JP2014092567A - Color filter coloring composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter coloring composition having superior brightness and heat resistance and a color filter produced using the same, and to provide a color filter coloring composition which offers superior balance in performance, such as a pattern shape and resolution, required for forming good filter segments when used as a photo-sensitive coloring composition and a high-definition color filter which is produced using the same and offers superior brightness.SOLUTION: A color filter coloring composition contains a colorant, a binder resin, and a solvent, where the colorant contains a naphthol-azo pigment [A] represented by a general formula (1) and the binder resin contains a resin [B1] having constituent units described below (b1)-(b3).

Description

  The present invention relates to a color liquid crystal display device, a color composition for a color filter used for producing a color filter used for a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. It is.

  In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. Other typical liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. Increasing demands are being made.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

  Quality items required for the color filter include brightness and contrast ratio. When a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal is disturbed, and when light must be blocked (OFF state), light must leak or be transmitted (ON) In other words, the transmitted light is attenuated in the state), resulting in a blurred screen. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

  If a color filter with low brightness is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend. Furthermore, as described above, since the color liquid crystal device has been used for televisions, personal computer monitors, and the like, the demand for high reliability and high lightness and contrast for color filters has also increased.

  Light filter such as diketopyrrolopyrrole pigment, anthraquinone pigment, perylene pigment or disazo pigment as a colorant for the red filter segment, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate In general, pigments excellent in heat resistance and heat resistance are used alone or in combination.

  Among the pigment types, C.I. which is a diketopyrrolopyrrole pigment from the viewpoint of lightness. I. Pigment Red 254 is an anthraquinone pigment from the viewpoint of contrast ratio. I. Pigment Red 177 is used as the main pigment. Among these, C.I. I. Pigment Red 177 has a spectral transmittance of C.I. I. Since it is lower than CI Pigment Red 254 and the spectral shape is poor, C.I. I. As Pigment Red 177 was added, there was a drawback of causing a decrease in brightness. Therefore, C.I. I. Development of an alternative material for Pigment Red 177 is desired.

  C. I. Examples of alternative materials for Pigment Red 177 include Patent Documents 1 to 3. In order to further improve the brightness of the red filter segment, C.I. I. Pigment red 176, C.I. I. Pigment red 242, and C.I. I. It has been proposed to use an azo pigment such as CI Pigment Orange 38 as a main pigment, but the brightness is not sufficient, and further improvement has been demanded.

  In recent years, there has been a demand for higher density for color filters, and it is necessary to increase the colorant concentration in the color composition to be used. However, exposure sensitivity and development can be improved by increasing the colorant concentration of the color composition. Properties that contribute to image line formation, such as solubility at the time, are relatively lowered. As a result, the solubility of the non-image area during development deteriorates, and the colored composition of the non-image area remains undissolved during development, or remains on the substrate as a peeled piece with the resist not dissolved. May cause color misregistration. As a result, there is a problem that the quality of the color filter is deteriorated and the yield is reduced during production.

JP 2002-131521 A JP 2002-250812 A JP 2003-4930 A JP 2004-333817 A Japanese Unexamined Patent Publication No. 57-90058

  The problem to be solved by the present invention is to provide a color filter coloring composition excellent in lightness and heat resistance, and a color filter using the same. Furthermore, when used as a photosensitive coloring composition, the color composition for a color filter having an excellent balance of performance necessary for forming a good filter segment, such as a pattern shape and resolution, and excellent in lightness using the same. Another object is to provide a high-definition color filter.

  As a result of intensive studies, the present inventors have found that the above-described problems can be solved by using a naphtholazo pigment [A] having a specific structure and a specific resin [B1]. Invented.

［一般式（１）中、Ａは、水素原子、ベンズイミダゾロン基、置換基を有してもよいフェニル基または置換基を有してもよい複素環基を表す。Ｒ¹は、水素原子、トリフルオロメチル基、炭素数１〜４のアルキル基、−ＯＲ⁷または−ＣＯＯＲ⁸を表す。Ｒ²〜Ｒ⁶は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、トリフルオロメチル基、炭素数１〜４のアルキル基、−ＯＲ⁹、−ＣＯＯＲ¹⁰、−ＣＯＮＨＲ¹¹、−ＮＨＣＯＲ¹²または−ＳＯ₂ＮＨＲ¹³を表す。Ｒ⁷〜Ｒ¹³は、それぞれ独立して、水素原子または炭素数１〜４のアルキル基を表す。］

（ｂ１）カルボキシル基を有する構成単位：２〜６０重量％
（ｂ２）一般式（２）または一般式（３）に示す芳香族環基を有する構成単位：２〜８０重量％
（ｂ３）化学式（４）または化学式（５）に示す脂肪族環基を有する構成単位：２〜４０重量％

[一般式（２）及び（３）中、Ｒ₁は、水素原子、またはベンゼン環を有していてもよい炭素数１〜２０のアルキル基である。]

That is, the present invention is a color filter coloring composition comprising a colorant, a binder resin, and a solvent, wherein the colorant comprises a naphtholazo pigment [A] represented by the following general formula (1): The binder resin contains a resin [B1] having the following structural units (b1) to (b3), and relates to a coloring composition for a color filter.

[In General Formula (1), A represents a hydrogen atom, a benzimidazolone group, an optionally substituted phenyl group, or an optionally substituted heterocyclic group. R ¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , -NHCOR ¹² or an -SO ₂ NHR ^13. R ^{7 to} R ¹³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

(B1) Structural unit having a carboxyl group: 2 to 60% by weight
(B2) Structural unit having an aromatic ring group represented by formula (2) or formula (3): 2 to 80% by weight
(B3) Structural unit having an aliphatic cyclic group represented by chemical formula (4) or chemical formula (5): 2 to 40% by weight

[In General Formulas (2) and (3), R ₁ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

  In addition, the present invention relates to the colored composition for a color filter, wherein the resin [B1] is a photosensitive resin.

In the present invention, the resin [B1]
A precursor of the structural unit (b2), a precursor of the structural unit (b3), and an ethylenically unsaturated monomer having an epoxy group are reacted to obtain a copolymer (i1-1). A copolymer (i1-2) is obtained by reacting the obtained copolymer (i1-1) with an unsaturated monobasic acid. Further, the obtained copolymer (i1-2) and a polybasic acid are obtained. A resin obtained by reacting an anhydride or a precursor of the structural unit (b1), a precursor of the structural unit (b2), and a precursor of the structural unit (b3) are reacted to produce a copolymer (i2 The color filter, which is a resin obtained by reacting the copolymer (i2-1) obtained next and an ethylenically unsaturated monomer having an epoxy group. The present invention relates to a coloring composition.

［一般式（６）中、Ａ¹は、それぞれ独立して、水素原子、置換基を有してもよいフェニル基または置換基を有してもよい複素環基を表す。Ｒ⁵¹は、水素原子、トリフルオロメチル基、炭素数１〜４のアルキル基、−ＯＲ⁵⁷または−ＣＯＯＲ⁵⁸を表す。Ｒ⁵⁷、Ｒ⁵⁸は、それぞれ独立して、水素原子または炭素数１〜４のアルキル基を表す。］ In the present invention, the colorant is further selected from the group consisting of a naphthol azo pigment [A ′], an azo pigment [C], a diketopyrrolopyrrole pigment, and an anthraquinone pigment represented by the following general formula (6). It is related with the said coloring composition for color filters characterized by including at least 1 sort (s).

[In General Formula (6), A ¹ each independently represents a hydrogen atom, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ⁵¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁵⁷ or —COOR ⁵⁸ . R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

  Further, the present invention relates to the color composition for color filters, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  The present invention also relates to a color filter comprising a filter segment formed on the base material from the color filter coloring composition.

  The color composition for color filter of the present invention has excellent brightness and heat resistance, good patterning suitability in alkali development, and balance of performance necessary for forming good filter segments such as pattern shape and resolution. An excellent coloring composition for a color filter is obtained.

Hereinafter, the present invention will be described in detail.
In the present specification, when expressed as “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, or “(meth) acrylamide” Unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. ".
Further, “CI” mentioned in the present specification means a color index (CI).

［一般式（１）中、Ａは、水素原子、ベンズイミダゾロン基、置換基を有してもよいフェニル基または置換基を有してもよい複素環基を表す。Ｒ¹は、水素原子、トリフルオロメチル基、炭素数１〜４のアルキル基、−ＯＲ⁷または−ＣＯＯＲ⁸を表す。Ｒ²〜Ｒ⁶は、それぞれ独立して、水素原子、ハロゲン原子、シアノ基、ニトロ基、トリフルオロメチル基、炭素数１〜４のアルキル基、−ＯＲ⁹、−ＣＯＯＲ¹⁰、−ＣＯＮＨＲ¹¹、−ＮＨＣＯＲ¹²または−ＳＯ₂ＮＨＲ¹³を表す。Ｒ⁷〜Ｒ¹³は、それぞれ独立して、水素原子または炭素数１〜４のアルキル基を表す。］ <Colorant>
(Naphthol azo pigment [A])
The colorant of the present invention contains a naphthol azo pigment [A] represented by the general formula (1).

[In General Formula (1), A represents a hydrogen atom, a benzimidazolone group, an optionally substituted phenyl group, or an optionally substituted heterocyclic group. R ¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , -NHCOR ¹² or an -SO ₂ NHR ^13. R ^{7 to} R ¹³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

Among the naphthol azo pigments [A] represented by the general formula (1), preferably, the azo pigment [A1] in which at least one of R ^{2 to} R ⁶ is a trifluoromethyl group, or R ^{2 to} R ⁶ Among them, an azo pigment [A2] in which at least one is —NHCOR ¹² is preferable because the pigment particles are easily miniaturized and the contrast ratio is excellent.

  As a naphthol azo pigment [A] represented by the general formula (1), when represented by a color index (CI) number, C.I. I. Pigment Red 31, 32, 146, 147, 150, 184, 187, 188, 210, 238.2245.247, 266, 268, 269, C.I. I. Violet 25, 50, etc. are mentioned. Among these, from the viewpoint of hue and lightness, C.I. I. Pigment Red 150, 170, 187, 266, 268, and 269 are preferable.

  In the general formula (1), in A, the “substituent” of the phenyl group which may have a substituent is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, cyano Of an acidic group selected from a group, a trifluoromethyl group, a nitro group, a hydroxyl group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, an N-substituted sulfamoyl group, a carboxyl group, a sulfo group, a carboxyl group or a sulfo group Trivalent metal salts (for example, sodium salt, potassium salt, aluminum salt, etc.) and the like can be mentioned. Therefore, specific examples of the phenyl group which may have a substituent include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, an o-triphenyl group. Fluoromethylphenyl group, p-chlorophenyl group, p-bromophenyl group, 2,4-dichlorophenyl group, 3-carbamoylphenyl group, 2-chloro-4-carbamoylphenyl group, 2-methyl-4-carbamoylphenyl group, 2 -Methoxy-4-carbamoylphenyl group, 2-methoxy-4-methyl-3-sulfamoylphenyl group, 4-sulfophenyl group, 4-carboxyphenyl group, 2-methyl-4-sulfophenyl group, etc. However, it is not limited to these.

  In A, the “substituent” of the heterocyclic group which may have a substituent is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, or trifluoro group. Monovalent to trivalent metal of an acidic group selected from methyl group, nitro group, hydroxyl group, carbamoyl group, N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, carboxyl group, sulfo group, carboxyl group or sulfo group Salt (for example, sodium salt, potassium salt, aluminum salt etc.) etc. are mentioned. “Heterocycle” means an atom in which one or more heteroatoms other than carbon atoms are contained in the atoms constituting the ring system, and may be a saturated ring or an unsaturated ring. Further, it may be a single ring or a condensed ring. Therefore, the heterocyclic ring includes pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, isoxazole ring, isothiazole ring. , Triazole ring, thiadiazole ring, oxadiazole ring, quinoline ring, benzofuran ring, indole ring, morpholine ring, pyrrolidine ring, piperidine ring, tetrahydrofuran ring and the like. Therefore, the heterocyclic group means a monovalent radical derived by removing a hydrogen atom from these heterocycles. Therefore, specific examples of the heterocyclic group which may have a substituent include 2- Pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-imidazolyl group, 2- Oxazolyl group, 2-thiazolyl group, piperidino group, 4-piperidyl group, morpholino group, 2-morpholinyl group, N-indolyl group, 2-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-quinolino group, N-carbazolyl group etc. are mentioned.

Examples of the halogen atom in R ^{2 to} R ⁶ and R ¹⁴ include fluorine, chlorine, bromine and iodine.

In addition, the alkyl group having 1 to 4 carbon atoms in R ^{1 to} R ¹⁴ may be linear or branched, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. , Sec-butyl group, and tert-butyl group.

As a pigment, it is preferable that A is a phenyl group which may have a substituent from a viewpoint of brightness. Furthermore, from the viewpoints of lightness and dispersibility, R ¹ is preferably an alkyl group having 1 to 4 carbon atoms or —OR ⁷ , and more preferably R ¹ is a methyl group or a methoxy group.

  The colorant of the present invention may have a chemical structure of the general formula (1) or a tautomer thereof, and may be a pigment having any crystal form, and any crystal called a so-called polymorph. It may be a mixed crystal of pigments having a form. The crystal form of these pigments can be confirmed by powder X-ray diffraction measurement or X-ray crystal structure analysis.

  The naphtholazo pigment [A] of the present invention is a water-insoluble pigment having excellent fastness to solvents and light, and by using this pigment, both brightness and contrast ratio are excellent. A colored composition for a color filter can be obtained.

  In the colorant of the present invention, the naphtholazo pigment [A] can be used alone or in admixture of two or more.

(Naphthol azo pigment [A1])
Among the naphthol azo pigments [A] represented by the general formula (1), the naphthol azo pigment [A1], in which at least one of R ^{2 to} R ⁶ is a trifluoromethyl group, is easily refined. This is preferable.

Among these, R ⁴ is preferably a -trifluoromethyl group, and R ² is preferably a -Cl group. By satisfying these requirements, the pigment can be made finer, so that high contrast can be achieved.

  Specific examples of the naphthol azo pigment [A1] include the following naphthol azo pigments, but the present invention is not limited thereto.

(Naphthol azo pigment [A2])
Among the naphthol azo pigments [A] represented by the general formula (1), the naphthol azo pigment [A2] in which at least one of R ^{2 to} R ⁶ is —NHCOR ¹² is excellent in lightness. Is preferred.
Among these, R ⁴ is preferably —NHCOR ¹² , and R ¹ is more preferably a methoxy group.

Specific examples of the naphthol azo pigment [A2] include the following naphthol azo pigments, but the present invention is not limited thereto.

(Method for producing naphtholazo pigment [A])
The naphthol azo pigment [A] of the present invention can be produced by coupling reaction of a diazonium salt and β-naphthols, as is well known in the pigment field. Also, as described below, two or more naphthol azo pigments can be synthesized simultaneously by using aromatic amines (diazo component), β-naphthols (coupler component), or both in the reaction. A plurality of naphthol azo pigment species may be included. In this case, a pigment composition that is excellent in miniaturization and gives excellent lightness may be obtained, which is more preferable.

  By simultaneously synthesizing two or more naphthol azo pigments, crystal growth can be inhibited, fine pigment particles can be obtained, and lightness can be improved for reasons such as improved transparency.

  The naphtholazo pigment [A] is produced by firstly adding an amide (diazo component) represented by the following general formula (7) in an acidic aqueous solution to which hydrochloric acid, sulfuric acid, acetic acid or the like is added, nitrous acid, nitrite or A diazonium salt represented by the following general formula (8) obtained by diazotization with a nitrite is produced.

[一般式（７）および（８）中、ＡおよびＲ¹は、一般式（１）におけるものと同義である。Ｘ−は、無機または有機アニオンを表す。］

[In General Formulas (7) and (8), A and R ¹ have the same meanings as in General Formula (1). X- represents an inorganic or organic anion. ]

Examples of the inorganic or organic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, CH ₃ COO—, C ₆ H ₅ COO—, and the like. Preferred are chloride ion, bromide ion, and CH ₃ COO—.

  Next, the diazonium salt represented by the general formula (8) and the β-naphthols (coupling component) represented by the following general formula (9) are usually reacted at 5 ° C. to 70 ° C. in an aqueous solvent. The naphthol azo pigment [A] of the general formula (1) is produced by post-treatment by a conventional method. Further, the coupling reaction may be performed in the presence of a surfactant, a resin, a pigment derivative, or an inert solvent. Moreover, the manufacturing method of the naphthol azo pigment [A] of this invention is not limited to these methods.

［一般式（９）中、Ｒ²〜Ｒ⁶は、一般式（１）におけるものと同義である。］

[R < ² > -R < ⁶ > is synonymous with the thing in General formula (1) in General formula (9). ]

Moreover, when manufacturing simultaneously 2 or more types of naphthol azo pigment seed | species, the method described below is mentioned, for example.
First, a mixture of at least one aromatic amine (diazo component) represented by the following general formula (7) is added to a nitrous acid, a nitrite or a nitrous acid in an acidic aqueous solution to which hydrochloric acid, sulfuric acid or acetic acid is added. A mixture of diazonium salts represented by the following general formula (8) obtained by diazotization with an ester is produced.

[一般式（７）、および（８）中、ＡおよびＲ¹は、一般式（１）におけるものと同義である。Ｘ−は、無機または有機アニオンを表す。］

[In general formulas (7) and (8), A and R ¹ have the same meanings as in general formula (1). X- represents an inorganic or organic anion. ]

Examples of the inorganic or organic anion include fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ion, CH ₃ COO ⁻ , C ₆ H ₅ COO ^{−, and the} like. Preferred are chloride ion, bromide ion, and CH ₃ COO 2 ^— .

Next, the mixture of the diazonium salt represented by the general formula (8) is converted into β-naphthols (coupler component) represented by the following general formula (9) and β-naphthols represented by the following chemical formula (10). The mixture of (coupler component) is usually reacted in an aqueous solvent at 5 ° C. to 70 ° C. and subjected to post-treatment by a conventional method to obtain a naphthol azo pigment [A] represented by the general formula (1) and the general formula A pigment composition containing the naphtholazo pigment [A ′] represented by (6) can be produced.
At this time, A ¹ in the general formula (6) is the same as A, and R ⁵¹ is the same pigment as R ¹ .
Further, the coupling reaction may be performed in the presence of a surfactant, a resin, a pigment derivative, or an inert solvent. Moreover, the manufacturing method of the pigment composition of this invention is not limited to these methods.

［一般式（９）中、Ｒ²〜Ｒ⁶は、一般式（１）におけるものと同義である。］

[R < ² > -R < ⁶ > is synonymous with the thing in General formula (1) in General formula (9). ]

  The mixing ratio of the aromatic amines of the general formula (7) used in the reaction and the mixing ratio of the β-naphthols of the general formula (9) and the chemical formula (10) are set between 60:40 and 100: 0, respectively. be able to. By adjusting these mixing ratios, a pigment composition having a target mass ratio can be obtained.

Thus, a coupler component composed of a mixture of a naphthol compound represented by the general formula (9) and a naphthol compound represented by the chemical formula (10), a diazo compound of an aromatic amine represented by the general formula (7), Can be reacted to produce a colorant containing the azo pigments represented by the general formula (1) and the general formula (6).
Such a colorant is excellent in lightness and contrast ratio, and is preferable.
At this time, the mass ratio of the mixture of the naphthol compound represented by the general formula (9) and the naphthol compound represented by the chemical formula (10) is preferably 60.0: 40.0 to 100.0: 0. In the case of 100.0: 0, the naphthol azo pigment [A] represented by the general formula (1) is the only product.

(Other colorants)
The color composition for color filter of the present invention includes other pigments or dyes other than the naphtholazo pigment [A] of the general formula (1) within the range of not impairing the effects of the present invention in order to adjust chromaticity. These colorants may be used in combination. These pigments / dyes can be used alone or in admixture of two or more at any ratio as required.

Colorants that can be used in combination include pigments such as diketopyrrolopyrrole pigments, azo pigments other than the naphtholazo pigment [A] of the general formula (1) such as azo, disazo, or polyazo, aminoanthraquinone, diamino Anthraquinone pigments such as dianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, quinacridone pigment, perinone pigment, perylene pigment, thioindigo pigment, isoindolinone pigment, isoindolinone pigment Examples thereof include pigments, quinophthalone pigments, selenium pigments, and metal complex pigments.
Examples of the dye include xanthene dyes, azo (pyridone, barbituric acid, metal complex, etc.) dyes, disazo dyes, anthraquinone dyes, and methine dyes. In addition, lake pigments obtained by lake- ing these dyes, inorganic salts of acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acidic dyes and nitrogen-containing compounds, sulfonic acid amides of acidic dyes It may be in the form of a compound or the like.

  Among these, azo pigments other than the naphthol azo pigment [A] of the general formula (1), diketopyrrolopyrrole pigments, and anthraquinone pigments are preferable from the viewpoint of brightness and coloring power.

  Examples of the azo pigments other than the naphthol azo pigment [A] of the general formula (1) include the naphthol azo pigment [A ′] represented by the general formula (6), and other azo pigments [C]. The naphtholazo pigment [A ′] represented by the general formula (6) is preferable because of its high brightness and contrast ratio.

［一般式（６）中、Ａ¹は、それぞれ独立して、水素原子、置換基を有してもよいフェニル基または置換基を有してもよい複素環基を表す。Ｒ⁵¹は、水素原子、トリフルオロメチル基、炭素数１〜４のアルキル基、−ＯＲ⁵⁷または−ＣＯＯＲ⁵⁸を表す。Ｒ⁵⁷、Ｒ⁵⁸は、それぞれ独立して、水素原子または炭素数１〜４のアルキル基を表す。］ (Naphthol azo pigment [A '])
The naphthol azo pigment [A ′] is a naphthol azo pigment represented by the general formula (6).

[In General Formula (6), A ¹ each independently represents a hydrogen atom, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ⁵¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁵⁷ or —COOR ⁵⁸ . R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

In A ¹ , the “substituent” of the phenyl group which may have a substituent and the “substituent” of the heterocyclic group which may have a substituent are the “substituent” in A of the general formula (1). Is the same as the substituent.

In addition, the alkyl group having 1 to 4 carbon atoms in R ⁵¹ , R ⁵⁷ and R ⁵⁸ may be linear or branched, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group. , Isobutyl group, sec-butyl group, and tert-butyl group.

As a pigment, from the viewpoint of brightness, A ¹ is preferably a phenyl group which may have a substituent. Furthermore, from the viewpoints of lightness and dispersibility, R ⁵¹ is preferably an alkyl group having 1 to 4 carbon atoms or —OR ⁵⁷ , and more preferably R ⁵¹ is a methyl group or a methoxy group.

  The colorant of the present invention may have a chemical structure of the general formula (6) or a tautomer thereof, or may be a pigment having any crystal form, and any crystal called a so-called polymorph. It may be a mixed crystal of pigments having a form. The crystal form of these pigments can be confirmed by powder X-ray diffraction measurement or X-ray crystal structure analysis.

  When the colorant contains a naphthol azo pigment [A ′] represented by the general formula (6), it is represented by the naphthol azo pigment [A] represented by the general formula (1) and the general formula (6). The weight ratio of the naphtholazo pigment [A ′] is preferably in the range of 60.0: 40.0 to 95.0: 5.0. More preferably, it is the range of 70.0: 30.0-90.0: 10.0. When the content of the naphtholazo pigment [A] is 60 or more or 95 or less, it is preferable because more excellent brightness can be obtained.

  Examples of the naphthol azo pigment represented by the general formula (6) include C.I. I. And CI Pigment Red 176.

(Other azo pigments [C])
The other azo pigment [C] is an azo such as azo, disazo or polyazo other than the naphthol azo pigment [A] represented by the general formula (1) and the azo pigment [A ′] represented by the general formula (6). And pigments.
Examples of such pigments include C.I. I. Pigment Red 2, 5, 7, 8, 9, 10, 11, 12, 14, 15, 16, 17, 18, 21, 22, 23, 95, 112, 114, 119, 136, 144, 164, 166, 170, 171, 175, 185, 208, 213, 214, 220, 221, 242, 253, 256, 258, C.I. I. Pigment Orange 1, 4, 15, 16, 22, 24, 38, 74, C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 7, 9, 10, 12, 13, 14, 15, 16, 17, 49, 55, 60, 63, 65, 73, 74, 75, 77, 81, 83, 87, 97, 98, 105, 106, 111, 113, 114, 116, 124, 126, 127, 130, 152, 155, 165, 167, 170, 172, 174, 176, 205, 214, 219 or the like. Among these, from the viewpoint of hue, brightness, and contrast ratio, C.I. I. Pigment red 185, 242 and C.I. I. Pigment Orange 38 is desirable.

  Specific examples of red pigments that can be used in combination are C.I. I. Pigment Red 7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, Use red pigments such as 166, 168, 176, 177, 178, 179, 184, 185, 187, 200, 202, 210, 221, 242, 246, 254, 255, 264, 270, 272, and 279 together Can do. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment red 177, C.I. I. Pigment red 254, C.I. I. Pigment Red 242 is preferably used, and these may be used together.

Examples of orange pigments and yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213, and 214, and the like.
Examples of the orange pigment include C.I. I. Pigment orange 38, 43, 71, or 73.
Among these, C.I. can be expanded in that the chromaticity region can be expanded. I. Pigment yellow 138, 139, 150, C.I. I. Pigment Orange 38 is preferable.

The dyes that can be used in combination are red and purple, and preferably have any form of oil-soluble dyes, acid dyes, direct dyes, and basic dyes.
Among these, use of a xanthene oil-soluble dye, a xanthene basic dye, and a xanthene acid dye is preferable because of excellent hue. In addition, lake pigments obtained by lake- ing these dyes, inorganic salts of acidic dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acidic dyes and nitrogen-containing compounds, sulfonic acid amides of acidic dyes It may be in the form of a compound or the like.

Xanthene oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, and C.I. I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet 10 and the like. Among them, CI solvent red 35, CI solvent red 36, CI solvent red 49, CI solvent red 109, CI solvent red, which are rhodamine-based oil-soluble dyes having high color development Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferable.
Examples of xanthene basic dyes include C.I. I. Basic Red 1 (Rhodamine 6 GCP), 8 (Rhodamine G), C.I. I. Basic violet 10 (Rhodamine B) and the like. Among these, C.I. I. Basic Red 1, C.I. I. Basic violet 10 is preferably used.
Examples of xanthene acid dyes include C.I. I. Acid Red 51 (erythrosin (edible red No. 3)), C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 87 (Eosin G (edible red No. 103)), C.I. I. Acid Red 92 (Acid Phloxin PB (edible red No. 104)), C.I. I. Acid Red 289, C.I. I. Acid Red 388, Rose Bengal B (Edible Red No. 5), Acid Rhodamine G, C.I. I. It is preferable to use Acid Violet 9.
Among these, in terms of heat resistance and light resistance, C.I. I. Acid Red 87, C.I. I. Acid Red 92, C.I. I. Acid Red 388 or rhodamine acid dye C.I. I. Acid Red 52 (Acid Rhodamine), C.I. I. Acid Red 289, Acid Rhodamine G, C.I. I. It is more preferable to use Acid Violet 9.
Among these dyes, C.I., which is a rhodamine acid dye, is particularly excellent in terms of color developability, heat resistance and light resistance. I. Most preferably, Acid Red 52 is used.

  When used in combination with the above-mentioned red pigment, yellow pigment, orange pigment, and dye, the content of the naphtholazo pigment [A] described by the general formula (1) is 10 to 90 wt% in a total of 100 wt% of the colorant. %, Preferably 20 to 80% by weight. By being in this content range, the chromaticity region can be expanded.

(Miniaturization of colorant)
The pigment used in the present invention can be used after being refined. The naphtholazo pigment [A] is also preferably used after being refined, but the refinement method is not particularly limited. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As illustrated, a salt milling process by a kneader method, which is a kind of wet grinding, can be performed. Any commercially available product may be used as the naphthol azo pigment [A] to be refined, and a naphthol azo pigment [A] produced by a coupling reaction between a diazonium salt corresponding to the naphthol azo pigment [A] and β-naphthols is used. Also good.

The primary particle size of the refined pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm.
The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is approximated to a cube having the obtained particle diameter to obtain an average volume, and the length of one side of the cube having this average volume is determined as the average primary The particle size.

  Salt milling is a process of heating a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent using a kneader such as a kneader, trimix, two-roll mill, three-roll mill, ball mill, attritor or sand mill. Then, after mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight with respect to 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

  When the salt is milled, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by weight with respect to 100 parts by weight of the pigment.

[一般式（２）及び（３）中、Ｒ₁は、水素原子、またはベンゼン環を有していてもよい炭素数１〜２０のアルキル基である。]

以下に、構成単位（ｂ１）、構成単位（ｂ２）、及び構成単位（ｂ３）について、順に説明する。
本明細書においては、各構成単位の含有重量％は各構成単位を樹脂［Ｂ１］にもたらす前駆体の重量％である。 <Binder resin>
(Resin [B1])
The binder resin contained in the colored composition of the present invention is characterized by containing a resin [B1] having the following structural units (b1) to (b3).

(B1); a structural unit having a carboxyl group: 2 to 60% by weight
(B2): Structural unit having an aromatic ring group represented by formula (2) or formula (3): 2 to 80% by weight
(B3); a structural unit having an aliphatic cyclic group represented by chemical formula (4) or chemical formula (5): 2 to 40% by weight

[In General Formulas (2) and (3), R ₁ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

Below, a structural unit (b1), a structural unit (b2), and a structural unit (b3) are demonstrated in order.
In this specification, the content weight% of each structural unit is the weight% of the precursor that brings each structural unit to the resin [B1].

[Structural unit (b1)]
The structural unit (b1) has a carboxyl group and functions as an alkali-soluble site during development. From the viewpoint of developability, the structural unit (b1) is 2 to 60% by weight based on the weight of all the structural units of the resin [B1]. If it is less than 2% by weight, the removability of the unexposed portion by the alkaline developer becomes insufficient, and if it exceeds 60% by weight, the dissolution rate in the alkali developer is increased and the exposed portion is dissolved.

  Examples of the precursor of the structural unit (b1) having a carboxyl group include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, or α-chloroacrylic acid, and unsaturated dicarboxylic acids such as maleic acid or fumaric acid. And compounds containing a carboxyl group such as an acid and having an ethylenically unsaturated double bond. Moreover, what half-esterified the anhydride of unsaturated dicarboxylic acid, such as maleic anhydride, with the (meth) acrylic compound which has hydroxyl groups, such as hydroxyalkyl (meth) acrylate, can also be used. Among these, (meth) acrylic acid is more preferable, and methacrylic acid is most preferable from the viewpoint of polymerizability (ease of control of molecular weight and the like). These can be used alone or in combination of two or more.

[一般式（２）及び（３）中、Ｒ₁は、水素原子、またはベンゼン環を有していてもよい炭素数１〜２０のアルキル基である。] [Structural unit (b2)]
The structural unit (b2) has a cyclic structure with an aromatic ring group represented by the general formula (2) and the general formula (3), and functions as an affinity site for a pigment or a pigment composition comprising a pigment and a dispersant. To do. Based on the weight of all the structural units of the resin [B1], the structural unit (b2) is 2 to 80% by weight from the viewpoints of developability, dispersion stability, and chemical resistance. If it is less than 2% by weight, the developability, dispersion stability and chemical resistance are lowered, and if it exceeds 80% by weight, the dissolution rate in an alkaline developer is slow, the development time is long, and the productivity is deteriorated. .

[In General Formulas (2) and (3), R ₁ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

  As the precursor of the structural unit (b2), styrene, α-methylstyrene, divinylbenzene, indene, acetylnaphthene, benzyl acrylate, benzyl methacrylate, bisphenol A diglycidyl ether di (meth) acrylate, (meth) of methylolated melamine Examples thereof include monomers / oligomers such as acrylic acid esters, and ethylenically unsaturated monomers represented by the general formula (7).

[一般式（１３）中、Ｒ₆は、水素原子、またはメチル基であり、Ｒ₇は、炭素数２若しくは３のアルキレン基であり、Ｒ₈は、ベンゼン環を有していてもよい炭素数１〜２０のアルキル基であり、ｎは、１〜１５の整数である。]

[In General Formula (13), R ₆ is a hydrogen atom or a methyl group, R ₇ is an alkylene group having 2 or 3 carbon atoms, and R ₈ is a carbon optionally having a benzene ring. It is a C1-C20 alkyl group, and n is an integer of 1-15. ]

Examples of the ethylenically unsaturated monomer represented by the general formula (13) include:
New Frontier CEA [EO-modified cresol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : methyl group, n = 1 or 2], NP-2 [n-nonylphenoxy polyethylene] Glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n = 2], N-177E [n-nonylphenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene Group, R ₈ : n-nonyl group, n = 16 to 17], or PHE [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1],
Daicel, IRR169 [ethoxylated phenyl acrylate (EO 1 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], or Ebecryl 110 [ethoxylated phenyl acrylate (EO 2 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 2],
Aronix M-101A manufactured by Toagosei Co., Ltd. [phenol EO modified (n≈2) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈2], M-102 [phenol EO modified ( n≈4) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈4], M-110 [paracumylphenol EO modified (n≈1) acrylate, R ₆ : hydrogen atom , R _7: an ethylene group, R _8: Parakumiru, n ≒ 1], M-111 [n- nonylphenol EO-modified (n ≒ 1) acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: n- Nonyl group, n≈1], M-113 [n-nonylphenol EO-modified (n≈4) acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈4], or M-117 [n-nonyl Phenol PO modified (n≈2.5) acrylate, R ₆ : hydrogen atom, R ₇ : propylene group, R ₈ : n-nonyl group, n≈2.5],
Kyoeisha light acrylate PO-A [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], P-200A [phenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R _7: an ethylene group, R _8: a hydrogen atom, n ≒ 2], NP-4EA [nonylphenol EO adduct acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: n-nonyl group, n ≒ 4 ], Or NP-8EA [[nonylphenol EO adduct acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group, n≈8], or light ester PO [phenoxyethyl methacrylate, R ₆ : Methyl group, R ₇ : propylene group, R ₈ : hydrogen atom, n = 1],
Manufactured by NOF Corporation Blemmer ANE-300 [nonylphenoxy polyethylene glycol acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: - nonyl group, n ≒ 5], ANP-300 [nonylphenoxy polypropylene glycol acrylate, R _6: a hydrogen atom, R _7: a propylene group, R _8: n-nonyl group, n ≒ 5], 43ANEP-500 [nonylphenoxy - polyethylene glycol - polypropylene glycol - acrylate, R _6: a hydrogen atom, R _7: an ethylene group And propylene group, R ₈ : -nonyl group, n≈5 + 5], 70ANEP-550 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group and propylene group, R ₈ : n -Nonyl group, n≈9 + 3], 75AN EP-600 [nonylphenoxy-polyethylene glycol-polypropylene glycol-acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group and propylene group, R ₈ : n-nonyl group, n≈5 + 2], AAE-50 [phenoxypolyethylene glycol Acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], AAE-300 [phenoxypolyethylene glycol acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen Atom, n≈5.5], PAE-50 [phenoxypolyethylene glycol methacrylate, R ₆ : methyl group, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], PAE-100 [phenoxypolyethylene glycol methacrylate, R _6: a methyl group, R _7: an ethylene group, R _8: a hydrogen atom, n = ], Or 43PAPE-600B [phenoxy - polyethylene glycol - polypropylene glycol - methacrylate, R _6: a methyl group, R _7: an ethylene group and a propylene group, R _8: a hydrogen atom, n ≒ 6 + 6],
Shin-Nakamura Chemical Co., Ltd. NK ESTER AMP-10G [phenoxy ethyleneglycol acrylate (EO1mol), R _6: a hydrogen atom, R _7: an ethylene group, R _8: a hydrogen atom, n = 1], AMP-20G [phenoxy ethyleneglycol acrylate (EO 2 mol), R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n≈2], AMP-60G [phenoxyethylene glycol acrylate (EO ₆ mol), R ₆ : hydrogen atom, R ₇ : ethylene group , R ₈ : hydrogen atom, n≈6], PHE-1G [phenoxyethylene glycol methacrylate (EO 1 mol), R ₆ : methyl group, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1],
Biscoat # 192 manufactured by Osaka Organic Chemical Co., Ltd. [phenoxyethyl acrylate, R ₆ : hydrogen atom, R ₇ : ethylene group, R ₈ : hydrogen atom, n = 1], or
Nippon Kayaku SR-339A [2-phenoxy ethyleneglycol acrylate, R _6: a hydrogen atom, R _7: an ethylene group, R _8: a hydrogen atom, n = 1], or SR-504 (ethoxylated nonylphenol acrylate, R ₆ : Hydrogen atom, R ₇ : ethylene group, R ₈ : n-nonyl group] and the like, but not limited thereto, two or more kinds may be used in combination.

In the ethylenically unsaturated monomer represented by the general formula (13), the alkyl group of R ₈ has 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group includes not only a linear alkyl group but also a branched alkyl group and an alkyl group having a benzene ring as a substituent. When the carbon number of the alkyl group of R ₈ is 1 to 10, the alkyl group becomes an obstacle and the penetration of ITO etching solution, metal etching solution, etc. is suppressed and the chemical resistance is improved. The steric hindrance effect increases, and the adhesion with the base material tends to be hindered. This tendency becomes more prominent as the carbon chain length of the alkyl group of R ₈ becomes longer. When the carbon number exceeds 20, the adhesion with the substrate is extremely lowered. Examples of the alkyl group having a benzene ring represented by R ₈ include a benzyl group and a 2-phenyl (iso) propyl group. By adding one side chain benzene ring, chemical resistance is further improved and developability is also improved.

  In the ethylenically unsaturated monomer represented by the general formula (13), n is preferably an integer of 1 to 15. When n exceeds 15, the hydrophilicity increases and the effect of solvation decreases, and the viscosity of the resin [B1] increases, and the viscosity of the photosensitive composition using the same also increases, affecting the fluidity. May give. From the viewpoint of solvation, n is particularly preferably 1 to 4.

  As the precursor of the structural unit (b2), styrene, α-methylstyrene, benzyl acrylate, benzyl methacrylate, or the general formula (13) is used from the viewpoints of copolymerization with other precursors and chemical resistance. The ethylenically unsaturated monomer shown by these is preferable. These are particularly preferable because a benzene ring can be introduced into the side chain of the resin [B1]. By introducing a benzene ring into the side chain of the vinyl resin, the side chain benzene ring is oriented to the pigment, so that the resin adsorption to the pigment is promoted and the pigment aggregation is also suppressed. Furthermore, benzyl acrylate and / or benzyl methacrylate are most preferred from the viewpoints of developability and dispersion stability.

[Structural unit (b3)]
The structural unit (b3) has a cyclic structure with an aliphatic ring group represented by the chemical formula (4) and the chemical formula (5), and serves as an affinity site for a pigment or a pigment composition comprising a pigment and a dispersant, and the like. Functions as a hydrophobic site for the alkaline developer. Based on the weight of all the structural units of the resin [B1], the structural unit (b3) is 2 to 40% by weight from the viewpoints of developability, dispersion stability, and chemical resistance. If it is less than 2% by weight, the lack of an affinity site for the pigment or the pigment composition composed of the pigment and the dispersant, the dispersion becomes poor and the contrast ratio becomes low, and a high-quality color filter cannot be obtained, The problem that the storage stability of the coloring composition for color filters worsens arises. Further, since the hydrophobicity at the time of development is insufficient, there may be a problem of pattern peeling or chipping in the pixel portion. If it exceeds 40% by weight, the dissolution rate in an alkali developer may be slow, and the development time may be long and the productivity of the color filter may deteriorate.

Examples of the precursor of the structural unit (b3) include an ethylenically unsaturated monomer represented by the general formula (14), an ethylenically unsaturated monomer represented by the general formula (15), and the like.

[一般式（１４）、一般式（１５）中、Ｒ₉は、水素原子、またはメチル基であり、Ｒ₁₀は、炭素数２若しくは３のアルキレン基であり、ｍは、１〜１５の整数である。]

[In General Formula (14) and General Formula (15), R ₉ is a hydrogen atom or a methyl group, R ₁₀ is an alkylene group having 2 or 3 carbon atoms, and m is an integer of 1 to 15. It is. ]

Examples of the ethylenically unsaturated monomer represented by the general formula (14) include:
FANCLIL FA-513A [dicyclopentanyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m = 0], or FA-513M [dicyclopentanyl methacrylate, R ₉ : methyl, R ₁₀ manufactured by Hitachi Chemical Co., Ltd. : None, m = 0] and the like, but not limited thereto, two or more kinds can be used in combination.

As an unsaturated ethylene monomer represented by the general formula (15), for example,
FANCLIL FA-511A [dicyclopentenyl acrylate, R ₉ : hydrogen atom, R ₁₀ : none, m = 0], FA-512A [dicyclopentenyloxyethyl acrylate, R ₉ : hydrogen atom, R ₁₀ : Ethylene group, m = 1], FA-512M [dicyclopentenyloxyethyl methacrylate, R ₉ : methyl group, R ₁₀ : ethylene group, m = 1], or FA-512MT [dicyclopentenyloxyethyl methacrylate, R _9: methyl group, R _10: an ethylene group, m = 1] and the like but can be exemplified, without limitation, can be used in combination of two or more kinds.

[Other structural units]
The other structural unit is not limited as long as it is a structural unit other than the structural unit (b1), the structural unit (b2), and the structural unit (b3). However, since the main function of the other structural unit is to provide developability, a small structure is formed with respect to the relatively large ring structure of the side chain of the structural unit (b2) having a chemical resistance function. It is preferable to take. Thereby, it is considered that developability can be imparted while maintaining the characteristics of the structural unit (b2) having a large side chain having chemical resistance.

Examples of other structural unit precursors include:
Methyl (meth) methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (Meth) acrylate, pentyl (meth) acrylate, isopentyl acrylate, neopentyl (meth) acrylate, t-pentyl (meth) acrylate, 1-methylbutyl (meth) acrylate, hexyl (meth) acrylate, hepta (meth) acrylate, octyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, cetyl (meth) acrylate, stearyl (meth) acrylate, isostearyl (meth) acrylate, Alkyl or alkenyl (meth) acrylates such as rohexyl (meth) acrylate, allyl (meth) acrylate, or oleyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, β-carboxyethyl (Meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) Acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di Various acrylic and methacrylic esters such as (meth) acrylate, dipentaerythritol hexa (meth) acrylate, isobornyl (meth) acrylate, ester acrylate, epoxy (meth) acrylate, urethane acrylate, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol Divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, acrylonitrile, dimethyl-2,2 '-[oxybis (methylene)] bis-2-propenoate, diethyl- 2,2 '-[oxybis (methylene)] bis-2-propenoate, dicyclohexyl-2,2'-[oxybis (methylene)] bis-2- Examples of monomers and oligomers such as propenoate and dibenzyl-2,2 ′-[oxybis (methylene)] bis-2-propenoate include, but are not limited to, other ethylenically unsaturated monomers. Can be selected, and two or more types can be used in combination. As described above, methyl (meth) acryl methacrylate or ethyl (meth) acrylate is preferably used from the viewpoint of developability.

Other ethylenically unsaturated monomers include, for example,
(Meth) acrylates having a heterocyclic substituent such as tetrahydrofurfuryl (meth) acrylate or 3-methyloxetanyl (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate or ethoxypolyethylene glycol (meth) acrylate; or
(Meth) acrylamide (in the case of “(meth) acrylamide”, it means acrylamide and / or methacrylamide; the same shall apply hereinafter), N, N-dimethyl (meth) acrylamide, N, N -(Meth) acrylamides such as diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholine.

Moreover, as a monomer other than the acrylic monomer, for example,
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; or
Examples include vinyl acetate, and fatty acid vinyls such as vinyl propionate. The monomer other than the acrylic monomer can be used in combination with the acrylic monomer.

[Introduction of ethylenically unsaturated double bond]
The resin [B1] of the present invention is preferably a photosensitive resin, and more preferably has a structural unit (b4) having an ethylenically unsaturated double bond. In order to introduce an ethylenically unsaturated double bond, an ethylenically unsaturated monomer having an epoxy group or an ethylenically unsaturated monomer having a hydroxyl group is obtained by the following method (i) or method (ii). Can also be used. Since these may become structural units other than other structural units depending on the modification, the final weight ratio of the structural unit (b1), the structural unit (b2), and the structural unit (b3) is taken into consideration. There is a need. The structural unit (b4) having an ethylenically unsaturated double bond is 2 to 60% by weight from the viewpoint of the pattern shape based on the weight of all the structural units of the vinyl resin [B1] (100% by weight). preferable. When it is 2% by weight or more, the pattern shape is good, and when it is 60% by weight or less, the resolution is good, which is preferable.

[Method (i)]
As the method (i), an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having an epoxy group are used to introduce an ethylenically unsaturated double bond, The method of doing is mentioned.

  For example, the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other ethylenically unsaturated monomers is ethylenic. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an unsaturated double bond, further reacting a polybasic acid anhydride with the generated hydroxyl group, introducing an ethylenically unsaturated double bond, and the function of the photosensitive resin And a method (i1) for introducing a carboxyl group having an alkali-soluble function.

  That is, in the present invention, a copolymer (i1-1) is prepared by reacting a precursor of the structural unit (b2), a precursor of the structural unit (b3), and an ethylenically unsaturated monomer having an epoxy group. Next, the copolymer (i1-1) obtained is reacted with an unsaturated monobasic acid to obtain a copolymer (i1-2), and the copolymer (i1) further obtained -2) and a resin obtained by reacting a polybasic acid anhydride are preferable because of excellent heat resistance.

  Moreover, since the carboxyl group of the unsaturated monobasic acid used in this method (i1) forms an ester bond after the addition reaction to the epoxy group, the structural unit (b1) of the resin [B1] in this specification includes This does not correspond to other structural units, and the polybasic acid anhydride forms a carboxyl group after reaction with a hydroxyl group, and thus corresponds to the structural unit (b1) of the resin [B1] in this specification.

  Alternatively, a part of the side chain carboxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other ethylenically unsaturated monomers. And the method (i2) of introducing an ethylenically unsaturated double bond and a carboxyl group by addition reaction of an ethylenically unsaturated monomer having an epoxy group.

  That is, in the present invention, a copolymer (i2-1) is obtained by reacting a precursor of the structural unit (b1), a precursor of the structural unit (b2), and a precursor of the structural unit (b3). Since the resin obtained by reacting the copolymer (i2-1) obtained next with an ethylenically unsaturated monomer having an epoxy group can obtain a coating film exhibiting high surface hardness. Is preferable.

  In this case, only the structural unit corresponding to the carboxyl group that is not used for the addition reaction with the epoxy group corresponds to the structural unit (a1) of the resin [B1] in this specification.

  Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, 2-glycidoxyethyl (meth) acrylate, and 3,4-epoxybutyl (meth) acrylate. And 3,4-epoxycyclohexyl (meth) acrylate, which may be used alone or in combination of two or more. Glycidyl (meth) acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step and from the viewpoint of substrate adhesion.

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, P-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano-substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together. Of these, (meth) acrylic acid is preferred.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can also be hydrolyzed. Further, when etrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

[Method (ii)]
As the method (ii), an ethylenically unsaturated double bond is introduced using an ethylenically unsaturated monomer having a hydroxyl group and an ethylenically unsaturated monomer having an isocyanate group to obtain a photosensitive resin. A method is mentioned.

  For example, a copolymer obtained by copolymerizing an unsaturated monobasic acid having another carboxyl group or another ethylenically unsaturated monomer using an ethylenically unsaturated monomer having a hydroxyl group There is a method in which an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group is reacted with the side chain hydroxyl group.

  Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, and glycerol. Examples thereof include hydroxyalkyl (meth) acrylates such as (meth) acrylate or cyclohexanedimethanol mono (meth) acrylate, and these may be used alone or in combination of two or more. In addition, polyether mono (meth) acrylates obtained by addition polymerization of the above hydroxyalkyl (meth) acrylates with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, (poly) ε-caprolactone And / or (poly) 12-hydroxystearic acid added (poly) ester mono (meth) acrylate can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl (meth) acrylate or glycerol (meth) acrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [(meth) acryloyloxy] ethyl isocyanate, and the like. In addition, two or more types can be used in combination.

The weight average molecular weight (Mw) of the resin [B1] is preferably in the range of 5,000 to 100,000, more preferably in the range of 5,000 to 80,000, still more preferably 5,000 to 30,000. Range. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.
When the weight average molecular weight (Mw) of the resin [B1] exceeds 100,000, the interaction between the resins becomes strong, and the viscosity of the photosensitive resin composition becomes high, so that the handling tends to be difficult. Further, if the weight average molecular weight (Mw) is less than 5,000, problems may occur in developability and adhesion to a substrate such as glass.

  The weight average molecular weight (Mw) of the resin [B1] is preferably in the range of 5,000 to 80,000, more preferably in the range of 7,000 to 50,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are connected to four separation columns in series in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation. This is a polystyrene equivalent molecular weight measured using “TSK-GEL SUPER H5000”, “H4000”, “H3000”, and “H2000” manufactured by the company and using tetrahydrofuran as the mobile phase.

  When the resin [B1] is used as a coloring composition for a color filter, a colorant adsorbing group and a carboxyl group that functions as an alkali-soluble group during development, an aliphatic group that functions as an affinity group for the colorant carrier and solvent, and The balance of the aromatic group is important for the dispersibility, penetrability, developability and durability of the colorant, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern does not remain by development.

  The resin [B1] is preferably used in an amount of 20 to 500 parts by weight with respect to 100 parts by weight of the colorant [A]. If it is less than 20 parts by weight, the film formability and various resistances are insufficient, and if it is more than 500 parts by weight, the concentration of the colorant becomes low and color characteristics cannot be expressed.

(Other resins)
The photosensitive resin composition of the present invention may further contain other resins other than the resin [B1]. As the other resin, a resin having a transmittance of preferably 80% or more, more preferably 95% or more is preferable in the entire wavelength region of 400 to 700 nm in the visible light region. Other resins include thermoplastic resins, thermosetting resins, and photosensitive resins, and these can be used alone or in admixture of two or more.

  Examples of the thermoplastic resin include butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin. , Acrylic resins, alkyd resins, polystyrene, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene, polybutadiene, polyimide resins, and the like. Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

  Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used

<Organic solvent>
In the coloring composition of the present invention, the colorant is sufficiently dispersed and permeated in the colorant carrier, and is applied on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. An organic solvent is included to facilitate the formation. The organic solvent is selected in consideration of good applicability of the coloring composition, solubility of each component of the coloring composition, and safety.

Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane. 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3- Methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether , Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol Monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used alone or in admixture of two or more at any ratio as required.

  Among them, the dispersibility of the colorant, the penetrability, and the coating property of the coloring composition are good, so ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl It is preferable to use glycol acetates such as ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone.

  In addition, the organic solvent can be used in an amount of 500 to 4000 parts by weight with respect to 100 parts by weight of the colorant because the colored composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness. Is preferred.

<Photopolymerizable monomer>
Photopolymerizable monomers that may be added to the colored composition of the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin.

Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy Luether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.
These photopolymerizable compounds can be used singly or in combination of two or more at any ratio as required.

  The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability. .

<Photopolymerization initiator>
In the colored composition of the present invention, a photopolymerization initiator is added to form a filter segment by photolithography by curing the composition by ultraviolet irradiation, and a solvent development type or alkali development type photosensitive coloring composition is added. It can be prepared in the form of

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as dimethyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3 ', 4 Benzophenone compounds such as 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) Nyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] Or an oxime ester compound such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) Phosphine compounds such as phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; An imidazole compound; or a titanocene compound or the like is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the colorant, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

<Sensitizer>
Furthermore, the coloring composition of the present invention can contain a sensitizer.
Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 ', or 4,4'-tetra (t-butylperoxycarbonyl) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the colored composition, and 5 to 50 parts by weight from the viewpoint of photocurability and developability. It is more preferable that

<Antioxidant>
The coloring composition for a color filter of the present invention can contain an antioxidant. Antioxidants are used to prevent the photopolymerization initiators and thermosetting compounds contained in the color filter coloring composition from oxidizing and yellowing due to thermal processes during thermal curing and ITO annealing. Can be high. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high coating film transmittance can be obtained.

  The “antioxidant” in the present invention may be a compound having an ultraviolet absorbing function, a radical scavenging function, or a peroxide decomposing function. Specifically, as an antioxidant, a hindered phenol type, a hindered amine type are used. , Phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylate-based, and triazine-based compounds, and known ultraviolet absorbers, antioxidants, and the like can be used.

  Among these antioxidants, a hindered phenol antioxidant, a hindered amine antioxidant, a phosphorus antioxidant, or a sulfur antioxidant is preferable from the viewpoint of achieving both transmittance and sensitivity of the coating film. Agents. More preferably, they are hindered phenolic antioxidants, hindered amine antioxidants, or phosphorus antioxidants.

  As the hindered phenol-based antioxidant, 2,4-bis [(laurylthio) methyl] -o-cresol, 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5-di- -T-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 2,6-di-t-butyl-4- Nonylphenol, 2,2'-isobutylidene-bis- (4,6-dimethyl-phenol), 4,4'-butylidene-bis- (2-tert-butyl-5-methylphenol), 2,2'-thio- Su- (6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,2′thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) ) -Propionate, 1,1,3-tris- (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -butane, 2,2′-methylene-bis- (6- (1-methyl) -Cyclohexyl) -p-cresol), 2,4-dimethyl-6- (1-methyl-cyclohexyl) -phenol, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydro Cinnamamide) and the like. In addition, oligomer-type and polymer-type compounds having a hindered phenol structure can also be used.

  Examples of hindered amine-based antioxidants include bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4 -Piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3, 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6 -Tetramethyl-4-piperidi ) Imino} hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazine-2,4-diyl) {(2, 2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-hydroxyethyl)- Polycondensate with 4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N′-4,7-tetrakis [4,6-bis {N-butyl-N- (1,2,2 , 6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazin-2-yl] -4,7-diazadecane-1,10-diamine, etc. Other oligomer type having a hindered amine structure as well as Rimmer type of compounds and the like can also be used.

  Phosphorous antioxidants include tris (isodecyl) phosphite, tris (tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di (tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl Phosphite, diphenyltridecyl phosphite, triphenyl phosphite, tris (nonylphenyl) phosphite, 4,4 ′ isopropylidenediphenol phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, tris (biphenyl) phosphite, distearyl pentaerythritol diphosphite, di (2 , 4-di-t-butylphenyl) pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4′-butylidenebis (3-methyl-) 6-t-butylphenol) diphosphite, hexatridecyl 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane triphosphite, 3,5-di-t-butyl -4-hydroxybenzyl phosphite diethyl ester, sodium bis (4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3 -Bis (diphenoxyphosphonoxy) -ben Zen, ethylbisphosphite (2,4-ditert-butyl-6-methylphenyl), and the like. In addition, oligomer type and polymer type compounds having a phosphite structure can also be used.

  As sulfur-based antioxidants, 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2,4-bis [(octylthio) methyl]- o-cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like. In addition, oligomer type and polymer type compounds having a thioether structure can also be used.

  As the benzotriazole-based antioxidant, oligomer-type and polymer-type compounds having a benzotriazole structure can be used.

  Specific examples of the benzophenone antioxidant include 2-hydroxy-4-methoxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2 -Hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4-methoxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2, -Hydroxy-4-methoxy-5sulfobenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-chlorobenzophenone and the like. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

  Examples of the triazine antioxidant include 2,4-bis (allyl) -6- (2-hydroxyphenyl) 1,3,5-triazine. In addition, oligomer-type and polymer-type compounds having a triazine structure can also be used.

  Examples of the salicylate ester antioxidant include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

  These antioxidants can be used singly or in combination of two or more at any ratio as required.

  Further, the content of the antioxidant is more preferably 0.5 to 5.0% by weight based on the solid content weight of the photosensitive coloring composition for a color filter because the brightness and sensitivity are good.

<Amine compound>
Moreover, the coloring composition of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

<Leveling agent>
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the colored composition of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.
Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

<Curing agent, curing accelerator>
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- Til-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine / isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins.

<Other additive components>
The coloring composition of the present invention may contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight with respect to 100 parts by weight of the colorant.

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, with respect to 100 parts by weight of the colorant in the coloring composition.

<Method for producing colored composition>
The coloring composition of the present invention comprises a coloring agent in a dye carrier such as a binder resin [B] and / or a solvent, preferably together with a dispersion aid, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal type. It can be produced by finely dispersing (pigment dispersion) using various dispersing means such as a sand mill, a vertical sand mill, an annular bead mill, or an attritor. At this time, the specific aluminum phthalocyanine dye and other colorants may be simultaneously dispersed in the colorant carrier, or those separately dispersed in the colorant carrier may be mixed. In addition, when the colorant has high solubility, specifically, it is highly soluble in the solvent to be used, and if it is dissolved by stirring and no foreign matter is confirmed, it is necessary to manufacture by finely dispersing as described above. There is no.

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition includes the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, additives, and the like. Can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant may be appropriately contained. Since the dispersion aid has a large effect of preventing reaggregation of the colorant after dispersion, the color composition obtained by dispersing the colorant in the colorant carrier using the dispersion aid has lightness and viscosity stability. Become good.

  Examples of the dye derivative include a compound obtained by introducing a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent into an organic pigment, anthraquinone, acridone, or triazine. 63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003 128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094773, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916 Gazettes, Japanese Patent No. 4585781 etc. can be used. These may be used alone or in combination of two or more. When a pigment derivative is used, one having a quinophthalone skeleton is preferable from the viewpoint of brightness.

  The content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the colorant from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.

  The resin-type dispersant has a colorant-affinity part having the property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to disperse the colorant to the colorant carrier. It works to stabilize. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide addition compound, phosphate ester-based and the like are used, they can be used alone or in admixture of two or more, not necessarily limited thereto.

  Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, and 170 manufactured by Big Chemie Japan. 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155, or Anti-Terra-U, 203, 204, or BYK -SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 160 manufactured by Nippon Lubrizol Corporation, such as P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, etc. 0, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc. -EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, manufactured by Japan 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7 54,1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

  Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate Anionic surfactants such as lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate; chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  When a resin-type dispersant and a surfactant are added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight with respect to 100 parts by weight of the colorant. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1 parts by weight, it is difficult to obtain the added effect. When the content is more than 55 parts by weight, the dispersion is affected by an excessive dispersant. May affect.

<Removal of coarse particles>
The colored composition of the present invention is prepared by means of centrifugal separation, filtration with a sintered filter or a membrane filter, and the like. Coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>
Next, the color filter of the present invention will be described.
The color filter of the present invention is a color filter comprising at least one filter segment formed from the coloring composition for a color filter of the present invention.
The color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one red filter segment is a red coloring composition for a color filter of the present invention. It is preferable to use a product. The color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.

  The green filter segment can be formed using a normal green coloring composition. Examples of the green coloring composition include C.I. I. It is a composition obtained by using a green pigment such as CI Pigment Green 7, 10, 36, 37, or 58. Green coloring compositions include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 82,185,187,188,193,194,198,199,213, or a yellow pigment 214 and the like can be used in combination.

  The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a colorant carrier. Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64 or the like is used.

  In addition, C.I. I. Purple pigments such as CI Pigment Violet 23, C.I. I. A metal lake pigment of a rhodamine dye such as CI Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, 81: 5 can be used in combination. Further, a basic dye or a salt forming compound of an acidic dye that exhibits blue or purple can be used.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.

  The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution.
In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an ink jet method or the like in addition to the above method, but the colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a substrate such as a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used for the liquid crystal display mode that performs colorization using color filters such as

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively. “PGMAC” means propylene glycol monomethyl ether acetate.

  The average primary particle diameter of the pigment, the identification method of the azo pigment, the weight average molecular weight (Mw) of the resin, and the acid value of the resin are as follows.

(Average primary particle diameter of pigment)
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission electron microscope (TEM). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

(Azo pigment identification method)
The identification of the azo pigment of the present invention was performed using a MALDI mass spectrometer autoflex III (hereinafter referred to as TOF-MS) manufactured by Bruker Daltonics, and the molecular ion peak of the obtained mass spectrum, the mass number obtained by calculation, Identified with the agreement.

(Resin polymerization average molecular weight (Mw))
Polymerization average molecular weight (Mw) of the resin is TSKgel column (manufactured by Tosoh Corporation), GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8120GPC), and measured in terms of polystyrene measured using THF as a developing solvent. It is a weight average molecular weight (Mw).

(Resin acid value)
To 0.5 to 1.0 part of the resin solution, 80 ml of acetone and 10 ml of water are added and stirred to dissolve uniformly, and a 0.1 mol / L KOH aqueous solution is used as a titrant and an automatic titrator (“COM-555”). Titration using Hiranuma Sangyo) and the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

  Subsequently, the naphthol azo pigment [A] used in Examples and Comparative Examples, other pigments, a method for producing a binder resin, a method for preparing a resin-type dispersant solution, a pigment dispersion, and a green photosensitive coloring composition And a method for producing a blue photosensitive coloring composition will be described.

<Method for producing naphtholazo pigment [A]>
(Production of naphtholazo pigment (a-1))
189 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide and 1344 parts of 25% aqueous sodium hydroxide solution were dissolved in 3500 parts of methanol to obtain a coupler solution.
On the other hand, 125 parts of 3-amino-4-methoxybenzanilide was dispersed in 2000 parts of water, adjusted to a temperature of 5 ° C. by adding ice, added with 205 parts of 35% aqueous hydrochloric acid and stirred for 1 hour, and then sodium nitrite 37 0.5 part was added to 110 parts of water, and the prepared aqueous solution was added thereto, followed by stirring for 2 hours. An aqueous solution consisting of 380 parts of an 80% aqueous acetic acid solution, 418 parts of a 25% aqueous sodium hydroxide solution, and 413 parts of water was added to form an aqueous diazonium salt solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.4. After stirring for 3 hours and confirming disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 307 parts of an azo pigment represented by the formula (A1-1). . As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described by the formula (A1-1).

  Subsequently, a salt milling process was performed. 100 parts of a naphthol azo pigment represented by the formula (A1-1), 1200 parts of sodium chloride and 120 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and salt milling. Processed. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a refined naphthol azo pigment (a-1) were obtained.

(Production of naphtholazo pigment (a-2))
In preparing the coupler solution, instead of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide, N- [5-trifluoromethylphenyl] -3-hydroxy- The same operation as in the production of the naphthol azo pigment (a-1) was performed except that 2-naphthalenecarboxamide was used, and 302 parts of azo compound 2 was obtained. As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A1-2).

  The obtained naphthol azo pigment represented by the formula (A1-2) was subjected to the same salt milling method as the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-2). The average primary particle size was 42 nm.

(Production of naphtholazo pigment (a-3))
A naphthol azo pigment was used except that 3-amino-4-methoxybenzamide was used instead of 3-amino-4-methoxybenzanilide used in the production of the naphthol azo pigment (a-1) in preparing the diazonium salt solution. The same operation as in the production of (a-1) was performed to obtain 306.5 parts of a naphthol azo pigment described in formula (A1-3). As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A1-3).

  The obtained naphthol azo pigment represented by the formula (A1-3) was subjected to the same salt milling method as the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-3). The average primary particle size was 45 nm.

(Production of naphtholazo pigment (a-4))
In preparing the coupler solution, instead of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide, N- [3,5-trifluoromethylphenyl] -3- A naphtholazo pigment (a) was used except that hydroxy-2-naphthalenecarboxamide was used, and 3-amino-4-methoxybenzamide was used in place of 3-amino-4-methoxybenzanilide when preparing the diazonium salt solution. The same operation as in the production of -1) was carried out to obtain 299 parts of a naphthol azo pigment described in formula (A1-7). As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment azo compound 7 described in formula (A1-7).

  The obtained naphthol azo pigment represented by the formula (A1-7) was subjected to the same salt milling method as the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-4). The average primary particle size was 47 nm.

(Production of naphtholazo pigment (a-5))
In preparing the coupler solution, instead of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide, N- [2-fluoro-5-trifluoromethylphenyl]- Naphthol azo pigments, except that 3-hydroxy-2-naphthalenecarboxamide was used and 3-amino-4-methoxybenzamide was used instead of 3-amino-4-methoxybenzanilide when preparing the diazonium salt solution The same operation as in the production of (a-1) was performed to obtain 301 parts of a naphthol azo pigment described in formula (A1-8). As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A1-8).

  The obtained naphthol azo pigment represented by the formula (A1-8) was subjected to the same salt milling method as the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-5). The average primary particle size was 42 nm.

(Production of naphtholazo pigment (a-6))
In preparing the diazonium salt solution, except that 3-amino-4-methylbenzamide was used instead of 3-amino-4-methoxybenzanilide used in the production of the naphtholazo pigment (a-1), a naphtholazo pigment ( Operation similar to manufacture of a-1) was performed, and 304 parts of naphthol azo pigments of a formula (A1-11) description were obtained. As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A1-11).

    The obtained naphthol azo pigment represented by the formula (A1-11) was subjected to a salt milling treatment similar to that for the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-6). The average primary particle size was 50 nm.

(Production of naphtholazo pigment (a-7))
A naphthol azo pigment (a-) was used except that the following compound (D) was used instead of 3-amino-4-methoxybenzanilide used in the production of the naphthol azo pigment (a-1) during the preparation of the diazonium salt solution. The same operation as in the production of 1) was performed to obtain 305 parts of a naphthol azo pigment described in formula (A1-14). As a result of mass spectrometry by TOF-MS, it was identified to be naphtholazo described in formula (A1-14).

  The obtained naphthol azo pigment represented by the formula (A1-14) was subjected to a salt milling method similar to that for the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-7). The average primary particle size was 40 nm.

(Production of naphtholazo pigment (a-8))
A naphthol azo pigment except that 3-amino-N-methylbenzamide was used in place of 3-amino-4-methoxybenzanilide used in the production of the naphthol azo pigment (a-1) in preparing the diazonium salt solution. Operation similar to manufacture of (a-1) was performed, and 305.5 parts of naphthol azo pigments of a formula (A1-16) description were obtained. As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment described in formula (A1-16).

  The obtained naphthol azo pigment represented by the formula (A1-16) was subjected to the same salt milling method as the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-8). The average primary particle size was 43 nm.

(Production of naphtholazo pigment (a-9))
63.4 parts of 3-amino-4-methoxybenzanilide are dispersed in 900 parts of water, adjusted to a temperature of 5 ° C. by adding ice, added with 104.0 parts of 35% aqueous hydrochloric acid and stirred for 1 hour, and then added with nitrous acid. An aqueous solution prepared by adding 19.9 parts of sodium to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did.
On the other hand, 88.4 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C. to prepare a coupler. It was set as the solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.5. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 141 parts of a naphthol azo pigment represented by the formula (A2-1). . As a result of mass spectrometry by TOF-MS, it was identified as a naphthol azo pigment of the formula (A2-1).

  Subsequently, a salt milling process was performed. 100 parts of a naphthol azo pigment represented by the formula (A2-1), 1200 parts of sodium chloride and 120 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and salt milling. Processed. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 97 parts of a refined naphthol azo pigment (a-9) were obtained.

(Production of naphtholazo pigment (a-10))
Disperse 43.5 parts of 3-amino-4-methylbenzanilide in 900 parts of water, add ice to adjust the temperature to 5 ° C., add 104.0 parts of 35% aqueous hydrochloric acid, and stir for 1 hour. An aqueous solution prepared by adding 19.9 parts of sodium to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. On the other hand, 88.4 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C. to prepare a coupler. It was set as the solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.2. After stirring for 3 hours and confirming the disappearance of the diazonium salt, it was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 123 parts of a naphtholazo pigment formula represented by the formula (A2-2). It was. As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment represented by formula (A2-2).

  A naphthol azo pigment (a-10) was obtained by subjecting the naphthol azo pigment represented by the formula (A2-2) to a salt milling method similar to that for the naphthol azo pigment (a-1).

(Production of naphthol azo pigment (a-11))
Disperse 43.5 parts of 3-amino-4-methoxybenzamide in 900 parts of water, add ice to adjust the temperature to 5 ° C., add 104.0 parts of 35% aqueous hydrochloric acid and stir for 1 hour, then sodium nitrite. 19.9 parts was added to 50 parts of water, the prepared aqueous solution was added, and the mixture was stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. On the other hand, 88.4 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C. to prepare a coupler. It was set as the solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.2. After stirring for 3 hours and confirming the disappearance of the diazonium salt, it was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 123 parts of a naphtholazo pigment formula represented by the formula (A2-3). It was. As a result of mass spectrometry by TOF-MS, it was identified to be a naphthol azo pigment represented by the formula (A2-3).

  The obtained naphthol azo pigment represented by formula (A2-3) was subjected to the same salt milling method as naphthol azo pigment (a-1) to obtain naphthol azo pigment (a-11).

(Production of naphtholazo pigment (a-12))
74.6 parts of an amine compound of the following formula (12-b) is dispersed in 900 parts of water, ice is added to adjust the temperature to 5 ° C., 104.0 parts of 35% hydrochloric acid aqueous solution is added, and the mixture is stirred for 1 hour. An aqueous solution prepared by adding 19.9 parts of sodium nitrate to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. On the other hand, 88.4 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C. to prepare a coupler. It was set as the solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.5. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 145 parts of a naphtholazo pigment represented by the formula (A2-8). . As a result of mass spectrometry by TOF-MS, it was identified as a naphthol azo pigment of the formula (A2-8).

  The obtained naphthol azo pigment represented by formula (A2-8) was subjected to the same salt milling method as naphthol azo pigment (a-1) to obtain naphthol azo pigment (a-12).

(Production of naphtholazo pigment (a-13))
125 parts of 3-amino-4-methoxybenzanilide are dispersed in 2000 parts of water, ice is added to adjust the temperature to 5 ° C., 205 parts of 35% aqueous hydrochloric acid is added, and the mixture is stirred for 1 hour. A water solution prepared by adding 110 parts to water was added, and the mixture was stirred for 2 hours. An aqueous solution consisting of 380 parts of an 80% aqueous acetic acid solution, 418 parts of a 25% aqueous sodium hydroxide solution, and 413 parts of water was added to form an aqueous diazonium salt solution.
Meanwhile, 154 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboxamide, N- [4- (2-oxo-2,3-dihydro-1H-benzimidazole] 5-yl)]-3-hydroxy-2-naphthalenecarboxamide 33.5 parts and 25% aqueous sodium hydroxide solution 1344 parts were dissolved in 3500 parts of methanol to obtain a coupler solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.4. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours. The azo pigment represented by formula (1-1) and the general formula (6 C. is an azo pigment represented by I. 309 parts of a mixture with Pigment Red 176 were obtained. As a result of mass spectrometry by TOF-MS, formula (1-1) and C.I. I. It was confirmed that the mass ratio of the pigment red 176 mixture of naphthol azo pigments was 82.1: 17.9.

  The obtained naphthol azo pigment mixture was subjected to the same salt milling method as that of the naphthol azo pigment (a-1) to obtain a refined naphthol azo pigment (a-13). The average primary particle size was 32 nm.

<Method for producing other pigments>
(Production of refined PR254 pigment (PR254-1))
Diketopyrrolopyrrole pigment C.I. I. 200 parts of Pigment Red 254 (“B-CF” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of a refined diketopyrrolopyrrole pigment (PR254-1) was obtained.

(Production of refined PR177 pigment (PR177-1))
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. Anthraquinone-based fine red pigment (PR177-1) was obtained.

(Miniaturized green pigment (PG58-1))
Phthalocyanine green pigment C.I. I. 200 parts of Pigment Green 58 (“FASTOGEN GREEN A110” manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine green pigment (PG58-1) was obtained.

(Miniaturized yellow pigment (PY150-1))
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine yellow pigment (PY150-1) was obtained.

(Miniaturized blue pigment (PB15: 6-1))
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyocolor Co., Ltd., specific surface area 60 m 2 / g) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho), 80 The mixture was kneaded at 6 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A fine blue pigment (PB15: 6-1) was obtained.

(Miniaturized purple pigment (PV23-1))
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. A purple refined purple pigment (PV23-1) was obtained.

<Method for producing binder resin solution>
(Preparation of resin solution (B1-1))
(Stage 1: Polymerization of resin main chain)
Place 100 parts of propylene glycol monomethyl ether acetate (PGMAC) in a reaction vessel equipped with a thermometer, cooling tube, nitrogen gas inlet tube, and stirrer in a separable four-necked flask, and heat to 120 ° C while injecting nitrogen gas into the vessel. At the same temperature, 16.2 parts of styrene, 35.5 parts of glycidyl methacrylate, 41.0 parts of dicyclopentanyl methacrylate, and azobisisobutyronitrile 1 as a catalyst required for the reaction of the precursor at this stage 0.0 part of the mixture was added dropwise over 2.5 hours to carry out the polymerization reaction.

(Step 2: Reaction to epoxy group)
Next, the inside of the flask was purged with air, and 17.0 parts of acrylic acid and 0.3 part of trisdimethylaminomethylphenol and 0.3 part of hydroquinone were added as catalysts required for the reaction of the precursor at this stage, Reaction was performed for 5 hours, and the resin solution whose weight average molecular weight is about 12000 (measurement by GPC) was obtained. The added acrylic acid is ester-bonded to the end of the epoxy group of the glycidyl methacrylate structural unit, so that no carboxyl group is generated in the resin structure.

(Step 3: Reaction to hydroxyl group)
Further, 30.4 parts of tetrahydrophthalic anhydride and 0.5 part of triethylamine as a catalyst required for the reaction of the precursor at this stage were added and reacted at 120 ° C. for 4 hours. In the added tetrahydrophthalic anhydride, one of two carboxyl groups generated by cleavage of the carboxylic anhydride moiety is ester-bonded to a hydroxyl group in the resin structure, and the other produces a carboxyl group terminal.

(Step 4: Adjustment of nonvolatile content)
Propylene glycol monomethyl ether acetate was added so that the nonvolatile content was 40% to obtain a resin solution (B1-1).

  The weight ratio of the structural unit in the resin solution (B1-1) is as follows: tetrahydrophthalic anhydride as the structural unit (b1); 21.7% by weight, styrene as the structural unit (b2); 11.6% by weight, structural unit (b3 ) As dicyclopentanyl methacrylate; 29.3% by weight; as other structural units, the total of glycidyl methacrylate and acrylic acid ester-bonded to the glycidyl terminal; 37.4% by weight.

(Preparation of resin solution (B1-2))
A synthetic reaction was carried out in the same manner as the resin solution (B1-1) except that dicyclopentanyl methacrylate in the resin solution (B1-1) was changed to dicyclopentenyl methacrylate to prepare a resin solution (B1-2). . The weight average molecular weight was 12500.

(Preparation of resin solution (B1-3))
Resin solution (B1-3) was obtained in the same manner as in steps 1, 2, and 4 of resin solution (B1-1). That is, in the production method of the resin solution (B1-1), the precursors corresponding to the structural units (b1) to (b4) and other structural units were replaced according to Table 1. The precursor corresponding to MAA (methacrylic acid) in the structural units (b1) to (b3) and the structural unit (b4) is mixed to carry out stage 1 of production, and then GMA (glycidyl methacrylate) is used as the precursor. In addition, stage 2 of the production was carried out and stage 4 was further carried out. The number of catalyst parts required for each stage was mixed in proportion to the total number of precursors mixed in each stage.

(Preparation of resin solution (B1-4))
70.0 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer in a separable four-necked flask, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. Thereafter, a mixture of 67.2 parts of benzyl methacrylate, 18.4 parts of methacrylic acid, 14.4 parts of dicyclopentanyl methacrylate, and 0.4 parts of 2,2′-azobisisobutyronitrile was added from the dropping tube over 2 hours. The solution was added dropwise to carry out a polymerization reaction. After completion of the dropping, the reaction was further continued for 3 hours to obtain an acrylic resin solution having a solid content of 30% by weight.
After cooling to room temperature, about 2 g of resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether so that the non-volatile content was 20% by weight in the previously synthesized resin solution. Acetate was added to prepare a resin solution (B1-4). The solid content acid value was 46.8 mgKOH / g, and the weight average molecular weight was 32,000.

(Preparation of resin solution (B2-1))
In the production method of the resin solution (B1-1), the precursors corresponding to the structural units (b1) to (b4) and other structural units were replaced according to Table 1, and the same as the resin solution (B1-1) The resin solution (B2-1) was obtained by the method. The number of catalyst parts required for each stage was mixed in proportion to the total number of precursors mixed in each stage.

(Preparation of resin solution (B2-2, 3))
Resin solutions (B2-2, 3) were obtained in the same manner as in steps 1, 2, and 4 of resin solution (B1-1). That is, in the production method of the resin solution (B1-1), the precursors corresponding to the structural units (b1) to (b4) and other structural units were replaced according to Table 1. The precursor corresponding to MAA (methacrylic acid) in the structural units (b1) to (b3) and the structural unit (b4) is mixed to carry out stage 1 of production, and then GMA (glycidyl methacrylate) is used as the precursor. In addition, stage 2 of the production was carried out and stage 4 was further carried out. The number of catalyst parts required for each stage was mixed in proportion to the total number of precursors mixed in each stage.

(Preparation of resin solution (B2-4))
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, and the temperature was raised to 80 ° C. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 40 wt% Thus, a resin solution (B2-4) was prepared. The weight average molecular weight (Mw) was 18000.

(Preparation of resin solution (B2-5))
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the non-volatile content was 40% by weight. Was added to prepare a resin solution (B2-5). The weight average molecular weight (Mw) was 26000.

The precursors of the structural units and the abbreviations of the structural units in Table 1 are described below.
MAA: methacrylic acid THPA: tetrahydrophthalic anhydride (4-cyclohexene-1,2-dicarboxylic anhydride)
BzMA: Benzyl methacrylate St: Styrene M110: Paracumylphenol ethylene oxide modified acrylate DCPMA: Dicyclopentanyl methacrylate GMA: Glycidyl methacrylate GMA-AA: A combination of acrylic acid and structural unit GMA MMA-GMA: Structural unit GMA added to methacrylic acid through addition reaction BMA: n-butyl methacrylate HEMA: 2-hydroxyethyl methacrylate

<Preparation of resin-type dispersant solution>
A commercially available resin type dispersant, EFKA4300 manufactured by BASF, and ethylene glycol monomethyl ether acetate were used to prepare a 40% by weight non-volatile solution and used as the resin type dispersant solution 1.

<Method for producing pigment dispersion>
(PR254 / Pigment dispersion (P-22))
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (P-22) whose non-volatile component is 20 weight% was produced.

Refined PR254 pigment (PR254-1): 11.0 parts acrylic resin solution (B1-1): 17.5 parts propylene glycol monomethyl ether acetate (PGMAC): 66.5 parts resin-type dispersant solution 1: 5.0 Part

(PR177 / Pigment dispersion (P-23))
PR177 / Pigment dispersion (P-22) in the same manner as the pigment dispersion (P-22) except that the refined PR254 pigment (PR254-1) pigment was changed to PR177-1 in the production method of the pigment dispersion (P-22). P-23) was produced.

(PG58 pigment dispersion (P-24))
PG58 / Pigment Dispersion (P-22) was prepared in the same manner as the Pigment Dispersion (P-22) except that the refined PR254 Pigment (PR254-1) pigment was changed to PG58-1 in the production method of the Pigment Dispersion (P-22). P-24) was produced.

(PY150 / Pigment dispersion (P-25))
PY150 / Pigment Dispersion (P-22) in the same manner as Pigment Dispersion (P-22) except that the refined PR254 Pigment (PR254-1) pigment in the production method of Pigment Dispersion (P-22) was changed to PY150-1. P-25) was produced.

(PB15: 6, pigment dispersion (P-26))
PB15: 6 · PB15: 6 ·· The same method as for the pigment dispersion (P-22) except that the refined PR254 pigment (PR254-1) pigment was changed to PB15: 6-1 in the production method of the pigment dispersion (P-22). A pigment dispersion (P-26) was produced.

(PV23 / Pigment dispersion (P-27))
PV23 / Pigment Dispersion (P-22) in the same manner as Pigment Dispersion (P-22) except that the finer PR254 Pigment (PR254-1) pigment was changed to PV23-1 in the production method of Pigment Dispersion (P-22). P-27) was prepared.

<Method for producing green and blue photosensitive coloring composition>
(Green photosensitive coloring composition (RG-1))
A mixture having the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to prepare a green photosensitive coloring composition (RG-1).
PG58 / pigment dispersion (P-24): 32.0 parts PY150 / pigment dispersion (P-25): 18.0 parts acrylic resin solution (B1-1): 7.5 parts photopolymerizable monomer ( "Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts dipentaerythritol hexaacrylate photopolymerization initiator ("OXE-02" manufactured by Ciba Japan): 1.5 parts Etanone, 1- [9-ethyl -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition (RB-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to produce a blue photosensitive coloring composition (RB-1).
PB15: 6 • Pigment dispersion (P-26): 45.0 parts PV23 • Pigment dispersion (P-27): 5.0 parts Acrylic resin solution (B1-1): 7.5 parts Photopolymerizable monomer Body ("Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator ("OXE-02" manufactured by Ciba Japan): 1.5 parts cyclohexanone: 39.0 parts

[Example 1]
(Naphthol azo pigment dispersion (P-1)
The following mixture was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The naphthol azo pigment dispersion (P-1) having a non-volatile component of 20% by weight was prepared.

Naphthol azo pigment (a-1): 11.0 parts Acrylic resin solution (B1-1): 17.5 parts Propylene glycol monomethyl ether acetate (PGMAC): 66.5 parts Resin-type dispersant solution 1: 5.0 parts

[Examples 1-16, Comparative Examples 1-5]
(Naphthol azo pigment dispersion (P-2 to 21))
A pigment dispersion (P-2 to 21) was prepared in the same manner as the naphthol azo pigment dispersion (P-1) except that the type of naphthol azo pigment was changed as shown in Table 2.

[Evaluation of coloring composition]
<Coating preparation and evaluation>
A red coating film was prepared using the obtained naphtholazo pigment dispersion (P-1 to 21), and the contrast ratio (CR) and heat resistance were evaluated by the following methods. Table 2 shows the evaluation results.

(Evaluation of contrast ratio (CR) of coating film)
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the coating film of the colored composition applied on the glass substrate, and reaches the other polarizing plate. At this time, if the polarizing planes of the polarizing plate and the polarizing plate are parallel, the light is transmitted through the polarizing plate, but if the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the colored composition, scattering or the like occurs by the colorant particles, and when a part of the polarization plane is displaced, the polarizing plate is transmitted in parallel. When the polarizing plate is orthogonal, part of the light is transmitted. This transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance when the polarizing plates were parallel and the luminance when they were orthogonal was calculated as the contrast ratio.

(Contrast ratio) = (Luminance when parallel) / (Luminance when orthogonal)

Therefore, when scattering occurs due to the colorant in the coating film, the luminance when parallel is reduced and the luminance when orthogonal is increased, the contrast ratio becomes low.

  A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, the measurement was performed through a black mask having a 1 cm square hole in the measurement portion.

The pigment dispersion (P-1 to 22) is applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 60 minutes. The coated substrate was prepared by heating and allowing to cool. The contrast ratio (CR) of the obtained coated substrate was measured. The prepared coated substrate was adjusted to a chromaticity of x = 0.620 with a C light source after heat treatment at 220 ° C.
The contrast ratio was determined according to the following criteria.

◎: 7000 or more ○: 6000 or more and less than 7000 Δ: 5000 or more and less than 6000 ×: less than 5000

(Evaluation of heat resistance of coating film)
The pigment dispersion (P-1 to 21) was applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, then dried at 70 ° C. for 20 minutes, and then at 220 ° C. for 60 minutes. The coated substrate was prepared by heating and allowing to cool. The prepared coated substrate was adjusted to a chromaticity of x = 0.620 with a C light source after heat treatment at 220 ° C. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 230 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following three stages.

ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)
◎: ΔEab * is less than 3.0 ○: ΔEab * is less than 5.0 Δ: ΔEab * is 5.0 or more and less than 10.0 ×: ΔEab * is 10.0 or more

  As shown in Table 2, the coloring composition for a color filter of the present invention containing the naphtholazo pigment represented by the general formula (1) and the binder resin [B1] having a specific structure has a high contrast ratio, The heat resistance was also excellent.

[Example 17]
(Red photosensitive coloring composition (RR-1))
The following mixture (100 parts in total) was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to obtain a red photosensitive coloring composition (R-1).

(Pigment dispersion) (Total 50 parts)
Naphtholazo pigment dispersion (P-1): 25.0 parts PR254 pigment dispersion (P-22): 25.0 parts resin solution (B1-1): 7.5 parts photopolymerizable monomer ( "Aronix M-402" manufactured by Toagosei Co., Ltd.): 2.0 parts Photopolymerization initiator ("OXE-02" manufactured by Ciba Japan): 1.5 parts PGMAC: 39.0 parts

[Examples 18 to 22, Comparative Examples 6 to 16]
(Red photosensitive coloring composition (RR-2 to 18))
The red photosensitive coloring composition (R-) was changed in the same manner as the red photosensitive coloring composition (RR-1) except that the pigment dispersion was changed to the type and blending amount (parts by weight) of the pigment dispersion shown in Table 3. 2-18) were obtained. In each photosensitive coloring composition, a total of 50 parts of the pigment dispersion is divided into x = 0.658 and y = 0.325 when the coating film substrate for evaluating the brightness of each coloring composition is C light source. Thus, the ratio of the pigment dispersion was adjusted to prepare 100 parts of a red photosensitive coloring composition.

[Evaluation of photosensitive coloring composition]
<Coating preparation and evaluation>
The contrast ratio, heat resistance, pattern shape, and resolution of the green coating film produced using the obtained red photosensitive coloring composition (RR-1 to 18) were evaluated by the following methods. Table 3 shows the evaluation results.

(Contrast ratio and evaluation of coating film)
The red photosensitive coloring composition (RG-1 to 18) was applied on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater, and then dried at 70 ° C. for 20 minutes to obtain ultrahigh pressure mercury. Using a lamp, UV exposure was performed with an integrated light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Then, after heating at 220 ° C. for 30 minutes and allowing to cool, the contrast ratio (CR) of the obtained coating film substrate was measured by the same method as the evaluation of the colored composition. The prepared coated substrate was adjusted to a chromaticity of y = 0.600 with a C light source after heat treatment at 220 ° C. The alkali developer was 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao Corporation), and 90% by weight of water. The thing which consists of was used.
The contrast ratio was determined according to the following criteria.

◎: 9000 or more ◎: 8000 or more ○: 7500 or more but less than 8000 Δ: 7000 or more but less than 7500 ×: less than 7000

(Brightness evaluation)
The red photosensitive coloring composition (RR-1 to 18) was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70 ° C. for 20 minutes, and then further heated to 230 ° C. at 60 ° C. A coated substrate was obtained in which the chromaticity of the substrate obtained by partial heating was such that x = 0.658 and y = 0.325 in a C light source. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The evaluation criteria are as follows.

◎ ... 19.2 or more ○ ... 19.0 or more but less than 19.2 △ ... 18.8 or more but less than 19.0 × ... less than 18.8

(Developability evaluation)
A substrate obtained by coating a red photosensitive coloring composition (RR-1 to 18) on a glass substrate having a size of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater at a rotation speed of 2 μm after drying. After drying at 70 ° C. for 20 minutes, spray development was performed using a sodium carbonate aqueous solution at 23 ° C., and the developability was evaluated in four stages. The alkali developer was 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao Corporation), and 90% by weight of water. The thing which consists of was used.
The developability evaluation was determined according to the following criteria.

◎: Can be completely removed within 30 seconds ○: Over 30 seconds but completely removed within 33 seconds Δ: Over 33 seconds but completely removed within 36 seconds ×: Over 36 seconds Can not be completely removed

(Pattern shape, resolution evaluation)
After coating the red photosensitive coloring composition (RR-1 to 18) on a 100 mm × 100 mm, 1.1 mm thick glass substrate, the solvent was removed by heating at 70 ° C. for 20 minutes in a clean oven, A coating film of about 2 μm was obtained. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask having a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm) using an ultrahigh pressure mercury lamp. Thereafter, this substrate was spray-developed using a sodium carbonate aqueous solution at 23 ° C., washed with ion-exchanged water, air-dried, and heated at 230 ° C. for 330 minutes in a clean oven. The spray development was performed in the shortest time during which a pattern can be formed without any development remaining on the coating film of each photosensitive coloring composition, and this was set as an appropriate development time. The alkali developer was 1.5% by weight of sodium carbonate, 0.5% by weight of sodium hydrogen carbonate, 8.0% by weight of an anionic surfactant (“Perex NBL” manufactured by Kao Corporation), and 90% by weight of water. The thing which consists of was used.
The film thickness of the coating film was determined using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

(Pattern shape evaluation)
A 100 μm photomask portion of the filter segment formed by the above method was cut into a 1 cm square glass and subjected to Pt / Pd vapor deposition with a Hitachi sputtering apparatus (E-1030), and then a Hitachi SEM (S-4300). ), The cross-sectional pattern shape of the filter segment was observed at an acceleration voltage of 15 kV and an observation magnification of 10,000 times, and was evaluated in four stages according to the angle (θ degrees) formed between the glass substrate and the edge portion of the cross section of the filter segment.

◎: θ <20 degrees, forward tapered shape ○: 20 degrees ≦ θ ≦ 45 degrees, forward tapered shape Δ: 45 degrees <θ ≦ 80 degrees, forward tapered shape ×: θ> 80 degrees, sharp forward taper to overhang

(Resolution evaluation)
The pattern in the 25 μm photomask portion of the filter segment formed by the above method was evaluated by observing with an optical microscope. The rank of evaluation is as follows. The poor resolution means that adjacent stripe patterns are connected or chipped. The resolution evaluation was determined according to the following criteria.

◎: Good resolution and linearity ○: Slightly inferior in linearity but good resolution △: Partially poor resolution ×: Poor resolution

  By including the naphthol azo pigment [A] represented by the general formula (1) of the present invention and the resin [B1], high brightness that could not be achieved conventionally is achieved. In addition, various properties such as contrast ratio and developability were improved, and the colored composition for color filter of the present invention obtained high evaluation results in all evaluations.

  In the combination with the naphthol azo pigment [A] represented by the general formula (1), in the structure containing a large amount of the structural unit (b1) of the resin (B1), the improvement in developability includes a large amount of the structural unit (b2). In the constitution, the contrast ratio was improved, and in the constitution containing a large amount of the structural unit (b3), the effect of suppressing the resolution tended to be recognized, and the coloring composition had high performance.

<Production of color filter>
The red photosensitive coloring composition (RR-1) of the present invention was applied by spin coating to a glass substrate on which a black matrix was previously formed, and then prebaked at 70 ° C. for 20 minutes in a clean oven. Next, the substrate was cooled to room temperature, and then exposed to ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp.
Thereafter, the substrate was spray-developed with a 0.2 wt% sodium carbonate aqueous solution at 23 ° C. for 30 seconds, washed with ion-exchanged water, and air-dried. Further, post-baking was performed at 230 ° C. for 30 minutes in a clean oven to form a striped colored pixel layer on the substrate.
Next, the green photosensitive coloring composition (RG-1) is used, the green coloring pixel layer is formed in the same manner as the red coloring pixel layer, and further the blue photosensitive coloring composition (RB-1) is used. In the same manner as the red colored pixel layer, a blue colored pixel layer was formed to obtain a color filter (CF-1). The formed film thickness of each colored pixel layer was 2.0 μm.

  The color filter using the red coloring composition of the present invention has high brightness and excellent contrast ratio, and the effect of the present invention has been proved.

Claims (6)

A color filter coloring composition comprising a colorant, a binder resin, and a solvent, wherein the colorant comprises a naphthol azo pigment [A] represented by the following general formula (1), and the binder resin is: A colored composition for a color filter comprising a resin [B1] having structural units (b1) to (b3).

[In General Formula (1), A represents a hydrogen atom, a benzimidazolone group, an optionally substituted phenyl group, or an optionally substituted heterocyclic group. R ¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , -NHCOR ¹² or an -SO ₂ NHR ^13. R ^{7 to} R ¹³ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]

(B1) Structural unit having a carboxyl group: 2 to 60% by weight
(B2) Structural unit having an aromatic ring group represented by formula (2) or formula (3): 2 to 80% by weight
(B3) Structural unit having an aliphatic cyclic group represented by chemical formula (4) or chemical formula (5): 2 to 40% by weight

[In General Formulas (2) and (3), R ₁ is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. ]

  Resin [B1] is a photosensitive resin, The coloring composition for color filters of Claim 1 characterized by the above-mentioned. Resin [B1]
A precursor of the structural unit (b2), a precursor of the structural unit (b3), and an ethylenically unsaturated monomer having an epoxy group are reacted to obtain a copolymer (i1-1). A copolymer (i1-2) is obtained by reacting the obtained copolymer (i1-1) with an unsaturated monobasic acid. Further, the obtained copolymer (i1-2) and a polybasic acid are obtained. A resin obtained by reacting an anhydride or a precursor of the structural unit (b1), a precursor of the structural unit (b2), and a precursor of the structural unit (b3) are reacted to produce a copolymer (i2 A resin obtained by reacting the copolymer (i2-1) obtained next with an ethylenically unsaturated monomer having an epoxy group. Or the coloring composition for color filters of 2. The colorant further comprises at least one selected from the group consisting of a naphthol azo pigment [A ′] represented by the following general formula (6), an azo pigment [C], a diketopyrrolopyrrole pigment, and an anthraquinone pigment. The coloring composition for a color filter according to any one of claims 1 to 3, which is contained.

[In General Formula (6), A ¹ each independently represents a hydrogen atom, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ⁵¹ represents a hydrogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁵⁷ or —COOR ⁵⁸ . R ⁵⁷ and R ⁵⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. ]   Furthermore, the coloring composition for color filters of any one of Claims 1-4 containing a photopolymerizable monomer and / or a photoinitiator.   A color filter comprising a filter segment formed from the colored composition for color filter according to any one of claims 1 to 5 on a substrate.