JP6217067B2 - Coloring composition for color filter and color filter - Google Patents

Description

  The present invention includes a color filter coloring composition used for manufacturing a color filter used in a color liquid crystal display device, an organic EL display device, a color image pickup tube element, and the like, and a filter segment formed using the same. The present invention relates to a color filter. The colored composition of the present invention can be applied to yellow, red, and green color filters.

  The color liquid crystal display device controls the amount of light passing through the second polarizing plate by controlling the degree of polarization of the light that has passed through the first polarizing plate by the liquid crystal layer sandwiched between the two polarizing plates. This is a display device that performs display by using a twisted nematic (TN) type liquid crystal. The liquid crystal display device can perform color display by providing a color filter between two polarizing plates. Therefore, liquid crystal display devices are being developed for use in televisions and personal computer monitors.

  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.

  In general, a color filter is formed in a fine strip (stripe) shape formed of a red filter layer (R), a green filter layer (G), and a blue filter layer (B) formed on the surface of a transparent substrate such as glass. The filter segments (pixels) are arranged in parallel or intersecting with each other, or the fine filter segments are arranged in a constant vertical and horizontal arrangement. 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. Recently, in addition to a red filter layer (R), a green filter layer (G), and a blue filter layer (B), a filter segment including a yellow filter layer (Y) has been used.

  A transparent electrode for driving a liquid crystal is generally formed on the color filter used in the color liquid crystal display device by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Is formed. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, it is necessary to perform the formation process at a high temperature of generally 200 ° C. or higher, preferably 230 ° C. or higher.

  Quality items required for the color filter include contrast ratio and brightness. 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, it is indispensable to increase the contrast ratio (high contrast).

  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. However, from the viewpoint of suppressing power consumption, the color filter has become highly bright.

  Furthermore, as described above, since color liquid crystal devices have been used for televisions, personal computer monitors, etc., there is a demand for a wide color reproduction region and high reliability as well as higher contrast and higher brightness for color filters. It is high.

In addition, a color image pickup device represented by C-MOS (Complementary Metal Oxide Semiconductor: Complementary Metal Oxide Semiconductor), CCD (Charge Coupled Device), etc. has a red filter layer (R) on the light receiving element. In general, color filters each including a primary color filter segment of an additive mixture of a green filter layer (G) and a blue filter layer (B) are disposed and separated. Further, since high sensitivity can be obtained compared to the primary color filter, a color filter having filter segments of cyan, magenta, and yellow (CMY) corresponding to the complementary colors of red, green, and blue is often used. Complementary color filters are often used in video cameras and the like that are difficult to use an auxiliary light source such as a flash.
In recent years, there is an increasing demand for high transmittance, that is, lightness and high reliability even for color filters used in color image pickup tube elements.

  The color filter production method includes a dyeing method using a dye or a salt-forming dye as a colorant, a dye dispersion method, a pigment dispersion method using a pigment as a colorant, a printing method, and an electrodeposition method. Among these, the dyeing method or the dye dispersion method has a drawback that the heat resistance and light resistance are slightly inferior because the colorant is a dye. Therefore, a pigment having excellent heat resistance and light resistance is used as a colorant for the color filter, and a pigment dispersion method is often used as a manufacturing method because of the accuracy and stability of the forming method.

  In the pigment dispersion method, a color resist is formed by mixing and blending a photosensitive agent or an additive into a resin in which pigment particles as a colorant are dispersed in a resin, and this color resist is applied onto a substrate by a coating device such as a spin coater. In this method, a color filter is produced by forming a coating film by the above, performing selective exposure through a mask with an aligner or a stepper, patterning by alkali development and thermosetting, and repeating this operation.

  In general, the pigment particles are subjected to a micronization treatment and a pigment dispersion in which the micronized pigment is brought close to the primary particles as much as possible is used to suppress light scattering by the pigment and achieve high contrast. In addition, since the transparency of the dispersion is improved, the spectral spectrum of the dispersion has high transmittance, and high brightness is realized. By using this dispersion as a color resist, a color filter having high contrast and high brightness can be obtained.

  Conventionally, as a colorant used for forming a green filter segment, a halogenated copper phthalocyanine pigment (for example, CI Pigment Green 36 or CI Pigment Green 7) has been conventionally used. Zinc halide phthalocyanine pigments (for example, CI Pigment Green 58) in which the central metal is replaced with zinc, which is a color material that exhibits a good color tone and a wide color display area and has a high coloring power, have been often used. (See Patent Documents 4 and 5). These green pigments include C.I. I. It is common to use yellow pigments such as CI Pigment Yellow 138, 139, 150, and 185 in combination.

  However, as mentioned above, there is a growing demand for higher contrast and higher brightness in the market. However, as long as conventional pigments are used in green filters, higher contrast and higher brightness are required. It is a difficult situation to achieve.

  Further, as described above, a method has been proposed in which a yellow filter segment (pixel) is added to a color filter having a red filter segment, a green filter segment, and a blue filter segment for the purpose of extending the color reproduction range of the color filter. (Patent Documents 1 and 2). Examples of the colorant used for forming the yellow filter segment include C.I. I. Examples include yellow pigments such as CI Pigment Yellow 138, 139, 150, and 185. However, the yellow filter segment is also required to have high contrast and high brightness. Again, as long as the conventionally used pigments are used, it is difficult to achieve further higher contrast and higher brightness.

In order to solve the above problems, a technique for dissolving a dye, not a pigment, in a resin or the like as a colorant has been proposed (for example, see Patent Document 3).
Further, a technique for achieving high brightness by using a pigment and a dye together has been proposed. (For example, refer to Patent Document 4).
Although it has been attempted so far to achieve high contrast and high brightness by using a pigment and a dye in combination, yellow dye materials have not been studied much. Currently. Among them, as yellow dyes for color filters, it has been proposed to use quaternary ammonium salt compounds such as quinoline acid dyes, azo acid dyes, aminoketone acid dyes, It did not come to the examination corresponding to high contrast. (For example, see Patent Document 5)

JP 2005-196166 A JP 2004-295116 A JP-A-6-75375 Republic of Korea Open Patent Gazette 2010-0010490 JP 2004-307391 A

  An object of the present invention is to provide a stable color composition for a color filter that has excellent color characteristics and resistance (heat resistance, light resistance, solvent solubility) and does not generate foreign matter on the coating film, and color characteristics using the same ( The present invention is to provide a color filter that has a high brightness and a high contrast ratio, and has excellent durability and adhesion to a transparent substrate such as glass. In particular, it is to provide a coloring composition and a color filter that maintain or improve high brightness and have excellent durability when used in a green filter in combination with a green pigment or a blue pigment, or when used in a yellow filter. .

  As a result of intensive studies to solve the above problems, the present inventors contain a salt-forming compound (A) that can be obtained by reaction of a resin having a cationic group in the side chain with a quinophthalone-based acidic compound. The coloring composition for color filters, especially for yellow and green applications, can achieve high brightness and a wide color reproduction range, has high storage stability, and no foreign matter is generated on the coating film. The inventors have found that the adhesiveness and the resistance are excellent, and have reached the present invention.

［一般式（１）中、Ｒ₁〜Ｒ₅およびＲ₆〜Ｒ₉は、それぞれ独立に、水素原子、ハロゲン原子、置換基を有しても良いアルキル基、置換基を有しても良いアリール基、置換基を有しても良いアルコキシル基を示す。Ｒ₁₀〜Ｒ₁₃は、それぞれ独立に、水素原子、ハロゲン原子、水酸基、置換基を有しても良いアルキル基、置換基を有しても良いアリール基、置換基を有しても良いアルコキシル基、−ＳＯ₃Ｈ；−ＣＯＯＨ；およびこれら酸性基の１価〜３価の金属塩またはアルキルアンモニウム塩を示す。Ｒ₁₀〜Ｒ₁₃の隣接した基は、一体となって置換基を有してもよい芳香環を形成してもよい。Ｒ₁₀〜Ｒ₁₃、およびＲ₁₀〜Ｒ₁₃の隣接した基で形成されうる芳香環の置換基のうち少なくとも一つは、酸性基である。］ That is, an embodiment of the present invention is a color filter coloring composition comprising at least a colorant, a binder resin, and an organic solvent, wherein the colorant includes a resin having a cationic group in a side chain and the following general formula: The present invention relates to a coloring composition for a color filter, which is a salt-forming compound (A) obtainable by reacting with a quinophthalone-based acidic compound represented by the formula (1).

[In General Formula (1), R _{1 to} R ₅ and R _{6 to} R ₉ may each independently have a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, or a substituent. An aryl group and an alkoxyl group which may have a substituent are shown. R _{10 to} R ₁₃ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group that may have a substituent, an aryl group that may have a substituent, or an alkoxyl that may have a substituent. Group, —SO ₃ H; —COOH; and monovalent to trivalent metal salts or alkylammonium salts of these acidic groups. The adjacent groups of R _{10 to} R ₁₃ may be combined to form an aromatic ring that may have a substituent. At least one of the substituents of the aromatic ring that can be formed by the adjacent groups of R _{10 to} R ₁₃ and R _{10 to} R ₁₃ is an acidic group. ]

Further, in an embodiment of the present invention, in the general formula (1), R _{10 to} R ₁₃ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, an alkoxyl group which may have a substituent, —SO ₃ H. ; -COOH; and a monovalent to trivalent metal salt or alkyl ammonium salt thereof acidic groups, at least one of R ₁₀ to R ₁₃ are, according to claim 1, wherein the acidic group The present invention relates to a coloring composition for a color filter.

In an embodiment of the present invention, R _{1 to} R ₅ and R _{6 to} R ₉ in the general formula (1) are each independently a hydrogen atom or a halogen atom. It is related with the coloring composition for color filters of description.

［一般式（２）中、Ｒ₁₄は水素原子、または置換もしくは無置換のアルキル基を表す。Ｒ₁₅〜Ｒ₁₇は、それぞれ独立に、水素原子、置換基を有しても良いアルキル基、置換基を有しても良いアルケニル基、または置換基を有しても良いアリール基を表し、Ｒ₁₅〜Ｒ₁₇のうち２つが互いに結合して環を形成しても良い。Ｑはアルキレン基、アリーレン基、―ＣＯＮＨ−Ｒ₁₈−、―ＣＯＯ−Ｒ₁₈−を表し、Ｒ₁₈はアルキレン基を表す。Ｙ^-は無機または有機のアニオンを表す。］ The resin having a cationic group in the side chain is an acrylic resin containing a structural unit represented by the following general formula (2).

[In General Formula (2), R ₁₄ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{15 to} R ₁₇ each independently represents a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent, Two of R _{15 to} R ₁₇ may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₁₈ —, —COO—R ₁₈ —, and R ₁₈ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

  An embodiment of the present invention also relates to the color filter coloring composition, wherein the colorant is a colorant further containing a pigment.

  An embodiment of the present invention also relates to the coloring composition for a color filter, wherein the pigment is at least one selected from the group consisting of a green pigment, a blue pigment, a red pigment, and a yellow pigment.

  An embodiment of the present invention also relates to the green coloring composition for a color filter, wherein the green pigment is a green pigment containing a polyhalogenated phthalocyanine pigment.

  An embodiment of the present invention also relates to the green coloring composition for a color filter, wherein the blue pigment is a blue pigment containing an aluminum phthalocyanine pigment.

  An embodiment of the present invention also relates to the coloring composition for a color filter, wherein the organic solvent is an organic solvent mainly composed of propylene glycol monomethyl ether acetate.

  The embodiment of the present invention further relates to the color composition for a color filter, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  An embodiment of the present invention also relates to a color filter comprising a red filter segment, a green filter segment, and a blue filter segment, wherein at least one filter segment is formed of the color filter coloring composition. .

  An embodiment of the present invention is a color filter comprising a red filter segment, a green filter segment, a blue filter segment, and a yellow filter segment, wherein at least one filter segment is formed of the coloring composition for a color filter. It relates to a color filter.

  By using the color filter formed by the color filter coloring composition according to the embodiment of the present invention, the color filter has high brightness and a wide color reproduction region, and has excellent resistance and adhesion by using a salt-forming compound. A filter can be obtained.

Hereinafter, the present invention will be described in detail.
In the present specification, “CI” means a color index (CI).

The color filter coloring composition of the present invention is a color filter coloring composition containing at least a colorant, a binder resin, and an organic solvent, wherein the colorant is a resin having a cationic group in the side chain and a quinophthalone series. It is a salt-forming compound (A) which can be obtained by reaction with an acidic compound.
The coloring composition for a color filter of the present invention uses a salt-forming compound (A) that can be obtained by a reaction between a resin having a cationic group in the side chain and a quinophthalone-based acidic compound as a colorant. Color reproducibility can be obtained, and furthermore, by chlorinating a quinophthalone-based acidic compound, it can have high heat resistance, light resistance, and organic solvent solubility.
The coloring composition for a color filter of the present invention is described in detail below.

<< Colorant >>
The colorant used in the present invention contains the salt-forming compound (A) as an essential component, and contains a pigment component as necessary. The salt-forming compound (A) can be obtained by a reaction between a resin having a cationic group in the side chain and a quinophthalone-based acidic compound.
<Salt-forming compound (A)>
(Quinophthalone-based acidic compounds)
The quinophthalone-based acidic compound for obtaining the salt-forming compound (A) used in the present invention will be described. The quinophthalone-based acidic compound in the present invention is represented by the general formula (1). First, the substituent of R < ₁ > -R < ₉ > in General formula (1) is demonstrated.

  Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

  Examples of the alkyl group which may have a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl, and n-octyl. Group, stearyl group, linear or branched alkyl group such as 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, diethylaminoethyl group, benzyl group, 4-methylbenzyl group, 4-tert-butyl Examples thereof include alkyl groups having a substituent such as a benzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, and a 2,4-dichlorobenzyl group.

  In addition, examples of the aryl group which may have a substituent include an aryl group such as a phenyl group, a naphthyl group, an anthranyl group, a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p- Methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2- Examples thereof include aryl groups having a substituent such as a naphthyl group, anthraquinonyl group, and 2-aminoanthraquinonyl group.

  Examples of the alkoxyl group which may have a substituent include methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutyloxy group, tert-butyloxy group, neopentyloxy group, 2, 3 -In addition to linear or branched alkoxyl groups such as dimethyl-3-pentoxy group, n-hexyloxy group, n-octyloxy group, stearyloxy group, 2-ethylhexyloxy group, trichloromethoxy group, trifluoromethoxy group, 2,2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitro Examples include an alkoxyl group having a substituent such as a propoxy group and a benzyloxy group.

Next, the substituent of R < ₁₀ > -R < ₁₃ > in General formula (1) is demonstrated.

The halogen atom, the alkyl group which may have a substituent, the aryl group which may have a substituent, and the alkoxy group which may have a substituent are as described for the substituents of R _{1 to} R _9. It is synonymous.

Examples of acidic groups include —SO ₃ H and —COOH, and monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, and aluminum salts. Etc. Examples of the alkyl ammonium salts include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine and stearylamine, quaternary alkylammonium salts such as palmityltrimethylammonium, dilauryldimethylammonium and distearyldimethylammonium salts. Is mentioned.

Moreover, the adjacent groups of R _{10 to} R ₁₃ are combined to form an aromatic ring which may have a substituent. The aromatic ring herein includes a hydrocarbon aromatic ring and a heteroaromatic ring. The hydrocarbon aromatic ring includes a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and the like, and the heteroaromatic ring includes pyridine. And a ring, a pyrazine ring, a pyrrole ring, a quinoline ring, a quinoxaline ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an indole ring, and a carbazole ring. As for the substituent is the same as those described for the substituent of R ₁₀ to R _13.

Among the above substituents, acidic groups such as —SO ₃ H and —COOH are essential, but other preferable substituents include a halogen atom, an alkyl group which may have a substituent, and a substituent. May be an alkoxyl group, and a more preferable substituent is a halogen atom.

  Specific examples of the quinophthalone compound of the present invention include the following quinophthalone-based acidic compounds (a) to (n), but the present invention is not limited thereto.

(Resin having a cationic group in the side chain)
Next, the resin having a cationic group in the side chain for obtaining the salt-forming compound (A) used in the present invention will be described. The resin having a cationic group in the side chain for obtaining the salt-forming compound (A) is not particularly limited as long as it has at least one onium base in the side chain. From the viewpoint of availability, etc., ammonium salts, iodonium salts, sulfonium salts, diazonium salts, and phosphonium salts are preferable. In view of storage stability (thermal stability), ammonium salts, iodonium salts, and sulfonium salts are preferable. More preferably, it is a salt. More preferred is an ammonium salt.

  When preparing a coloring composition for a color filter containing the salt-forming compound (A) and exhibiting properties as a color filter, it is possible to use the same type of resin as the binder resin constituting the coloring composition for the color filter. desirable. In the present invention, an acrylic resin is preferably used as a binder resin in the color filter coloring composition. Therefore, the resin having a cationic group in the side chain for obtaining the salt-forming compound (A) is an acrylic resin. It is desirable to be.

  Moreover, as resin which has a cationic group in a side chain, the acrylic resin containing the structural unit represented by following General formula (2) is preferable.

[In General Formula (2), R ₁₄ represents a hydrogen atom or a substituted or unsubstituted alkyl group. R _{15 to} R ₁₇ each independently represents a hydrogen atom, an alkyl group that may have a substituent, an alkenyl group that may have a substituent, or an aryl group that may have a substituent, Two of R _{15 to} R ₁₇ may be bonded to each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₁₈ —, —COO—R ₁₈ —, and R ₁₈ represents an alkylene group. Y ^- is representative of an inorganic or organic anion. ]

Examples of the alkyl group for R ₁₄ include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, and a cyclohexyl group. As an alkyl group, a C1-C12 alkyl group is preferable, a C1-C8 alkyl group is more preferable, and a C1-C4 alkyl group is especially preferable.

When the alkyl group represented by R ₁₄ has a substituent, examples of the substituent include a hydroxyl group and an alkoxyl group.

Among the above, R ₁₄ is most preferably a hydrogen atom or a methyl group.

R _{15 to} R ₁₇ each independently include a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted aryl group.

The alkyl group in R ₁₅ to R _17, for example, straight-chain alkyl group (methyl, ethyl, n- propyl, n- butyl, n- pentyl, n- octyl, n- decyl, n- dodecyl, n -Tetradecyl, n-hexadecyl, n-octadecyl, etc.), branched alkyl groups (isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, isohexyl, 2-ethylhexyl and 1,1,3,3) -Tetramethylbutyl etc.), cycloalkyl groups (cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl etc.) and bridged cyclic alkyl groups (norbornyl, adamantyl and pinanyl etc.). As this alkyl group, a C1-C18 alkyl group is preferable, More preferably, it is a C1-C8 alkyl group.

Examples of the alkenyl group in R _{15 to} R ₁₇ include linear or branched alkenyl groups (allyl, 2-propenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl). And a cycloalkenyl group (such as 2-cyclohexenyl and 3-cyclohexenyl). As this alkenyl group, a C2-C18 alkenyl group is preferable, More preferably, it is a C2-C8 alkenyl group.

Examples of the aryl group in R _{15 to} R ₁₇ include a monocyclic aryl group (phenyl, tolyl, xylyl, etc.), a condensed polycyclic aryl group (naphthyl, anthryl, phenanthryl, anthraquinolyl, fluorenyl, naphthoquinolyl, etc.) and aromatic. Heterocyclic hydrocarbon groups (thienyl (group derived from thiophene), furyl (group derived from furan), pyranyl (group derived from pyran), pyridyl (group derived from pyridine), 9-oxoxan Tenyl (a group derived from xanthone) and 9-oxothioxanthenyl (a group derived from thioxanthone)).

When the alkyl group, alkenyl group or aryl group represented by R _{15 to} R ₁₇ has a substituent, examples of the substituent include a halogen atom, a hydroxyl group, an alkoxyl group, an aryloxy group, an alkenyl group, an acyl group, Examples include a substituent selected from an alkoxycarbonyl group, a carboxyl group, a phenyl group, and the like. Among these substituents, a halogen atom, a hydroxyl group, an alkoxyl group, and a phenyl group are particularly preferable.

R _{15 to} R ₁₇ are preferably an alkyl group which may be substituted from the viewpoint of stability and the like, and more preferably an unsubstituted alkyl group.

R _{15 to} R ₁₇ may be bonded to each other to form a ring.

In the general formula (2), Q connecting the acrylic moiety and the ammonium base represents —CONH—R ₁₈ — or —COO—R ₁₈ —. Among them, for the reasons of polymerizability and availability, —CONH— R ₁₈ -and -COO-R ₁₈ -are preferred. R ₁₈ is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

Y ⁻ in the general formula (2) constituting the counter anion of the resin may be an inorganic or organic anion. As the anion, known ones can be used without limitation. Specifically, hydroxide ions; halogen ions such as chloride ions, bromide ions and iodide ions; carboxylate ions such as formate ions and acetate ions; Complexes such as ions, bicarbonate ions, nitrate ions, sulfate ions, sulfite ions, chromate ions, dichromate ions, phosphate ions, cyanide ions, permanganate ions, and hexacyanoferrate (III) ions And ions. From the viewpoint of synthesis suitability and stability, halogen ions and carboxylate ions are preferable, and halogen ions are most preferable. When the anion is an organic acid ion such as a carboxylate ion, the organic acid ion may be covalently bonded to the resin to form an inner salt.

  In order to obtain an acrylic resin containing the structural unit represented by the general formula (2) which is a preferred embodiment of the present invention, only a method of copolymerizing an ethylenically unsaturated monomer having an ammonium base as a monomer component is used. Alternatively, after obtaining an acrylic resin having an amino group obtained by copolymerizing an ethylenically unsaturated monomer having an amino group as a monomer component, it may be obtained by a method in which an onium chlorinating agent is reacted and ammonium salified. good.

  Below, the specific example of the ethylenically unsaturated monomer which can be used in order to obtain the acrylic resin containing the structural unit represented by General formula (2) which is a preferable aspect of this invention is shown. In addition, in this specification, when showing either or both of "acryl, methacryl", it may describe as "(meth) acryl". Similarly, when one or both of “acryloyl and methacryloyl” are indicated, it may be described as “(meth) acryloyl”.

  Examples of the ethylenically unsaturated monomer having a quaternary ammonium base include (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meta ) Alkyl (meth) acrylate quaternary ammonium salts such as acryloyloxyethylmethylmorpholino ammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzyl Alkyl (meth) acryloylamide quaternary ammonium salts such as ammonium chloride, dimethyl Luzia Lil ammonium methyl sulfate, trimethyl vinyl phenyl ammonium chloride.

  Examples of the ethylenically unsaturated monomer having an amino group include dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dipropylaminoethyl (meth) acrylate, diisopropylaminoethyl (meth) acrylate, and dibutylamino. Ethyl (meth) acrylate, diisobutylaminoethyl (meth) acrylate, di-t-butylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylamide, diethylaminopropyl (meth) acrylamide, dipropylaminopropyl (meth) acrylamide, diisopropyl Aminopropyl (meth) acrylamide, dibutylaminopropyl (meth) acrylamide, diisobutylaminopropyl (meth) acrylamide, di-t-butyl Examples include (meth) acrylic acid esters having a dialkylamino group such as minopropyl (meth) acrylamide or (meth) acrylamide, and styrenes having a dialkylamino group such as dimethylaminostyrene and dimethylaminomethylstyrene, diallylmethylamine, diallylamine And amino group-containing aromatic vinyl monomers such as N-vinylpyrrolidine, N-vinylpyrrolidone and N-vinylcarbazole.

  Examples of the onium chloride agent include alkyl sulfates such as dimethyl sulfate, diethyl sulfate, or dipropyl sulfate, sulfonate esters such as methyl p-toluenesulfonate, or methyl benzenesulfonate, methyl chloride, ethyl chloride, propyl chloride, or Examples thereof include alkyl chlorides such as octyl chloride, alkyl bromides such as methyl bromide, ethyl bromide, propyl bromide, and octyl chlorobromide, benzyl chloride, and benzyl bromide.

  The reaction between the ethylenically unsaturated monomer having an amino group and the onium chlorinating agent is usually performed by dropping an equimolar amount or less of the onium chlorinating agent into the amino group-containing ethylenically unsaturated monomer solution. Can be done. The temperature during the ammonium chlorination reaction is about 90 ° C. or less, and particularly when the vinyl monomer is ammonium chlorinated, it is preferably about 30 ° C. or less, and the reaction time is about 1 to 4 hours.

  Other examples of the ethylenically unsaturated monomer that can be used other than the structural unit represented by the general formula (2) include (meth) acrylic acid esters, crotonic acid esters, vinyl esters, and maleic acid. Diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, vinyl ethers, vinyl alcohol esters, styrenes, (meth) acrylonitrile and the like are preferable.

Specific examples of such vinyl monomers include the following compounds.
Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (meth) acrylic acid 2- Ethylhexyl, t-octyl (meth) acrylate, dodecyl (meth) acrylate, octadecyl (meth) acrylate, acetoxyethyl (meth) acrylate, phenyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-Methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate 2- (2-methoxyethoxy) ethyl (meth) acrylate, 3-phenoxy-2-hydroxypropyl (meth) acrylate, benzyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, (meth) acrylic acid Diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol monoethyl ether, ( Β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclo (meth) acrylate Pentenyloxyethyl, trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, tribromophenyl (meth) acrylate And (meth) acrylic acid tribromophenyloxyethyl.

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

Examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.

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

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

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

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

  In addition, the ethylenically unsaturated monomer that can be used other than the structural unit represented by the general formula (2) may further include a copolymer unit derived from a monomer having an acid group.

  As monomers having an acid group, unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid; maleic acid, maleic anhydride, fumaric acid, itaconic acid, anhydrous Unsaturated dicarboxylic acids such as itaconic acid, citraconic acid, citraconic anhydride and mesaconic acid or their anhydrides; trivalent or higher unsaturated polycarboxylic acids or their anhydrides; succinic acid mono (2-acryloyloxyethyl) ), Succinic acid mono (2-methacryloyloxyethyl), phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl) monovalent polyvalent carboxylic acid mono [ (Meth) acryloyloxyalkyl] esters; ω-carboxy-polycaprolactone monoacrylate, ω-carboxy-polycaprolacto Include mono (meth) acrylates such as both terminal carboxy polymers such monomethacrylate.

  Examples of a method for obtaining an acrylic resin containing the structural unit represented by the general formula (2) suitable for the present invention include anionic polymerization, living anionic polymerization, cationic polymerization, living cationic polymerization, free radical polymerization, and living radical polymerization. Any known method can be used. Of these, free radical polymerization or living radical polymerization is preferred.

  In the case of the free radical polymerization method, it is preferable to use a polymerization initiator. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), or 2,2′-azobis [2- (2-imidazolin-2-yl ) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, and diacetyl peroxide. These polymerization initiators can be used alone or in combination of two or more. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

  In the living radical polymerization method, side reactions that occur in general radical polymerization are suppressed, and further, since the growth of polymerization occurs uniformly, it is possible to easily synthesize block polymers and resins with uniform molecular weight.

  Among them, the atom transfer radical polymerization method using an organic halide or a sulfonyl halide compound as an initiator and a transition metal complex as a catalyst is applicable to a wide range of monomers, and has a polymerization temperature applicable to existing equipment. It is preferable in that it can be adopted. The atom transfer radical polymerization method can be carried out by the methods described in the following references 1 to 8 and the like.

(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. Rev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) WO96 / 030421
(Reference 6) WO97 / 018247
(Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-41117

  It is preferable to use an organic solvent for the polymerization. The organic solvent is not particularly limited, but for example, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether Acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, or the like is used. These organic solvents may be used as a mixture of two or more.

The amount of the cationic group present in the resin having a cationic group in the side chain used in the present invention is not particularly limited, but the cation salt value of the resin is preferably 10 to 200 mgKOH / g, More preferably, it is 20-130 mgKOH / g. The cation salt value is expressed as an onium salt value, a quaternary ammonium salt value, or an amine salt value.
In addition, among them, the amount of ammonium base and amine base present in the acrylic resin containing the structural unit represented by the general formula (2) suitable for the present invention is such that the ammonium salt value of the resin and the amine salt value are 10 to 200 mgKOH. / G is preferable, and 20 to 130 mgKOH / g is more preferable.

  The molecular weight of the acrylic resin containing the structural unit represented by the general formula (2) used in the present invention is not particularly limited, but the converted weight average molecular weight measured by gel permeation chromatography (GPC). Is preferably 1000 to 50000, and more preferably 3000 to 15000.

  Moreover, it is preferable that acrylic resin containing the structural unit represented by General formula (2) suitable for this invention has a characteristic melt | dissolved in the solvent widely used for the coloring composition for color filters. Thereby, the coating film without a foreign material generation | occurrence | production can be obtained. In particular, it is more preferable to dissolve in propylene glycol monomethyl ether acetate.

  In the resin having a cationic group in the side chain, the total content of the structural unit represented by the general formula (2) is not particularly limited, but the entire structure contained in the resin having a cationic group in the side chain When the unit is 100% by weight, the total content of the structural unit represented by the general formula (2) is 5% by weight or more from the viewpoint of solvent solubility and coloring power of the salt-forming compound. Preferably, it is 10 to 50% by weight.

(Salt formation)
The salt-forming compound (A) used in the present invention is a resin having a cationic group in the side chain and agitated or vibrated in an aqueous solution in which a quinophthalone-based acidic compound is dissolved, or having a cationic group in the side chain And an aqueous solution of a quinophthalone-based acidic compound can be easily obtained by mixing under stirring or vibration. In the aqueous solution, the cationic group of the resin and the anionic group of the quinophthalone-based acidic compound are ionized, and these are ionically bonded, and the ion-bonded portion becomes water-insoluble and precipitates. On the contrary, a salt composed of a counter anion of a resin and a counter cation of a quinophthalone-based acidic compound is water-soluble and can be removed by washing or the like. The resin having a cationic group in the side chain to be used and the quinophthalone-based acidic compound may be used alone or in a plurality of types having different structures.

  As an aqueous solution used for salt formation, a mixed solution of water and a water-soluble organic solvent may be used in order to dissolve the resin having a cationic group in the side chain and the quinophthalone-based acidic compound. Examples of the water-soluble organic solvent include methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, n-butanol, isobutanol, 2- (methoxymethoxy) ethanol, 2- Butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, ethylene glycol, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol, propylene glycolic monomethyl ether acetate, dipropylene glycol, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol, triethylene glycol monomethyl ether, polyethylene glycol, glycerin, tetraethylene glycol, dipropylene glycol, acetone, diacetone alcohol, aniline, pyridine, ethyl acetate, isopropyl acetate, methyl ethyl ketone , N, N-dimethylformamide, dimethyl sulfoxide, tetrahydrofuran (THF), dioxane, 2-pyrrolidone, 2-methylpyrrolidone, N-methyl-2-pyrrolidone, 1,2-hexanediol, 2,4,6-hexanetriol , Tetrafurfuryl alcohol, 4-methoxy-4-methylpentanone and the like. These water-soluble organic solvents are preferably used in an amount of 5 to 50% by weight, and most preferably 5 to 20% by weight, based on the total weight of the aqueous solution (100% by weight).

  The content of the effective pigment component derived from the quinophthalone-based acidic compound in the salt-forming compound (A) can be adjusted to a range of 10 to 60% by weight, particularly 15 to 15%, based on 100% by weight of the salt-forming compound (A). A range of 55% by weight is preferred. By controlling in this range, a salt-forming compound (A) excellent in solvent solubility can be obtained.

In addition, the weight percentage of the effective pigment component (residue obtained by removing counter cations such as metal ions from the quinophthalone-based acidic compound) in the quinophthalone-based acidic compound contained in the salt-forming compound (A) is adjusted to the same concentration. (A) It can calculate by measuring each spectral spectrum of a solution and a quinophthalone type acidic compound, and calculating | requiring the ratio of the spectral intensity in each maximum absorption wavelength. For example, it can be calculated by the method described below.
First, using a solvent (N-methyl-2-pyrrolidone or the like) that can well dissolve both the salt-forming compound (A) and the quinophthalone-based acidic compound, the salt-forming compound (A) solution has the same concentration. And a quinophthalone-based acidic compound solution are prepared. Subsequently, the absorbance of these adjusted solutions is measured, and the absorbance at each maximum absorption wavelength is measured. Here, the absorbances of the salt-forming compound (A) solution and the quinophthalone-based acidic compound solution are Xa and Xb, respectively. On the other hand, when the number of counter cations in the quinophthalone-based acidic compound is Na, the formula weight of the counter cation is Ma, and the molecular weight of the quinophthalone-based acidic compound is Mb, the weight% of the effective dye component in the quinophthalone-based acidic compound is Is given by the following equation.

(1-Ma × Na / Mb) × 100 [wt%]

And the weight% of the effective pigment | dye component in the quinophthalone type acidic compound contained in a salt-forming compound (A) can be computed from a following formula using this formula.

(Xa / Xb) × (1-Ma × Na / Mb) × 100 [wt%]

<Pigment>
The colored composition comprising the salt-forming compound (A) of the present invention has a yellow hue itself, and when used in combination with a pigment, it is a colored composition that exhibits the same yellow color and further green color. It is possible to obtain a colorant having excellent durability, color development and color reproducibility.
Above all, the colored composition of the present invention can be used in combination with a green pigment and / or a blue pigment to obtain a green colorant having a high brightness and used for a green filter segment.
In addition, the coloring composition of the present invention is a yellow colorant used in a yellow filter segment which is used in combination with a yellow pigment, or is a salt-forming compound (A) alone, has excellent durability and high coloring power while maintaining high brightness. Can be obtained.
The pigments that can be used for these are described below.

  The green colorant for forming the green filter segment is composed of the green pigment and / or blue pigment described below and the salt-forming compound (A) of the present invention.

(Pigment forming green filter segment)
[Green pigment]
As the green pigment, a polyhalogenated phthalocyanine pigment is preferable. The polyhalogenated phthalocyanine pigment represents a phthalocyanine pigment having at least two or more halogen atoms in the molecule. Specifically, C.I. I. Pigment green 7, 36, 37, 58, and the like.

[Blue pigment]
The blue pigment forming the green filter segment is preferably an aluminum phthalocyanine pigment. Aluminum phthalocyanine pigments are preferred pigments because they have higher coloring power than halogenated phthalocyanine pigments. Thereby, the addition amount of a pigment can be reduced or the film thickness of a color filter can be reduced. Moreover, the point which does not contain a halogen atom is also preferable from an environmental viewpoint.

[Yellow pigment]
The green colorant may further use a yellow pigment. Examples of 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, Mention may be made of yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220 or 221.

The usage ratio of the green / blue pigment and the salt-forming compound (A) is preferably 1 to 1200 parts by weight of the salt-forming compound (A) with respect to 100 parts by weight of the pigment. More preferably, it is 5 to 600 parts by weight. In consideration of the color composition, the blending ratio of the pigment and the content of the dye component derived from the quinophthalone-based acidic compound in the salt-forming compound (A) is 100 parts by weight of the pigment in the salt-forming compound (A). The effective pigment component is preferably 1 to 400 parts by weight. More preferably, the effective pigment component in the dye is in the range of 5 to 300 parts by weight with respect to 100 parts by weight of the pigment.
Moreover, what becomes favorable when the salt-forming compound (A) is used in combination with the pigment is that it is adsorbed to the pigment while being dissolved and dispersed in the solvent.
Particularly preferred pigments include aluminum phthalocyanine and zinc phthalocyanine (CI Pigment Green 58).

(Pigment forming yellow filter segment)
[Yellow pigment]
When forming a yellow filter segment, in addition to the salt-forming compound (A), the following yellow pigment can be used in combination.
C. 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, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 or the like. I. Pigment Yellow 138, 139, 150, and 185 are preferably used.

The use ratio of the yellow pigment and the salt-forming compound (A) is preferably 1 to 1200 parts by weight of the salt-forming compound (A) with respect to 100 parts by weight of the yellow pigment. More preferably, it is 5 to 600 parts by weight.
In consideration of the color composition, the blending ratio of the yellow pigment and the content of the effective dye component in the quinophthalone-based acidic compound in the salt-forming compound (A) is 100 parts by weight of the yellow pigment. ) Is preferably 1 to 400 parts by weight. More preferably, the effective pigment component in the dye is in the range of 5 to 300 parts by weight with respect to 100 parts by weight of the yellow pigment. These blends can be appropriately adjusted and used in consideration of the heat resistance, light resistance, and brightness of the colorant.
Moreover, what becomes favorable when the salt-forming compound (A) is used in combination with the pigment is that it is adsorbed to the pigment while being dissolved and dispersed in the solvent.
Particularly preferred pigments here are C.I. I. Pigment Yellow 138, 139, 150, and 185.

(Miniaturization of pigment)
The pigment used in the colored composition of the present invention can be refined by performing a salt milling treatment. The primary particle diameter of the 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, for 100 or more pigment particles, 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. At this time, the pigment particles were sampled on a grid mesh to prepare a sample for TEM observation.

Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After 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 total 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 total 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. It is preferable that the usage-amount of resin is 5-200 weight part with respect to 100 weight part of the total weight of a pigment.

<Binder resin>
The binder resin is one that disperses a colorant, particularly a salt-forming compound, or that dyes and permeates the salt-forming compound, and examples thereof include thermoplastic resins and thermosetting resins.
The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region.
Moreover, when using with the form of an alkali image development type colored resist material, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.
In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain for an alkali development resist for color filters, no coating foreign matter is generated after the salt-forming compound (A) is applied. The stability of the salt-forming compound (A) in the resist material is preferably improved. When a linear resin that does not have an ethylenically unsaturated double bond in the side chain is used, the dye is not easily trapped in the resin and dye mixture, and the dye has a degree of freedom. The components tend to aggregate and precipitate, but by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain, the dye is easily trapped in the resin and dye mixture, Dye components are less likely to agglomerate and precipitate, and even when exposed to active energy rays to form a film, the resin is three-dimensionally cross-linked to fix the dye molecules, and the solvent can be removed in the subsequent development process. It is estimated that the dye component is less likely to aggregate and precipitate.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000 in order to disperse the colorant preferably. 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 binder resin is used as a photosensitive coloring composition for a color filter, from the viewpoints of dispersibility, penetrability, developability, and heat resistance of pigments and salt-forming compounds, a colorant adsorbing group and alkali at the time of development can be used. The balance of the carboxyl group that acts as a soluble group, the aliphatic group that acts as an affinity group for the colorant carrier and the solvent, and the aromatic group, dispersibility, permeability, developability, and durability of the pigment and salt-forming compound (A) It is important 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, no fine pattern remains.

  The binder resin is preferably used in an amount of 30 parts by weight or more based on 100 parts by weight of the total weight of the colorant because the film formability and various resistances are good, and the colorant concentration is high, and good color characteristics are obtained. Since it can be expressed, it is preferably used in an amount of 500 parts by weight or less.

(Thermoplastic resin)
Examples of the thermoplastic resin used for the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate. , Polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. . Among them, it is preferable to use an acrylic resin.

Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group.
Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the following methods (a) and (b).

[Method (a)]
As the method (a), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group and one or more other monomers is used. Then, the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to convert the unsaturated ethylenic double bond and the carboxyl group into There is a way to introduce.

Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth) acrylate, methyl glycidyl (meth) acrylate, and 2-glycidoxyethyl (meth).
An acrylate, 3,4 epoxy butyl (meth) acrylate, and 3,4 epoxy cyclohexyl (meth) acrylate are mentioned, These may be used independently or may use 2 or more types together. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)
Acrylate is preferred.

As unsaturated monobasic acids, (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro,
Examples thereof include monocarboxylic acids such as cyano-substituted products, and these may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like.
More than one type may be used together. 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. It can also be hydrolyzed. Moreover, when an etrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be increased.

  As a method similar to the method (a), for example, a side chain of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group and one or more other monomers. There is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of a carboxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (b)]
As the method (b), an unsaturated ethylenic monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group with a side chain hydroxyl group of the obtained copolymer.

Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3
-Hydroxyalkyl (meth) acrylates such as 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or cyclohexanedimethanol mono (meth) acrylate may be mentioned. The above may be used together. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth) acrylate, (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 unsaturated ethylenic 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.

(Thermosetting resin)
Examples of the thermosetting resin used for the binder resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins, and phenol resins.

<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. A solvent can be included to facilitate formation.

  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- Methylformamide, 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 mono Ethyl 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.

  Among them, since the dispersion and dissolution of the pigment of the present invention and the salt-forming compound (A) are good, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether It is preferable to use glycol acetates such as acetate, aromatic alcohols such as benzyl alcohol, and ketones such as cyclohexanone. In particular, propylene glycol monomethyl ether acetate is more preferable from the viewpoint of health and safety and low viscosity.

These organic solvents can be used individually by 1 type or in mixture of 2 or more types. When it is set as 2 or more types of mixed solvents, it is preferable that said preferable organic solvent is contained 65 to 95 weight% in 100 weight part of the whole organic solvent. In particular, propylene glycol monomethyl ether acetate is preferably the main component, and specifically, it is preferably contained in an organic solvent used in the coloring composition in an amount of 65 to 100% by weight.
Moreover, since the organic solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment having a desired uniform film thickness, the amount of the organic solvent is 800 to 4000 parts by weight with respect to 100 parts by weight of the total colorant. It is preferable to use it.

<Method for producing colored composition>
The coloring composition of the present invention comprises a colorant containing a salt-forming compound (A) obtained by reacting a resin having a cationic group in the side chain with a quinophthalone-based acidic compound, and the resin, if necessary. Finely dispersed in a colorant carrier comprising a solvent, preferably together with a dispersing aid such as a pigment derivative, using various dispersing means such as a three roll mill, a two roll mill, a sand mill, a kneader, or an attritor. Can be manufactured. Further, when the salt-forming compound (A) is highly soluble, specifically, it is highly soluble in the solvent to be used. There is no need to manufacture.
The colored composition of the present invention can also be produced by mixing pigments, salt-forming compounds (A), and other colorants separately dispersed in a colorant carrier.

(Dispersing aid)
When dispersing the colorant in the colorant carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, and a surfactant can be appropriately used. The dispersion aid is excellent in dispersion of the colorant and has a large effect of preventing reaggregation of the colorant after dispersion. Therefore, a dispersion composition is used to disperse the colorant in the colorant carrier using the dispersion aid. When used, a color filter having a high spectral transmittance can be obtained.
In the present invention, the salt-forming compound (A) can also serve as a dispersion aid for the pigment used in combination.

  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, etc. can be used. These can be used alone or in combination of two or more.

  The blending amount 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, and most preferably 35 parts by weight or less with respect to 100 parts by weight of the colorant.

  The resin-type dispersant has a pigment-affinity part having a property of adsorbing to the colorant and a part compatible with the colorant carrier, and adsorbs to the colorant to stabilize dispersion in the colorant carrier. It works. 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 adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is 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- P104, P104S, 220S, 6919, or SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 1600 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS, or Bykumen. 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, 75 4,1101,120,150,1501,1502,1503, 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. May affect.

  The colored composition of the present invention can be used as a photosensitive colored composition for a color filter by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

<Photopolymerizable monomer>
Photopolymerizable monomers that can be used in the present invention include monomers or oligomers that are cured by ultraviolet rays or heat to produce transparent resins, and these may be used alone or in combination of two or more. Can do. The blending amount of the 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.

  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.

<Photopolymerization initiator>
In the coloring composition for a color filter of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, a photopolymerization initiator or the like is added to add a solvent developing type or an alkali developing type coloring. It can be adjusted in the form of a resist material. The blending amount when using the photopolymerization initiator is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the total amount of the colorant, and 10 to 150 parts by weight from the viewpoint of photocurability and developability. It is more preferable.

  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 benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-meth) Cyphenyl) -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-benzoyloxy) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 5 to 200% by weight based on the total amount of the colorant in the color filter coloring composition (100% by weight), and 10 from the viewpoint of photocurability and developability. More preferably, it is -150 weight%.

<Sensitizer>
Furthermore, the coloring composition for a color filter 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) benzophen Non, 4,4′-diethylaminobenzophenone and the like.

  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.

  Two or more kinds of sensitizers may be used in any ratio as required. The blending amount when using the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the total weight of the photopolymerization initiator contained in the colored composition, and is photocurable and developable. From the viewpoint, it is more preferably 5 to 50 parts by weight.

<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. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight in a total of 100% by weight of the coloring composition.

  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- D Ru-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 colored composition of the present invention can contain a storage stabilizer in order to stabilize the viscosity of the composition over 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 total amount 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, based on 100 parts by weight of the total amount of the colorant in the coloring composition.

<Removal of coarse particles>
The colored composition of the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, by means of centrifugation, sintered filter, membrane filter or the like. It is preferable to remove 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 comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment. Further, in addition to the three color filter segments, a yellow filter segment may be provided.
Preferably, at least one green filter segment is formed using the green pigment and / or the blue pigment and the coloring composition for a color filter of the present invention.
Further, at least one yellow filter segment is formed using the colored composition of the present invention, or preferably formed using a yellow pigment and the colored composition for a color filter of the present invention.

The blue filter segment can be formed using a normal blue coloring composition containing a blue pigment and a resin. Examples of the blue coloring composition include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78,
A blue pigment such as 79 is used.

  The blue coloring composition includes C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, Purple pigments such as 37, 39, 42, 44, 47, 49, and 50 can be used in combination.

  Moreover, a red filter segment can be formed using the normal red coloring composition containing a red pigment and resin. Examples of red coloring compositions include 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, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287 are used. Among them, C.I. I. Pigment Red 177, 179, 254 is preferably used.

  The red coloring composition includes C.I. I. Pigment orange 43, 71, or 73, and / or 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, 181 182,185,187,188,193,194,198,199,213,214,218,219,220, or yellow pigments such as 221, may be used in combination orange pigment.

  As the transparent substrate constituting the color filter, a glass plate such as soda lime glass, low alkali borosilicate glass or non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, or the like is used. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.

<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 filter segments by printing methods allows patterning by simply printing and drying the colored composition prepared as a printing ink, making it a low cost and excellent mass productivity as a color filter manufacturing method. Yes. 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. Further, it is important to control the fluidity of the ink on the printing press, and the viscosity of the ink 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 material, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can 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 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. In addition, 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.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. Unless otherwise specified, “parts” means “parts by weight”.

  The weight average molecular weight (Mw) of the acrylic resin is GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with a RI detector using a TSKgel column (manufactured by Tosoh Corporation), and tetrahydrofuran (THF) is used as a developing solvent. It is the weight average molecular weight (Mw) in terms of polystyrene measured. The specific surface area of the pigment particles was determined by the BET method using nitrogen adsorption. For the measurement, an automatic vapor adsorption amount measuring device (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) was used.

  First, acrylic resin solutions (binder resin components), fine pigments, quinoline acidic dyes, resins having a cationic group in the side chain, quinophthalone-based acidic compounds, salt-forming compounds (A), pigments used in Examples and Comparative Examples The manufacturing method of the dispersion, the blue resist material, and the red resist material will be described.

<Method for producing acrylic resin solution>
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. The methoxypropyl acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Acrylic resin solution 1 was prepared by addition.

<Production method of fine pigment>
(Preparation of blue fine pigment 1)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (“LIONOL BLUE ES” manufactured by Toyo Ink Manufacturing Co., Ltd., specific surface area 60 m 2 / g), 200 parts of sodium chloride, 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho). It knead | mixed at 80 degreeC 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. 190 parts of blue fine pigment 1 were obtained. The specific surface area of the blue fine pigment 1 was 80 m ² / g.

(Preparation of purple fine pigment 1)
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyo Ink Manufacturing 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 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. 190 parts of purple fine pigment 1 were obtained. The specific surface area of the purple fine pigment 1 was 95 m ² / g.

(Preparation of blue fine pigment 2)
A glass 4-necked flask was charged with 60.0 parts of phthalonitrile, 300 parts of 1-chloronaphthalene, and 15.6 parts of aluminum chloride, and stirred under reflux for 6 hours. Thereafter, heating was stopped, the mixture was allowed to cool to about 200 ° C., filtered while hot, and washed by sprinkling with 600 parts of hot toluene and 300 parts of acetone. The obtained wet cake was dispersed in 250 parts of toluene and stirred and refluxed for 3 hours. The mixture was again filtered while hot, sprinkled and washed with 600 parts of hot toluene and 300 parts of acetone, dispersed in 1500 parts of ion-exchanged water, and heated and stirred at 60 to 70 ° C. for 60 minutes. Filtration, washing with water and vacuum drying at 50 ° C. gave a blue solid aluminum phthalocyanine pigment (AlPc—Cl) having the desired structure. 30 parts of the obtained pigment were gradually dissolved in 1200 parts of concentrated sulfuric acid while keeping the temperature at about 5 ° C., and stirred at this temperature for 1 hour. This was added to 6000 parts of ice water with stirring so that the temperature did not exceed 5 ° C., and further stirred for 1 hour after the end of the addition. After filtration and washing with water, it was redispersed in 6500 parts of ion exchange water and filtered again. After washing with water, the wet cake was redispersed in 2500 parts of 4% aqueous ammonia and stirred under reflux for 6 hours. After filtration, the cake was washed with ion-exchanged water and then vacuum-dried at 50 ° C. to obtain a blue solid aluminum phthalocyanine pigment (AlPc—OH) having the desired structure.
50 parts of this (AlPc-OH) pigment, 150 parts of sodium chloride, and 25 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 6 hours. Next, the kneaded product is poured into 5 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. A blue fine pigment 2 was obtained. The obtained pigment had a volume average primary particle size of 28 nm and a specific surface area of 50 m ² / g.

(Preparation of green fine pigment 1)
Phthalocyanine green pigment C.I. I. CI Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC, specific surface area 45 m ² / g) was used as it was on the market. The specific surface area of the green fine pigment 1 was 45 m ² / g.

(Preparation of yellow fine pigment 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. 190 parts of yellow fine pigment 2 were obtained. The specific surface area of the yellow fine pigment 2 was 65 m ² / g.

(Preparation of yellow fine pigment 2)
Quinophthalone yellow pigment C.I. I. 200 parts of Pigment Yellow 138 (“Pariotol Yellow K0960-HD” 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 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. 190 parts of yellow fine pigment 3 were obtained. The specific surface area of the yellow fine pigment 3 was 67 m ² / g.

(Preparation of red fine pigment 1)
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“Chromophthalred A2B” manufactured by Ciba Japan Co., Ltd.), 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 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. 190 parts of red fine pigment 1 were obtained. The specific surface area of the red fine pigment 1 was 80 m ² / g.

(Preparation of red fine pigment 2)
Diketopyrrolopyrrole red pigment C.I. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals) 200 parts, 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. did. 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. 190 parts of red fine pigment 2 were obtained. The specific surface area of the red fine pigment 2 was 69 m ² / g.

<Method for producing quinoline acid dye>
(Acid dye B)
The solvent component in BASF acid dye, Basacid Yellow 099 Liquid was distilled off under reduced pressure, washed with ethanol, dried, pulverized and powdered to obtain acid dye B represented by the following chemical formula.

The acid dye B was identified by a mass spectrometer after being separated by a liquid chromatograph. About the measuring apparatus, it measured using Waters 2695 separations module (Waters 2695 separation module) as LC part, and Waters Micromass ZQ (Waters micromass ZQ) as MS part.
From the liquid chromatograph, the purity of the main component was 80% or more, and from mass spectrometry, it was confirmed that the detected mass peak was 402 derived from the formula weight of the anion.

<Method for preparing resin having cationic group in side chain>
(Preparation of resin 1 having a cationic group in the side chain)
Into a four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser, 67.3 parts of methyl ethyl ketone was charged and heated to 75 ° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2′-azobis (2,4-dimethylvaleronitrile) ) And 25.1 parts of methyl ethyl ketone were made uniform, charged in a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 6830, and then cooled to 50 ° C. To this solution, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, reacted at 50 ° C. for 2 hours, heated to 80 ° C. over 1 hour, and further reacted for 2 hours. Thus, Resin 1 having a cationic group in the side chain of 47% by weight of the resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

  Here, the weight average molecular weight (Mw) of the resin having a cationic group in the side chain was measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The ammonium salt value of the resin having a cationic group in the side chain was determined by titrating with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted into an equivalent amount of potassium hydroxide. It indicates the ammonium salt value of the solid content.

(Preparation of resin 2 having a cationic group in the side chain)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 62.4 parts of isopropyl alcohol and heated to 75 ° C. under a nitrogen stream. Separately, 32.1 parts of ethyl methacrylate, 25.1 parts of n-propyl methacrylate, 25.1 parts of lauryl methacrylate, 17.7 parts of methacryloylaminopropyltrimethylammonium chloride, 2,2′-azobis (2,4-dimethylvaleronitrile 5.7) and 15.6 parts of methyl ethyl ketone were made uniform, charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7420, and then cooled to 50 ° C. 72 parts of isopropyl alcohol was added to this solution to obtain a resin 2 having a cationic group in the side chain of 40% by weight of the resin component. The ammonium salt value of the obtained resin was 45 mgKOH / g.

(Preparation of resin 3 having a cationic group in the side chain)
A 4-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a condenser was charged with 82.0 parts of methyl ethyl ketone and heated to 75 ° C. under a nitrogen stream. Separately, 23.5 parts of ethyl methacrylate, 26.0 parts of t-butyl methacrylate, 25.0 parts of lauryl methacrylate, Kayamer PM-21 (manufactured by Nippon Kayaku Co., Ltd., 1 mol of ε-caprolaclone 1-hydroxyethyl methacrylate phosphate ester) ) 10.0 parts, diethylaminopropyl methacrylate 17.5 parts, 2,2′-azobis (2,4-dimethylvaleronitrile) 6.0 parts, and methyl ethyl ketone 25.6 parts, and then a dropping funnel Was attached to a four-necked separable flask and dropped over 2 hours. Two hours after the completion of dropping, it was confirmed that the polymerization yield was 98% or more from the solid content and the weight average molecular weight (Mw) was 7010, and then cooled to 50 ° C. Thus, Resin 3 having a cationic group in the side chain with a resin component of 48% by weight was obtained. The amine salt value of the obtained resin was 49 mgKOH / g.
Here, the amine value of the resin having a cationic group in the side chain was determined by potentiometric titration using a 0.1N aqueous hydrochloric acid solution, and then converted to an equivalent amount of potassium hydroxide.

<Method for producing quinophthalone-based acidic compound>
Prior to the method for producing a quinophthalone-based acidic compound, a method for identifying a quinophthalone-based acidic compound used in the present invention will be described.

(Identification method of quinophthalone acid compound)
A MALDI TOF-MS spectrum was used to identify the quinophthalone compound used in the present invention. The MALDI TOF-MS spectrum uses the MALDI mass spectrometer “autoflex III” manufactured by Bruker Daltonics, Inc. to identify the obtained compound with the coincidence between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. It was.

(Production of quinophthalone-based acidic compound (a))
To 100 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 82 parts of phthalic anhydride, and 93 parts of benzoic acid were added, heated to 180 ° C., and stirred for 6 hours while distilling off water. After cooling to room temperature, the reaction mixture was added to 1200 parts of methanol and stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, 900 parts of water and 150 parts of potassium hydroxide were added to the product, heated to 90 ° C., and stirred for 16 hours. After cooling to room temperature, 200 parts of 36% hydrochloric acid was added dropwise. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure. Subsequently, the product was added to 250 parts of methyl benzoate, 137 parts of a 4-sulfophthalic acid aqueous solution (50%) was further added, and the mixture was heated to 180 ° C. and stirred for 5 hours while distilling off water. After cooling to room temperature, the reaction mixture was added to 1400 parts of methanol and stirred at room temperature for 1 hour. Further, 450 parts of 35% hydrochloric acid was added to the above reaction mixture solution with stirring, and the mixture was stirred at room temperature for 1 hour. The precipitated crystals were separated by filtration, further washed with methanol, and dried under reduced pressure to obtain 107 parts of quinophthalone-based acidic compound (a) (yield: 85%). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (a).

(Production of quinophthalone-based acidic compound (b))
Similar to the production of the quinophthalone-based acidic compound (a) except that 53 parts of trimellitic anhydride was used instead of 137 parts of the 4-sulfophthalic acid aqueous solution (50%) used in the production of the quinophthalone-based acidic compound (a). Then, 103 parts (yield: 88%) of the quinophthalone-based acidic compound (b) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (b).

(Production of quinophthalone-based acidic compound (c))
Except for using 159 parts of tetrachlorophthalic anhydride instead of 82 parts of phthalic anhydride used in the production of the quinophthalone-based acidic compound (a), the same operation as in the production of the quinophthalone-based acidic compound (a) was performed, 143 parts of quinophthalone-based acidic compound (c) (yield: 89%) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (c).

(Production of quinophthalone-based acidic compound (d))
Except for using 159 parts of tetrachlorophthalic anhydride instead of 82 parts of phthalic anhydride used in the production of the quinophthalone-based acidic compound (b), the same operation as in the production of the quinophthalone-based acidic compound (b) was performed, 137 parts (yield: 90%) of quinophthalone-based acidic compound (d) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (d).

(Production of quinophthalone-based acidic compound (e))
Except for using 258 parts of tetrabromophthalic anhydride in place of 82 parts of phthalic anhydride used in the production of the quinophthalone-based acidic compound (a), the same operation as in the production of the quinophthalone-based acidic compound (a) was performed. 183 parts (yield: 89%) of an acidic compound (e) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (e).

(Production of quinophthalone-based acidic compound (f))
The quinophthalone series was used except that 77 parts of 6-sulfo-2,3-naphthalenedicarboxylic acid anhydride was used instead of 137 parts of the 4-sulfophthalic acid aqueous solution (50%) used in the production of the quinophthalone type acidic compound (a). The same operation as in the production of the acidic compound (a) was performed to obtain 121 parts (yield: 87%) of the quinophthalone-based acidic compound (f). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (f).

(Production of quinophthalone-based acidic compound (g))
Quinophthalone, except that 92 parts of 3,4,6-trichloro-5-sulfophthalic anhydride was used instead of 137 parts of the 4-sulfophthalic acid aqueous solution (50%) used in the production of the quinophthalone-based acidic compound (a). The same operation as in the production of the acidic compound (a) was performed to obtain 135 parts (yield: 89%) of the quinophthalone acidic compound (g). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (g).

(Production of quinophthalone-based acidic compound (h))
The quinophthalone series was used except that 146 parts of a 4-hydroxy-5-sulfophthalic acid aqueous solution (50%) was used instead of 137 parts of the 4-sulfophthalic acid aqueous solution (50%) used in the production of the quinophthalone-based acidic compound (a). Operation similar to manufacture of an acidic compound (a) was performed, and 107 parts (yield: 82%) of the quinophthalone type acidic compound (h) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (h).

(Production of quinophthalone-based acidic compound (i))
The quinophthalone-based acidic compound (a) was used except that 72 parts of 4-methoxy-5-sulfophthalic anhydride was used instead of 137 parts of the 4-sulfophthalic acid aqueous solution (50%) used in the production of the quinophthalone-based acidic compound (a). ) To give 111 parts (yield: 83%) of the quinophthalone-based acidic compound (i). As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (i).

(Production of quinophthalone-based acidic compound (j))
The same operation as in the production of the quinophthalone-based acidic compound (a) was performed except that 90 parts of 4-methylphthalic anhydride was used instead of the 82 parts of phthalic anhydride used in the production of the quinophthalone-based acidic compound (a). 110 parts (yield: 85%) of quinophthalone-based acidic compound (j) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (j).

(Production of quinophthalone-based acidic compound (k))
The same operation as in the production of the quinophthalone-based acidic compound (a) except that 130 parts of 4-trifluoromethylphthalic anhydride was used instead of the 82 parts of phthalic anhydride used in the production of the quinophthalone-based acidic compound (a). And 120 parts (yield: 84%) of the quinophthalone-based acidic compound (k) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (k).

(Production of quinophthalone-based acidic compound (l))
The same operation as in the production of the quinophthalone-based acidic compound (a) was performed except that 109 parts of 4-methoxyphthalic anhydride was used instead of the 82 parts of phthalic anhydride used in the production of the quinophthalone-based acidic compound (a). 108 parts (yield: 81%) of quinophthalone-based acidic compound (l) were obtained. As a result of mass spectrometry by TOF-MS, it was identified as the quinophthalone compound (l).

(Production of quinophthalone-based acidic compound (m))
The production of the quinophthalone-based acidic compound (a) except that 45 parts of 6-fluoro-8-aminoquinaldine was used instead of 40 parts of 8-aminoquinaldine used in the production of the quinophthalone-based acidic compound (a). The same operation was performed to obtain 114 parts (yield: 85%) of the quinophthalone-based acidic compound (m). As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (m).

(Production of quinophthalone-based acidic compound (n))
Similar to the production of the quinophthalone-based acidic compound (a) except that 59 parts of 6-phenyl-8-aminoquinaldine was used instead of the 40 parts of the aminoquinaldine used in the production of the quinophthalone-based acidic compound (a). Then, 123 parts (yield: 85%) of quinophthalone-based acidic compound (n) was obtained. As a result of mass spectrometry by TOF-MS, it was identified as a quinophthalone compound (n).

<Method for Producing Salt-Forming Compound (A)>
(Salt-forming compound (A-1))
The salt-forming compound (A-1) that can be obtained by the reaction of the quinophthalone-based acidic compound (a) and the resin 1 having a cationic group in the side chain was produced by the following method.
The resin 1 having a cationic group in the side chain of 51 parts was added to 2000 parts of water, sufficiently stirred and mixed, and then heated to 60 ° C. to prepare a resin solution. On the other hand, an aqueous solution in which 10 parts of the quinophthalone-based acidic compound (a) was dissolved in 90 parts of water was prepared and added dropwise to the previously prepared resin solution. After completion of dropping, the reaction was carried out by stirring at 60 ° C. for 120 minutes. The end point of the reaction was judged to be that the salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared was the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 33 parts of the salt-forming compound (A-1) Got. The content of the effective pigment component derived from the quinophthalone-based acidic compound (a) in the obtained salt-forming compound (A-1) was 33% by weight.

(Salt-forming compounds (A-2) to (A-14))
Except that the quinophthalone-based acidic compound (a) used in the production of the salt-forming compound (A-1) was changed to the quinophthalone-based acidic compound shown in Table 1, it was the same as the salt-forming compound (A-1) described above. Salt-forming compounds (A-2) to (A-14) were obtained. Table 1 shows the yield of the obtained salt-forming compound and the content of the effective pigment component derived from each quinophthalone-based acidic compound.

(Salt Forming Compound (A-15))
A salt-forming compound (A-15) that can be obtained by the reaction of the quinophthalone-based acidic compound (a) and the resin 2 having a cationic group in the side chain was produced by the following method.
The resin 2 having a cationic group in the side chain of 88 parts was added to 2000 parts of a 10% aqueous methanol solution, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. to prepare a resin solution. On the other hand, an aqueous solution in which 10 parts of the quinophthalone-based acidic compound (a) was dissolved in 90 parts of water was prepared and added dropwise to the previously prepared resin solution. After completion of dropping, the reaction was carried out by stirring at 60 ° C. for 120 minutes. The end point of the reaction was judged to be that the salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared was the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 44 parts of the salt-forming compound (A-15) ) At this time, the content of the effective pigment component derived from the quinophthalone-based acidic compound (a) in the salt-forming compound (A-15) was 24% by weight.

(Salt-forming compounds (A-16) to (A-18))
Except for changing the quinophthalone-based acidic compound (a) used in the production of the salt-forming compound (A-15) to the quinophthalone-based acidic compound shown in Table 2, the same manner as the salt-forming compound (A-15) described above. Salt-forming compounds (A-16) to (A-18) were obtained. Table 2 shows the yield of the obtained salt-forming compound and the content of the effective pigment component derived from each quinophthalone-based acidic compound.

(Salt Forming Compound (A-19))
A salt-forming compound (A-19) that can be obtained by the reaction of the quinophthalone-based acidic compound (a) and the resin 3 having a cationic group in the side chain was produced by the following method.
The resin 3 having a cationic group in the side chain of 63.2 parts was added to 2000 parts of 20% acetic acid, and the mixture was sufficiently stirred and mixed, and then heated to 60 ° C. to ammonium chloride of the tertiary amino group of the side chain. Went. On the other hand, an aqueous solution in which 10 parts of the quinophthalone-based acidic compound (a) was dissolved in 90 parts of water was prepared and added dropwise little by little to the above-mentioned ammonium chloride resin solution. After completion of dropping, the reaction was carried out by stirring at 60 ° C. for 120 minutes. The end point of the reaction was judged to be that the salt-forming compound was obtained with the reaction solution dropped onto the filter paper and the point where the bleeding disappeared was the end point. After cooling to room temperature with stirring, suction filtration is performed, and after washing with water, the salt-forming compound remaining on the filter paper is dried by removing moisture with a dryer, and 39 parts of the salt-forming compound (A-19) ) At this time, the content of the effective pigment component derived from the quinophthalone-based acidic compound (a) in the salt-forming compound (A-19) was 25% by weight.

(Salt-forming compounds (A-20) to (A-23))
Except for changing the quinophthalone-based acidic compound (a) used in the production of the salt-forming compound (A-19) to the quinophthalone-based acidic compound shown in Table 3, the same as the salt-forming compound (A-19) above. Thus, salt-forming compounds (A-20) to (A-23) were obtained. Table 3 shows the yield of the obtained salt-forming compound and the content of the effective pigment component derived from each quinophthalone-based acidic compound.

<Method for producing pigment dispersion>
(Preparation of pigment dispersion (DP-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. And a pigment dispersion (DP-1) was produced.

Blue fine pigment 1 (CI Pigment Blue 15: 6): 11.0 parts acrylic resin solution 1: 40.0 parts propylene glycol monomethyl ether acetate (PGMAC): 48.0 parts Resin-type dispersant (Ciba Japan) "EFKA4300"): 1.0 part

  Hereinafter, pigment dispersions (DP-2 to 8) were produced in the same manner as the pigment dispersion (DP-1) except that the pigments were changed to the pigments shown in Table 4.

<Method for producing blue resist material>
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a blue resist material (B-1).

Pigment dispersion (DP-1): 48.0 parts Pigment dispersion (DP-2): 12.0 parts Acrylic resin solution 1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (Shin-Nakamura Chemical Co., Ltd.) "NK ester ATMPT"
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan): 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts propylene glycol monomethyl ether acetate (PGMAC) : 23.2 parts

<Method for producing red resist material>
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a red resist material (R-1).

Pigment dispersion (DP-7): 6.8 parts Pigment dispersion (DP-8): 53.2 parts Acrylic resin solution 1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (Shin Nakamura Chemical Co., Ltd.) "NK ester ATMPT"
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan): 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts propylene glycol monomethyl ether acetate (PGMAC) : 23.2 parts

[Example 1]
(Preparation of colored composition (DA-1))
The following mixture was stirred and mixed so as to be uniform, and then filtered through a 5.0 μm filter to prepare a colored composition (DA-1).

Salt-forming compound (A-1): 11.0 parts Acrylic resin solution 1: 40.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

[Examples 2 to 22, Comparative Example 1]
(Preparation of colored composition (DA-2 to DA-22, DC-1))
Hereinafter, except that the salt-forming compound (A-1) was changed to the salt-forming compound (A) or the acid dye B shown in Table 5, the colored composition (DA-1) was used in the same manner as the colored composition (DA-1). DA-2 to DA-22, DC-1) were prepared. Table 5 shows the content of the effective pigment component at this time.
Here, the pigment content A represents the effective pigment component content (% by weight) in the salt-forming compound (A) or the acidic dye B, and the pigment content B represents the effective pigment component content ( (% By weight).

(Coating foreign material test method)
A colored composition or a pigment dispersion was applied on a transparent substrate so that the dried coating film became 2.0 μm, and heated in an oven at 230 ° C. for 20 minutes to obtain a test substrate. The surface of the obtained test substrate was observed using a metal microscope “BX60” manufactured by Olympus System. The magnification was set to 500 times, and the number of particles of the coating film foreign matter that could be observed in any five visual fields by transmission was measured. The evaluation criteria are shown below.

A: Less than 5 (very good)
○: 5 or more, less than 20 (good)
Δ: 20 or more and less than 100 (no problem in use)
×: 100 or more (coating unevenness (spots) due to foreign matter occurs, causing problems in use)

Table 6 shows the evaluation results.

(Spectral evaluation)
A colored composition or a pigment dispersion is applied to a transparent substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm using a spin coater, then dried at 70 ° C. for 20 minutes, and then heated at 220 ° C. for 20 minutes and allowed to cool. Thus, a coated substrate was produced. The prepared coated substrate was subjected to heat treatment at 220 ° C. so that the transmittance at a wavelength of 450 nm was 5%, and the transmittance of the coated film at a wavelength of 550 nm was measured with a microspectrophotometer (“OSP-” manufactured by Olympus Optical Co., Ltd.). SP100 "). The higher the transmittance at 550 nm, the better the brightness. The evaluation criteria are shown below.

○: 99% or more (good)
Δ: 97 or more and less than 99% (defect)
X: Less than 97% (very poor)

Table 6 shows the evaluation results.

From the results of Table 6, by treating with a resin having a cationic group in the side chain, the quinophthalone-based acidic compound was solubilized, and the substrate evaluation showed very good results with little foreign matter. However, acid dye B (Comparative Example 1) that is not treated with a resin having a cationic group in the side chain is difficult to use because a large amount of foreign matter is generated in the coating film.
The colored compositions containing the salt-forming compound (A) all showed excellent spectral characteristics, whereas the conventionally known DP-5 to DP-6 (Comparative Examples 2 to 3) were coated foreign matter. Although the test was extremely good or good, the spectral evaluation was poor or very poor.

[Example 23]
(Preparation of resist material G-1)
The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 μm filter to obtain a green resist material.

Pigment dispersion (DP-3): 6.0 parts Colored composition (DA-1): 54.0 parts Acrylic resin solution 1: 11.0 parts Trimethylolpropane triacrylate: 4.2 parts (Shin Nakamura Chemical Co., Ltd.) "NK ester ATMPT"
Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan): 1.2 parts sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.): 0.4 parts propylene glycol monomethyl ether acetate (PGMAC) : 23.2 parts

[Examples 24 to 52, Comparative Examples 4 to 10]
(Preparation of resist materials G-2 to 31, Y-1 to 6)
Hereinafter, the resist materials (G-2 to 31, Y-1 to Y-1) are the same as the resist material G-1, except that the coloring composition and the pigment dispersion are changed to the total amount of 60 parts as shown in Table 7. 6) was obtained.

(Evaluation of resist material)
Each evaluation shown below was performed about Y (brightness), the coating-film foreign material, heat resistance, light resistance, and solvent resistance of the obtained resist material (G-1 to 31 and Y-1 to 6). The test results are shown in Table 8.

(Y (brightness) evaluation)
A resist material was applied to a glass substrate, and the substrate was heated at 230 ° C. for 20 minutes. Thereafter, the brightness (Y) of the obtained substrate was measured using a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The resist material was applied by changing the film thickness depending on the color,
The resist materials G-1 to 31 have film thicknesses such that x = 0.264 and y = 0.600 in the C light source, and the resist materials Y-1 to 6 have x = 0.440 and y = 0.506. A resist material was applied to such a film thickness as follows.

(Coating foreign material test method)
A resist material is applied on a transparent substrate so that the dry coating thickness is about 2.5 μm, and the whole surface is exposed to ultraviolet light with an integrated light amount of 150 mJ / cm ² using an ultra-high pressure mercury lamp, and then heated at 230 ° C. in an oven. An evaluation substrate was obtained by heating and cooling for 20 minutes. The surface of the obtained test substrate was observed using a metal microscope “BX60” manufactured by Olympus System. The magnification was 500 times, and the number of particles that could be confirmed in any five visual fields by transmission was measured. The evaluation criteria are shown below.

A: Less than 5 (very good)
○: 5 or more, less than 20 (good)
Δ: 20 or more and less than 100 (no problem in use)
×: 100 or more (coating unevenness (spots) due to foreign matter occurs, causing problems in use)

(Method of coating heat resistance test)
A resist material was applied on the transparent substrate so that the dried coating film was about 2.5 μm, and UV exposure was performed with an integrated light quantity of 150 mJ / cm ² using a super high pressure mercury lamp through a mask having a predetermined pattern. Thereafter, an alkaline developer was sprayed by spraying to dissolve and remove the uncured portion, thereby creating a desired pattern (test substrate). As an alkaline developer, sodium carbonate 1.5% by mass, sodium hydrogen carbonate 0.5% by mass, an anionic surfactant (“Perex NBL” manufactured by Kao Corporation) 8.0% by mass, and water 90% by mass. What was used. Next, after heating in an oven at 230 ° C. for 20 minutes and allowing to cool, the chromaticity 1 (L * (1), a * (1), b * (1)) with a C light source is microscopically measured for the obtained test substrate. Measurement was performed using a spectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). Further, the same test substrate was heated in an oven at 250 ° C. for 1 hour, and chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source was measured.
Using the measured chromaticity 1 and chromaticity 2, the color difference ΔEab * was calculated by the following calculation formula, and the heat resistance of the coating film was evaluated in the following four stages.

ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)

○: ΔEab * is less than 2.5 (good)
Δ: ΔEab * is 2.5 or more and less than 5.0 (no problem in use)
×: ΔEab * is 5.0 or more (defect)

(Method of coating light resistance test)
A test substrate was prepared in the same procedure as the coating film heat resistance test. Next, with respect to the obtained test substrate, the chromaticity 1 (L * (1), a * (1), b * (1)) with a C light source was changed to a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.). ). Further, the same test substrate was irradiated with light for 500 hours with a light resistance tester (“SUNTEST CPS +” manufactured by TOYOSEIKI), then the substrate was taken out, and the chromaticity 2 (L * (2), a * (2) with a C light source was removed. ), B * (2)). The color difference ΔEab * was calculated in the same manner as the coating film heat resistance test, and the light resistance of the coating film was evaluated according to the same evaluation criteria as the heat resistance.

(Method of coating solvent resistance test)
A test substrate was prepared in the same procedure as the heat resistance test, and a chromaticity 1 (L * (1), a * (1), b * (1)) with a C light source was measured with a microspectrophotometer (Olympus Optical Co., Ltd. “ OSP-SP200 "). Thereafter, the substrate was immersed in N-methylpyrrolidone at 25 ° C. for 30 minutes. After removing the substrate, measure chromaticity 2 (L * (2), a * (2), b * (2)) with a C light source, and calculate the color difference ΔEab * in the same manner as the coating film heat resistance test. Then, the solvent resistance of the coating film was evaluated according to the same evaluation criteria as the heat resistance.

The resist materials (G-1 to 4, 7 to 28, Y-1 to 4) of Examples 23 to 48 have extremely good brightness and coating film foreign matter evaluation, and are related to heat resistance, light resistance, and solvent resistance. Also good results.
On the other hand, the resist materials (G-33, Y-5) of Comparative Examples 6 and 9 were difficult to actually use because there were many foreign substances. The resist materials (G-5, 6, 30, 31, Y-6) of Comparative Examples 4, 5, and 7 to 10 had lower brightness (Y) than the examples.

  The lightness evaluation of the examples was better than the lightness evaluation of the comparative example. Specifically, in green, the brightness was maintained and improved when compared between examples using the same pigment dispersion (Comparison with Examples 23 to 26 and Comparative Examples 4 and 5, and Examples 27 to 48). And a comparison with Comparative Examples 6 to 8), a difference of 2.5% or more was observed. In addition, even in yellow, the brightness is maintained and improved by 1.5% or more, and it can be said that this difference is remarkably excellent.

[Example 65]
(Color filter (CF-1))
A black matrix is patterned on a glass substrate, and a red resist material (R-1) is applied onto the substrate with a spin coater to a film thickness such that x = 0.640, y = 0.340. A colored coating was formed. The coating was irradiated with 300 mJ / cm ² of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development is performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to dissolve and remove the unexposed portions, and then the substrate is washed with ion-exchanged water. Formed. In the same manner, the green resist material (G-7) is formed to a thickness such that x = 0.264 and y = 0.600, and x = 0.150 using the blue resist material (B-1). Each was applied to a film thickness such that y = 0.060, and a green filter segment and a blue filter segment were formed to obtain a color filter (CF-1).

(Production of liquid crystal display device)
A transparent ITO electrode layer was formed on the obtained RGB color filter, and a polyimide alignment layer was formed thereon. A color display device was produced on the other surface of this glass substrate in combination with a three-wavelength CCFL light source of a polarizing plate. Formed. On the other hand, a TFT array and a pixel electrode were formed on one surface of another (second) glass substrate, and a polarizing plate was formed on the other surface. The two glass substrates prepared in this manner are arranged to face each other so that the electrode layers face each other, and are aligned using spacer beads while keeping the distance between the two substrates constant, and an opening for injecting a liquid crystal composition The periphery was sealed with a sealant so as to leave After injecting the liquid crystal composition from the opening, the opening was sealed. A liquid crystal display device thus produced was combined with a three-wavelength CCFL light source of a backlight unit to produce a color display device.

[Examples 53 to 55, Comparative Examples 11 and 12]
(Color filter (CF-2 to 5))
Hereinafter, the color filters (CF-2˜) of Examples 53 to 55 and Comparative Examples 11 and 12 were combined with the resist material shown in Table 9 and the three-wavelength CCFL light source by the same method as the production of the color filter (CF-1). 5) and a color display device were produced.

  Thereafter, in the obtained color display device, a light source was emitted to display a color image, and the brightness of each color filter segment portion was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.). The results are shown in Table 9.

  The lightness evaluation of the examples was better than the lightness evaluation of the comparative example. Specifically, when Example 53 and Comparative Example 11 are compared, the color filter (CF-1) formed from the color filter coloring composition containing the salt-forming compound (A) of the present invention is conventionally used. Compared with the filter segment containing the pigment, the brightness of the green filter segment was improved. As a result, the brightness of the white display was improved by 2% or more, and the performance as a color filter was confirmed. This difference was remarkably excellent. It can be said that it is a difference.

Further, when Examples 54 and 55 are compared with Comparative Example 12, the color filter formed with the color filter coloring composition containing the salt-forming compound (A) of the present invention is a filter containing a conventionally used pigment. Compared to the segment, the brightness of the color filter (CF-4) containing at least one filter segment (yellow) containing the salt-forming compound (A) of the present invention is improved, and as a result, the brightness of white display is 1.5% or more. It was confirmed that the color filter performance was improved.
Furthermore, when both the green and yellow compounds (A-3) of the present invention contain the salt-forming compound (A) (CF-3), it was confirmed that the brightness was further improved, and as a result, the brightness of white display was improved by 2% or more. Is a remarkably excellent difference.
From the above results, by using the salt-forming compound (A) of the present invention, the lightness of the color filter can be remarkably improved and can be preferably used.

Claims (10)

A color filter coloring composition comprising at least a colorant, a binder resin, and an organic solvent, wherein the colorant is a resin having a cationic group in a side chain and a quinophthalone represented by the following general formula (1): A coloring composition for a color filter, which is a salt-forming compound (A) which can be obtained by reacting with an acidic compound.

[In the general formula _{(1), R 1 ~ R} 5 are each independently a hydrogen atom, a halogen atom, an alkyl group optionally substituted by a halogen atom, an aryl group or an alkoxyl group.
R _{6 to} R ₉ represent a hydrogen atom.
R ₁₀ , R ₁₂ and R ₁₃ each independently represent a hydrogen atom, a halogen atom, a hydroxyl group or an alkoxyl group, and R ₁₁ represents —SO ₃ H. ] The coloring composition for a color filter according to claim 1, wherein R ₁ to R ₅ are each independently a hydrogen atom or a halogen atom. The color composition for a color filter according to claim 1 or 2, wherein the resin having a cationic group in the side chain is an acrylic resin containing a structural unit represented by the following general formula (2).

[In General Formula (2), R ₁₄ represents a hydrogen atom or an unsubstituted alkyl group. R _{15 to} R ₁₇ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, or an aryl group. R _{15 to} R ₁₇ may combine with each other to form a ring. Q represents an alkylene group, an arylene group, —CONH—R ₁₈ —, or —COO—R ₁₈ —. R ₁₈ represents an alkylene group. Y ⁻ represents an inorganic or organic anion. ]   The coloring composition for a color filter according to any one of claims 1 to 3, wherein the colorant further contains a pigment.   The colored composition for a color filter according to claim 4, wherein the pigment is at least one selected from the group consisting of a green pigment, a blue pigment, a red pigment, and a yellow pigment.   The green coloring composition for a color filter according to claim 5, wherein the green pigment contains a polyhalogenated phthalocyanine pigment and / or the blue pigment contains an aluminum phthalocyanine pigment.   The coloring composition for a color filter according to any one of claims 1 to 6, wherein the organic solvent contains propylene glycol monomethyl ether acetate as a main component.   Furthermore, the coloring composition for color filters of any one of Claims 1-7 containing a photopolymerizable monomer and / or a photoinitiator.   A color filter comprising a red filter segment, a green filter segment, and a blue filter segment, wherein the at least one filter segment is formed by the color filter coloring composition according to any one of claims 1 to 8. .   In a color filter comprising a red filter segment, a green filter segment, a blue filter segment, and a yellow filter segment, at least one filter segment is formed of the coloring composition for a color filter according to any one of claims 1 to 8. Color filter.