group. A ¹ is an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, or a substituent. Represents a monovalent organic group having a group selected from the group consisting of an organic dye structure or a heterocyclic ring and a hydroxyl group, and n A ^{1 s} may be the same or different . m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer skeleton. ]   The colored photosensitive composition according to claim 1, wherein the polymer compound is contained in an amount of 20 to 100 parts by mass with respect to 100 parts by mass of the pigment.   The colored photosensitive composition according to any one of claims 1 to 7, wherein a ratio of the pigment in components other than the solvent in the colored photosensitive composition is 30% by mass to 50% by mass. object.   A color filter comprising the colored photosensitive composition according to claim 1.   A coating film of the colored photosensitive composition according to any one of claims 1 to 8 is formed on a substrate by slit coating directly or through another layer, and then prebaking, pattern exposure, and alkali development are sequentially performed. A method for producing a color filter, which is performed.