JP2018169505A - Coloring composition for color filter - Google Patents

Abstract

The present invention relates to a coloring composition for a color filter which has a low viscosity even when containing a high concentration of pigment, is excellent in dispersion stability, particularly has good storage stability, and has high coloring power and high contrast. And a filter segment formed using the object to provide a color filter with high contrast. A coloring composition for a color filter comprising an isoindoline pigment having a by-product content of 3% by weight or less, a dye derivative, a pigment dispersant, and a binder resin. The by-product is a compound represented by a specific formula. [Selection figure] None

Description

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

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

Therefore, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used. The color filter is mainly produced by the following two methods. Is manufactured.
In the first method, a photosensitive coloring composition in which a pigment is dispersed in a photosensitive transparent resin solution is applied to a transparent substrate such as glass, and after removing the solvent by drying, pattern exposure of one filter color is performed. Next, the unexposed area is removed in the development process to form a pattern of the first color, and a process such as heating is applied as necessary, and then the same operation is sequentially repeated for all filter colors to produce a color filter. is there.

  In the second method, a colored composition in which a pigment is dispersed in a transparent resin solution is applied to a transparent substrate such as glass, and the solvent is removed by drying to form a pigment-dispersed coating film. A resist such as a mold resist is applied, pattern exposure of one filter color is performed, a resist pattern is formed by development, and this is used as an etching resist to remove the pigment-dispersed coating film with no resist pattern attached with an etching solution Then, the resist coating film is peeled off to form a first color pattern. This is a method for producing a color filter by repeating the same operation for all the filter colors in sequence after applying heat treatment or the like as necessary. Note that the development of the resist and the etching of the pigment-dispersed coating film can be performed simultaneously.

In the production of such a color filter, the dispersibility of the pigment in the coloring composition is important, and when a color filter is produced using a coloring composition with low dispersibility, hue failure, reduction in contrast, increase in viscosity, Cause sediment. Regarding dispersibility, it is described in Patent Document 1 that the greater the amount of by-products contained in the pigment, the better the dispersibility, but on the other hand, it has an adverse effect on sediment and coloring power. It has been confirmed.
Therefore, it has been a problem to improve dispersibility while the content of by-products is smaller.

JP 63-161061 A

As described above, there are increasing demands on the physical properties of coloring compositions used in the production of color filters, such as dispersion stability, storage stability, coloring power, and coating uniformity when forming filter segments. However, it has become difficult to cope with conventional pigments. In particular, in recent years, liquid crystal display devices have been applied to television monitor applications, and high-density color filters containing a large amount of pigment are required to produce panels.
Therefore, the present invention provides a coloring composition for color filters that has a low viscosity even when containing a high concentration of pigment, is excellent in dispersion stability, particularly has good storage stability, and provides high coloring power and high contrast. The present invention aims to provide a color filter having a high contrast by forming a filter segment using the filter segment.

（式中、Ｘは、Ｏ、またはＮＨを表す。Ｒ₁〜Ｒ₄はそれぞれ独立に、水素原子、置換基を有してもよいアルキル基、置換基を有してもよいアリール基、置換基を有してもよい脂環基、置換基を有してもよいアラルキル基、置換基を有してもよい複素環基、置換基を有してもよいアルコキシ基、置換基を有してもよいアリールオキシ基、置換基を有してもよいアルキルチオ基、置換基を有してもよいアリールチオ基、置換基を有してもよいアルキルアミノ基、置換基を有してもよいジアルキルアミノ基、置換基を有してもよいアリールアミノ基、置換基を有してもよいジアリールアミノ基、ハロゲン原子、ニトロ基、スルホン酸基、カルボキシル基、ホルミル基、置換基を有してもよいフタルイミドメチル基、または置換基を有してもよいスルホンアミド基を表す。） The present invention provides a coloring composition for a color filter comprising an isoindoline pigment having a by-product content of 5% by weight or less, a dye derivative, a pigment dispersant, and a binder resin. In addition, the present invention relates to a coloring composition for a color filter, wherein the by-product is a compound represented by the following general formula (1).

(In the formula, X represents O or NH. R _{1 to} R ₄ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An alicyclic group which may have a group, an aralkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, and a substituent Aryloxy group which may have a substituent, alkylthio group which may have a substituent, arylthio group which may have a substituent, alkylamino group which may have a substituent, dialkyl which may have a substituent An amino group, an arylamino group which may have a substituent, a diarylamino group which may have a substituent, a halogen atom, a nitro group, a sulfonic acid group, a carboxyl group, a formyl group, or a substituent A good phthalimidomethyl group or an optionally substituted substituent It represents a Hon'amido group.)

  The present invention also relates to the above color filter coloring composition, wherein the weight ratio of by-product / pigment derivative is in the range of 0.05 to 0.6.

  The present invention also relates to the above color filter coloring composition, wherein the isoindoline pigment is C.I. Pigment Yellow 185 pigment.

  The present invention also relates to the above color filter coloring composition, further comprising a photopolymerization initiator and / or a photopolymerization initiator.

Moreover, this invention relates to the color filter characterized by including the filter segment formed from the said coloring composition for color filters.

The coloring composition for a color filter of the present invention enables dispersion stability and sediment control by controlling the content of the compound represented by the general formula (1), which is a by-product during pigment synthesis, The coating film formed using this coloring composition has high coloring power.
And the color filter which comprises a filter segment with high coloring power can be manufactured by using the coloring composition for color filters of this invention.

First, the coloring composition for a color filter of the present invention will be described.
The coloring composition for a color filter of the present invention comprises at least a pigment carrier comprising a transparent resin, a precursor thereof or a mixture thereof, an organic pigment, and a compound represented by the above general formula (1). To do.
Among the compounds represented by the above general formula (1), the compound in which X is NH is a cyanomethyl amidomethyl and 1,3-diiminoisoindoline compound at a pH of 8 to 11 and a temperature of 10 to 100 ° C. It can synthesize | combine by making it react under.
In addition, among the compounds represented by the general formula (1), a compound in which X is O can be obtained by heating a compound in which X is NH, for example, in an acetic acid aqueous solution.

Here, when it illustrates about R < ₁ > -R < ₄ > in General formula (1), there exist a fluorine, chlorine, a bromine, an iodine etc. as a halogen atom in R < ₁ > -R < ₄ > in General formula (1).
Examples of the alkyl group which may have a substituent include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group, and stearyl. Group, 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2- There are ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group and the like.
As the aryl group which may have a substituent, phenyl group, naphthyl group, anthranyl group, p-methylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl Group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group And 2-aminoanthraquinolyl group.

Examples of the alicyclic group which may have a substituent include a cyclopentyl group, a 2,5-dimethylcyclopentyl group, a cyclohexyl group, a 4-tert-butylcyclohexyl group and an adamantyl group.
Examples of the aralkyl group which may have a substituent include a benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group and the like. There is.
Examples of the heterocyclic group that may have a substituent include a pyridinyl group, a 3-methylpyridinyl group, a pyrazinyl group, a pipedinyl group, an N-methylpipedinyl group, a pyranyl group, a morpholinyl group, an n-methylpyrrolinyl group, and an acridinyl group. is there.
Examples of the alkoxy group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutyloxy group, a tert-butyloxy group, a neopentyloxy group, and an 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-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group and the like.

As the aryloxy group which may have a substituent, a phenoxy group, a naphthoxy group, an anthranyloxy group, a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, Examples include pentafluorophenoxy group and 2-methyl-4-chlorophenoxy group.
Examples of the alkylthio group which may have a substituent include methylthio group, ethylthio group, propylthio group, isopropylthio group, n-butylthio group, isobutylo group, tert-butylthio group, neopentylthio group, n-hexylthio group, n -There is an octylthio group.
Examples of the arylthio group which may have a substituent include a phenylthio group, a naphthylthio group, a p-methylphenylthio group, a p-nitrophenylthio group, and a p-methoxyphenylthio group.

Examples of the alkylamino group which may have a substituent include a methylamino group and an ethylamino group.
Examples of the dialkylamino group which may have a substituent include a dimethylamino group, a dimethylamino group, a diisopropyl group, and a cyclohexylamino group.
Examples of the arylamino group which may have a substituent include a phenylamino group, a p-nitrophenylamino group, and a 4-methylphenylamino group.
Examples of the diarylamino group which may have a substituent include a diphenylamino group and a di (4-methoxyphenyl) amino group.
Examples of the phthalimidomethyl group which may have a substituent include a 4-nitrophthalimidomethyl group and a tetrachlorophthalimidomethyl group.
R _{1 to} R ₄ are not limited to these.

  The test method for measuring the pigment precursor and its by-product concentration in the pigment as defined in the present invention is shown below. 95 g of MEK (methyl ethyl ketone) was added to 5 g of the pigment, and the mixture was placed in an ultrasonic bath for 6 hours. After the pigment and the liquid were filtered off with a filter having a pore size of 1 μm or less, the pigment on the filter was washed with 50 g of MEK, and the pigment on the filter paper was dried at 100 ° C. for 1 hour. Pigment precursor and its by-product concentration in the pigment = (pigment weight before treatment (5 g) −pigment weight after drying (g)) / pigment weight before treatment (5 g) By-product concentration was defined.

  The isoindoline pigment in the present invention is not particularly limited as a method for reducing the concentration of the pigment precursor and its by-products in the pigment. I. Pigment Yellow 185 is preferably prepared by washing with a solvent in order to obtain a pigment having a lower impurity concentration. The cleaning solvent used in the present invention can be freely selected as long as it is a solvent that does not dissolve the pigment itself but dissolves the pigment precursor and its by-products.

Specific examples of the cleaning solvent include alcohols, ether alcohols, ethers, ketones, carboxylic acid amides, carboxylic acid esters, and mixtures thereof. Specific examples include:
Aliphatic and araliphatic, mono- or polyhydric alcohols having up to 10 carbon atoms, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, amyl alcohol, isoamyl alcohol, Hexanol, isohexanol, heptanol, octanol, 2-ethylhexanol, ethylene glycol, 1,2-propylene glycol, and 1,3-propylene glycol, cyclohexanol, methylcyclohexanol, benzyl alcohol, and 2-phenylethanol;
Mono-C2 -C3 -alkylene glycol mono-C1 -C4 -alkyl ether, and di-C2 -C3 -alkylene glycol mono-C1 -C4 -alkyl ether, such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol Monobutyl ether, and diethylene glycol monomethyl ether, and diethylene glycol monoethyl ether;
Acyclic and cyclic aliphatic ethers having up to 10 carbon atoms, such as dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether;
Acyclic and cycloaliphatic and araliphatic ketones having up to 10 carbon atoms, such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, diethyl ketone, methyl isopropyl ketone, methyl isobutyl Ketones, cyclopentanone, cyclohexanone, methylcyclohexanone, acetophenone, and propiophenone;
Amides, and C1-C4 alkylamides of aliphatic carboxylic acids having up to 4 carbon atoms, such as formamide, N, N-dimethylformamide, and N, N-diethylformamide, N, N-dimethylacetamide, and N , N-diethylacetamide, N, N-dimethylpropionic acid amide, and N, N-diethylpropionic acid amide, and N-methylpyrrolidone;
Aromatic carboxylic acid esters having a total of up to 12 carbon atoms, such as dimethyl phthalate and diethyl phthalate.

  In this case, it is preferable to use a solvent that can be easily removed after the pigment washing and in the post-treatment.

Particularly preferred solvents are methanol, ethanol, propanol, isopropanol, butanol, isobutanol, t-butanol, amyl alcohol, isoamyl alcohol, hexanol, isohexanol, heptanol, octanol, 2-ethylhexanol, ethylene glycol, 1,2-propylene Glycols, and alcohols such as 1,3-propylene glycol, cyclohexanol, methylcyclohexanol, benzyl alcohol, and 2-phenylethanol, dipropyl ether, diisopropyl ether, dibutyl ether, diisobutyl ether, tetrahydrofuran, dioxane, diethylene glycol dimethyl ether, and Acyclic and cyclic, such as diethylene glycol diethyl ether Aliphatic ethers, acetone, methyl ethyl ketone, methyl propyl ketone, ketones such as methyl butyl ketone, diethyl ketone, methyl isopropyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, methylcyclohexanone, acetophenone, and propiophenone.
These solvents are preferable because they have high solubility for impurities other than pigments and can be easily removed by post-treatment.

  You may perform the said washing | cleaning once or 2 times or more as needed.

The isoindoline pigment in the present invention is not only washed with the above solvent to lower the concentration of the pigment precursor and its by-products in the pigment, but also with water, dilute acetic acid solution, dilute sulfuric acid solution, dilute phosphoric acid solution, dilute hydrochloric acid. You may wash | clean with a solution. Thereby, the pigment precursor and its by-product density | concentration in a pigment can further be reduced.
Below, the specific example of the organic pigment which can be used for the coloring composition for color filters of this invention is shown with a color index number.

<Colorant>
The colorant that can be used in the coloring composition of the present invention can be arbitrarily selected from conventionally known various pigments and dyes. The following are typical pigments and dyes that can be used in the present invention.

  Examples of red pigments that can be used in the present invention include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202, 206, 207, 208,209,210,216,220,221,224,226,242,246,254,255,264,270,272,273,274,276,277,278,279,280,281,2 2,283,284,285,286,287 or diketopyrrolopyrrole pigment described in JP-T 2011-523433 discloses the like, but not particularly limited thereto. Red dyes such as xanthene, azo, disazo, anthraquinone, and dipyrromethene can also be used. Specifically, C.I. I. Examples thereof include salt-forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  Examples of the orange pigment that can be used in the present invention include C.I. I. Pigment Orange 38, 43, 71, 73, etc. are mentioned, but it is not particularly limited to these.

Examples of yellow pigments that can be used in the present invention include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147, 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 quinophthalone pigment described in Japanese Patent No. 4999326 Although it is mentioned, it is not particularly limited to these. Also, yellow dyes such as quinoline, azo, methine, coumarin, and isoindoline can be used.

  Examples of the green pigment that can be used in the present invention include C.I. I. Zinc phthalocyanine described in CI Pigment Green 7, 10, 36, 37, 58, JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, International Publication No. 2015/118720, etc. Examples thereof include, but are not particularly limited to, pigments, and aluminum talocyanine pigments described in Japanese Patent No. 4893859. In addition, blue-green dyes such as triarylmethane, phthalocyanine, and squarylium can be used.

  Examples of blue pigments that can be used in the present invention include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, JP 2004-333817, Examples include aluminum phthalocyanine pigments described in Japanese Patent No. 4893859, but are not limited thereto.

  Purple pigments that can be used in the present invention include, for example, 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, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned, but not limited thereto.

  The coloring composition for a color filter of the present invention includes metal oxides such as titanium dioxide, iron oxide, antimony pentoxide, zinc oxide, and silica, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc, and yellow lead. Inorganic pigments such as carbon black can also be used.

  The preferred colorant content in all the non-volatile components of the colored composition according to the present invention is 10 to 90% by weight, more preferably 15 to 85% by weight from the viewpoint of sufficient color reproducibility and stability. Most preferably, it is 20 to 80% by weight.

Inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean (red iron (III) oxide), cadmium red, ultramarine, bitumen, chromium oxide green, cobalt green, amber And synthetic iron black. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability and the like while maintaining a balance between saturation and lightness.
The colorant used in the present invention contains the pigment, but in addition, for color matching, a dye may be contained within a range in which the heat resistance is not lowered.

In the coloring composition for a color filter of the present invention, the compound represented by the general formula (1) is preferably contained in a proportion of 0.1 to 5 parts by weight or less, more preferably 100 parts by weight of the organic pigment. It is more preferably 3 parts by weight or less, and more preferably 0.5 to 1.5 parts by weight with respect to 100 parts by weight of the organic pigment from the viewpoint of storage stability and coloring power. If the content of the compound represented by the general formula (1) is less than the above range, the pigment dispersion stabilizing effect is not sufficiently exhibited. Conversely, if the content is more than the above range, the hue of the filter segment is unfavorable. The possibility of change arises, and the production cost is also a problem.

As described above, the pigment carrier in which the organic pigment and the compound represented by the general formula (1) are dispersed is composed of a transparent resin, a precursor thereof, or a mixture thereof. The transparent resin is a resin having a 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. Transparent resins include resin-type dispersants, thermoplastic resins, thermosetting resins, and photosensitive resins, and precursors thereof include monomers or oligomers that cure upon irradiation to produce transparent resins. These can be used alone or in admixture of two or more.

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

  As a site | part with high affinity to a dispersion medium of the resin type dispersing agent of this invention, the at least 1 sort (s) of polymer unit chosen from polyester, polyether, and poly (meth) acrylate is preferable.

  For example, as polyester, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol 1,4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, One or more alcohols such as glycerin or hexanetriol, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid ,Guru Conic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexa And polyester polyols obtained by cocondensation with one or more carboxylic acids such as tricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid.

  For example, as the polyether, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexane Diol, 1,4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol , Alcohols such as glycerin or hexanetriol, ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether Others include modified polyether polyols and the like obtained by ring-opening polymerization of various (cyclic) ether bond-containing compounds such as allyl glycidyl ether.

  For example, as poly (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, oxetane (meth) acrylate, etc. Alkoxypolyalkylene glycol (meth) acrylates such as xypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate, (meth) acrylamide, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meta) ) N-substituted (meth) acrylamides such as acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl ( Examples include homopolymers and copolymers such as amino group-containing (meth) acrylates such as (meth) acrylate and nitriles such as (meth) acrylonitrile. These may be used alone or in combination, or may be in the form of a block polymer, graft polymer or random polymer.

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

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

As a site | part with high affinity to a dispersion medium of the resin type dispersing agent of this invention, the at least 1 sort (s) of polymer unit chosen from polyester, polyether, and poly (meth) acrylate is preferable.

For example, as polyester, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol 1,4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, One or more alcohols such as glycerin or hexanetriol, succinic acid, adipic acid, sebacic acid, azelaic acid, phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid ,Guru Conic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehycarboxylic acid, 1,2,4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexa And polyester polyols obtained by cocondensation with one or more carboxylic acids such as tricarboxylic acid or 2,5,7-naphthalenetricarboxylic acid.

For example, as the polyether, ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexane Diol, 1,4-bis (hydroxymethyl) cyclohesan, bisphenol A, hydrogenated bisphenol A, hydroxypivalylhydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol , Alcohols such as glycerin or hexanetriol, ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether Others include modified polyether polyols and the like obtained by ring-opening polymerization of various (cyclic) ether bond-containing compounds such as allyl glycidyl ether.

For example, as poly (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (Meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, oxetane (meth) acrylate, etc. Alkoxypolyalkylene glycol (meth) acrylates such as xypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate, (meth) acrylamide, and N, N-dimethyl (meth) acrylamide, N, N-diethyl (meta) ) N-substituted (meth) acrylamides such as acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl ( Examples include homopolymers and copolymers such as amino group-containing (meth) acrylates such as (meth) acrylate and nitriles such as (meth) acrylonitrile. These may be used alone or in combination, or may be in the form of a block polymer, graft polymer or random polymer.

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

As the resin-type dispersant, an acidic resin-type dispersant having an aromatic carboxyl group is particularly preferable, a polymer having a hydroxyl group at one end, an aromatic tricarboxylic acid anhydride and / or an aromatic tetracarboxylic acid dianhydride. Most preferably, the dispersant is obtained by reacting with. Examples of such resin-type dispersants include Japanese Patent No. 40201050, Japanese Patent Application Laid-Open No. 2007-140487, International Publication No. 2008/007776, Japanese Patent Application Laid-Open No. 2010-163500, and Japanese Patent Application Laid-Open No. 2010-223888. And exhibits excellent effects such as compatibility between fluidity and dispersibility.

Among these, a preferable resin-type dispersant is a radical polymerization of an ethylenically unsaturated monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule described in WO2008 / 007776 pamphlet. A polyester dispersant produced by reacting a hydroxyl group in a vinyl copolymer having two hydroxyl groups in one terminal region with an acid anhydride group in tetracarboxylic dianhydride is preferable. More preferably, the polyester dispersant is characterized in that the tetracarboxylic dianhydride contains an aromatic tetracarboxylic dianhydride. Color filter coloring compositions using these polyester dispersants are preferable because they are excellent in pigment dispersion stability, and are synthesized using the method described in WO2008 / 007776 pamphlet or the like. be able to.

Moreover, as a preferable resin type dispersing agent, the resin type dispersing agent shown by the following formula as described in Unexamined-Japanese-Patent No. 2007-140487 etc. is mentioned.
_{(HOOC-) m -R 14 - (} - COO - [- R 16 -COO-] q -R 15) t
[Wherein R ₁₄ is a tetravalent tetracarboxylic acid compound residue, R ₁₅ is a monoalcohol residue, R ₁₆ is a lactone residue, m is 2 or 3, q is an integer of 1 to 50, and t is (4 -M). ]

A coloring composition for a color filter using an acidic resin type dispersant having an aromatic carboxyl group has very excellent pigment dispersion stability.

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

Examples of the photosensitive resin include (meth) acrylic compounds having a reactive substituent such as an isocyanate group, an aldehyde group, and an epoxy group on a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group, A resin obtained by reacting an acid and introducing a photocrosslinkable group such as a (meth) acryloyl group or a styryl group into the linear polymer is used. Further, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. Half-esterified products are also used.
The content of the transparent resin is preferably 30 to 700 parts by weight and more preferably 60 to 450 parts by weight with respect to 100 parts by weight of the organic pigment. If the content of the transparent resin is less than 30 parts by weight, the developing performance is lowered, and if it exceeds 700 parts by weight, it is not preferable from the viewpoint of causing curability of the coloring composition and poor hue.

Monomers and oligomers that are precursors of transparent resins include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, trimethylolpropane tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, melamine (meth) acrylate, various acrylic esters such as epoxy (meth) acrylate and methacrylic acid Examples include esters, (meth) acrylic acid, styrene, vinyl acetate, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, and acrylonitrile.
The content of the monomer and oligomer is preferably 10 to 300 parts by weight with respect to 100 parts by weight of the organic pigment, more preferably 10 to 200 parts by weight from the viewpoint of photocurability and developability. Particularly preferred is 15 to 150 parts by weight. When the content of the monomer and oligomer is more than 300 parts by weight, it is not preferable because the shape of the filter segment is poor, and when it is less than 10 parts by weight, the photocurability is insufficient, which is not preferable.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Acetophenone photopolymerization initiators such as hydroxycyclohexyl phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl Benzoin photopolymerization initiators such as ether and benzyldimethyl ketal, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzene Benzophenone photopolymerization initiators such as zoyl-4′-methyldiphenyl sulfide, thioxanthone light such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Polymerization initiator, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloro) Methyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4 -Bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis ( Lichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, Triazine photopolymerization initiators such as 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, borate photopolymerization initiators, carbazole photopolymerization initiators, imidazole photopolymerization initiators, and the like are used. .
The content of the photopolymerization initiator used in the color filter coloring composition is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the organic pigment, and is 10 to 10 from the viewpoint of photocurability and developability. More preferably, it is 150 parts by weight. When the content of the photopolymerization initiator is more than 200 parts by weight, it is not preferable because the shape of the filter segment is poor, and when it is less than 5 parts by weight, the photocurability is insufficient.

The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone. , Camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone, etc. It can also be used together.
The content of the sensitizer used in the color filter coloring composition is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the color composition, and is photocurable. From the viewpoint of developability, it is more preferably 5 to 50 parts by weight. When the content of the sensitizer is less than 3 parts by weight, there is a possibility that sufficient photocurability may not be obtained, and when it is more than 60 parts by weight, it is not preferable because it causes a defective shape of the filter segment. .

  The coloring composition for a color filter of the present invention is a method of dispersing an organic pigment in a pigment carrier solution, or a method of mixing an organic pigment in water or an organic solvent to prepare a pigment dispersion and then mixing with the pigment carrier solution. Manufactured by. The method for dispersing the pigment is not particularly limited, but a method using a bead mill, a sand mill, a ball mill, a three roll mill, a two roll mill or the like is preferable. The organic pigment and the compound represented by the general formula (1) can be separately dispersed in the pigment carrier solution and then mixed. However, in order to improve the dispersibility of the organic pigment, the organic pigment is dispersed. It is preferable to add a compound represented by the general formula (1).

When the coloring composition for color filter contains two or more kinds of pigments, etc., the coloring composition is mixed with two or more kinds of pigments, and then the resulting pigment mixture is finely divided in a pigment carrier by a known method. It can be dispersed and manufactured. Moreover, the coloring composition for color filters can also be produced by mixing finely dispersed pigments in a pigment carrier.
When the organic pigment is dispersed in the pigment carrier, a dispersion aid such as a surfactant or a dye derivative can be appropriately used. The dispersion aid can be used in an amount of 0.1 to 40 parts by weight with respect to 100 parts by weight of the organic pigment.

  Surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl Anionic surfactants such as triethanolamine sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate; Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene ether Nonionic surfactants such as kill 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. These can be used alone or in admixture of two or more.

Moreover, the coloring composition for color filters of this invention can contain a pigment derivative and / or a dispersing agent.
The pigment derivative is a compound represented by the following general formula (2), and there are those having a basic substituent and those having an acidic substituent.
Formula (2)
AB
A: Organic pigment residue B: Basic substituent or acidic substituent

  In the formula (2), the organic pigment constituting the organic pigment residue of A includes diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, polyazo, copper phthalocyanine, halogenated copper phthalocyanine, metal-free phthalocyanine, etc. Phthalocyanine pigments, aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone, anthraquinone pigment, quinacridone pigment, dioxazine pigment, perinone pigment, perylene pigment, thioindigo Pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, selenium pigments, metal complex pigments, and the like.

式（４）

式（５）

式（６）

In the formula (2), examples of the basic substituent of B include substituents represented by the following formula (3), formula (4), formula (5), and formula (6). , Substituents represented by formula (7), formula (8), and formula (9).
Formula (3)

Formula (4)

Formula (5)

Formula (6)

式（８）

式（９）

Formula (7)

Formula (8)

Formula (9)

X: represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ — or a direct bond.
n represents an integer of 1 to 10.
R ₁ and R ₂ : each independently an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, an optionally substituted phenyl group, or R ₁ and R ₂ together represent an optionally substituted heterocycle containing an additional nitrogen, oxygen or sulfur atom.
R ₃ represents an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group.
R ₄ , R ₅ , R ₆ , R ₇ : each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or a substituent Represents an optionally substituted phenyl group.

Y: represents —NR ₈ —Z—NR ₉ — or a direct bond.
R ₈ and R ₉ are each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, or an optionally substituted phenyl group. Represents.
Z: represents an optionally substituted alkylene group having 1 to 36 carbon atoms, an optionally substituted alkenylene group having 2 to 36 carbon atoms, or an optionally substituted phenylene group.
R: represents a substituent represented by the formula (10) or a substituent represented by the formula (11).
Q: A hydroxyl group, an alkoxyl group, a substituent represented by the formula (10) or a substituent represented by the formula (11).

式（１１）

Formula (10)

Formula (11)

M: represents a hydrogen atom, calcium atom, barium atom, strontium atom, manganese atom or aluminum atom.
i: represents the valence of M.
R ₁₀ , R ₁₁ , R ₁₂ , R ₁₃ : each independently a hydrogen atom, an optionally substituted alkyl group having 1 to 36 carbon atoms, an optionally substituted alkenyl group having 2 to 36 carbon atoms, substitution Represents an optionally substituted phenyl group or polyoxyalkylene group.

  Examples of the amine component used to form the substituents represented by formula (3) to formula (6), formula (10), and formula (11) include dimethylamine, diethylamine, N, N-ethylisopropyl, and the like. Amine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine, N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, disec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine, diisoamylamine, dihexylamine, di (2-ethylhexyl) amine, dioctylamine N, N-methyloctadecylamine, didecyl Min, diallylamine, N, N-ethyl-1,2-dimethylpropylamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine, N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N -Diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N Methyl-laurylaminopropylamine, N, N-ethyl-hexylaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecholine, 3-pipecoline, 4-pipecoline, 2,4-lupetidine, 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonicopetinate, ethyl isonicopetinate, 2-piperidineethanol, Pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecoline, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecoline, N-aminopropyl- 4-Pipecoline, N-aminopropylmorpholine, N-methylpiperazine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like can be mentioned.

  The amine component used to form the sulfonic acid amine salt of formula (9) may be any of primary, secondary, tertiary and quaternary amines. For example, primary amines have side chains. Hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, nonadecylamine, Examples thereof include amines such as eicosylamine, or unsaturated amines corresponding to the number of carbon atoms.

Secondary, tertiary and quaternary amines include dioleylamine, distearylamine, dimethyloctylamine, dimethyldecylamine, dimethyllaurylamine, dimethylstearylamine, dilaurylmonomethylamine, trioctylamine, dimethyldidodecylammonium chloride, Dimethyl dioleyl ammonium chloride, dimethyl didecyl ammonium chloride, dimethyl dioctyl ammonium chloride, trimethyl stearyl ammonium chloride, dimethyl distearyl ammonium chloride, trimethyl decyl ammonium chloride, trimethyl hexadecyl ammonium chloride, trimethyl octadecyl ammonium chloride, dimethyl dodecyl tetradecyl ammonium chloride , Dimethyl hexadecyl octadec Ammonium chloride, and the like.
Further, when any of R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ in the formula (9) represents a polyoxyalkylene group, examples thereof include a polyoxyethylene group and a polyoxypropylene group.

  Furthermore, in the coloring composition for a color filter of the present invention, an organic pigment is sufficiently dispersed in a pigment carrier and applied on a transparent substrate such as a glass substrate so that the dry film thickness is 0.5 to 3.0 μm. In order to facilitate the formation of the filter segment, a solvent can be contained. Examples of the solvent include cyclohexanone, ethyl cellosolve acetate, butyl cellosolve acetate, 1-methoxy-2-propyl acetate, diethylene glycol dimethyl ether, ethylbenzene, ethylene glycol diethyl ether, xylene, ethyl cellosolve, methyl-n-amyl ketone, propylene glycol monomethyl ether toluene, Examples include methyl ethyl ketone, ethyl acetate, methanol, ethanol, isopropyl alcohol, butanol, isobutyl ketone, petroleum solvent, and the like. These may be used alone or in combination. The solvent can be used in an amount of 800 to 4000 parts by weight with respect to 100 parts by weight of the organic pigment.

  The coloring composition for color filter of the present invention can be prepared in the form of gravure offset printing ink, waterless offset printing ink, silk screen printing ink, solvent development type or alkali development type colored resist material. The colored resist material is composed of a pigment carrier, a thermosetting resin, a thermoplastic resin or a photosensitive resin and a monomer, and if necessary, a composition containing a photopolymerization initiator, an organic pigment, and a general formula (1) The compound shown is dispersed.

The organic pigment is preferably contained in a coloring composition containing a solvent in a ratio of 1 to 7% by weight when the filter segment is formed by a photolithography method, and when the filter segment is formed by a printing method. In the coloring composition containing a solvent, it is contained in a proportion of 1 to 50% by weight. In any case, the organic pigment is preferably contained in the final filter segment (solid content of the coloring composition) in a proportion of 10 to 55% by weight, more preferably 20 to 50% by weight, with the remainder depending on the pigment carrier. It consists essentially of the resinous binder provided.
The colored composition for a color filter of the present invention is a coarse particle of 5 μm or more, preferably a coarse particle of 1 μm or more, more preferably a particle of 0.5 μm or more by means of centrifugation, a sintered filter, a membrane filter or the like. It is preferable to remove the mixed dust.

Next, the color filter of the present invention will be described.
The color filter of the present invention comprises one or a plurality of color filter segments formed using the colored composition for color filter of the present invention on a transparent or reflective substrate. ), G (green), and B (blue) filter segments, and Y (yellow), M (magenta), and C (cyan) filter segments. . The filter segment of each color can be formed by a printing method or a photolithography method.

As the transparent substrate, a glass plate such as quartz glass, borosilicate glass, alumina silicate glass, soda lime glass whose surface is coated with silica, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate is used.
As the reflective substrate, silicon or a substrate in which an aluminum, silver, silver / copper / palladium alloy thin film or the like is formed on the transparent substrate is used.

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

  When each color filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied to a transparent or reflective substrate by spray coating, spin coating, slit coating, roll coating. By a coating method such as the above, the coating is applied so that the dry film thickness is 0.2 to 5 μm, and is dried as necessary to form a pigment-dispersed coating film. Next, ultraviolet exposure is performed through a mask having a predetermined pattern in contact with or non-contact with the film. Then, after immersing in a solvent or an alkaline developer, or spraying the developer with a spray 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 alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like in addition to the above method, but the color filter coloring composition of the present invention can be used in any method. The electrodeposition method uses a transparent conductive film formed on a transparent or reflective substrate to produce a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. Is the method.
The transfer method is a method in which a colored composition layer is previously formed on the surface of a peelable transfer base sheet, and the colored composition layer is transferred to a desired transparent or reflective substrate.

  If the black matrix is formed in advance before forming the filter segment on the transparent substrate or the reflective substrate, the contrast ratio of the liquid crystal display panel can be further increased. 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 a filter segment may be formed. By forming the filter segment on the TFT substrate, the aperture ratio of the liquid crystal display panel can be increased and the luminance can be improved.

On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary.
The color filter and the counter substrate are bonded together using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by pasting together.
Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically compensated bend (OCB). It can be used for a liquid crystal display mode in which colorization is performed using a color filter.

  Hereinafter, the present invention will be described by way of examples. In the examples, “parts” and “%” represent “parts by weight” and “% by weight”, respectively.

(Production example 1 of isoindoline pigment)
10 parts of a 40% methylamine methanol solution were added to 14.7 parts of ethyl cyanoacetate, and the mixture was heated and stirred at the boiling point for 2 hours. After cooling to 50 ° C., 300 parts of methanol and 19 parts of 1,3-diiminoisoindoline were added, and the mixture was further stirred at 50 ° C. for 2 hours, and then cooled to room temperature. Washing was performed 3 times with 100 parts of methanol to obtain a product (A) which is an isoindoline pigment intermediate.

(Identification by-product production example 2)
19 parts of barbituric acid dissolved in 1000 parts of a 60% aqueous acetic acid solution was added to 30 parts of the product (A) obtained in Production Example 1 and reacted at 70 to 90 ° C., and then cooled to room temperature. After washing with water, an isoindoline pigment A containing a by-product (B) having the following structure was obtained. The isoindoline pigment A was further washed with water to obtain an isoindoline pigment B.

The compounds obtained in Production Examples 1 and 2 were identified by ¹ H-NMR and LC / MS, and it was confirmed that the target compounds were obtained.

(Production example 2 of isoindoline pigment)
After adding 2000 ml of methyl ethyl ketone to 100 g of the isoindoline pigment A, the mixture was stirred at 60 ° C. for 12 hours. After the pigment was filtered off, the press cake was dried at 70 ° C. in an air forced circulation drying shelf and pulverized with an atomizer (mesh size: 0.8 mm) to prevent agglomeration, whereby isoindoline pigment C shown in Table 1 was obtained.
Further, it was further washed with methyl ethyl ketone to obtain isoindoline pigment D shown in Table 1.
Similarly, Pigment A was washed twice with methanol instead of methyl ethyl ketone to obtain isoindoline pigment E shown in Table 1, and isoindoline pigment F was obtained by washing once with methanol.

(Production Method of Dispersant X1-1)
(Dispersant X1-1 solution)
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 100 parts of methyl methacrylate, 100 parts of n-butyl acrylate, and 40 parts of propylene glycol monomethyl ether acetate were charged and replaced with nitrogen gas. After heating the inside of the reaction vessel to 80 ° C. and adding 12 parts of 3-mercapto-1,2-propanediol, 0.2 part of 2,2′-azobisisobutyronitrile is divided into 20 portions. It was added every minute and reacted for 12 hours at 80 ° C., and it was confirmed by solid content measurement that 95% had reacted. Next, 30 parts of pyromellitic anhydride, 190 parts of propylene glycol monomethyl ether acetate, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst were added. Reacted for hours. It was confirmed by titration that 98% or more of the acid anhydride had been half-esterified, and the reaction was completed. In this way, a dispersant X1-1 solution having a poly (meth) acrylate skeleton having an acid value of 63 mgKOH / g per solid content and a nonvolatile content of 40% by weight and having an aromatic carboxyl group was obtained.

(Preparation of acrylic resin solution)
Put 800 parts of cyclohexanone in a reaction vessel, heat to 100 ° C. while injecting nitrogen gas into the vessel, and at the same temperature, 60.0 parts of methacrylic acid, 65.0 parts of methyl methacrylate, 65.0 parts of butyl methacrylate from the dropping tube. A mixture of 60.0 parts of 2-hydroxyethyl methacrylate and 10.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to carry out the polymerization reaction. After the dropwise addition, the mixture was further reacted at 80 ° C. for 3 hours, then 2.0 parts of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 80 ° C. for 1 hour to obtain a weight average molecular weight. A solution of about 40,000 acrylic resin was obtained.
After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20%. An acrylic resin solution was prepared.

[Examples 1-6 and Comparative Examples 1-6]

(Preparation of colored composition 1 (YP-1))
After isoindoline pigment A is stirred and mixed so as to be uniform with the following mixture, it is dispersed for 5 hours with Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm. Then, the mixture was filtered through a 5.0 μm filter to prepare Colored Composition 1 (RP-1).
Hereinafter, solid content weight is shown.
Isoindoline pigment A 9.60 parts Dye derivative 2.4 parts Dispersant (X1-1) 8.5 parts Acrylic resin solution 1 11.5 parts Propylene glycol monomethyl ether acetate 68.0 parts

A colored composition (YP-2 to 11) was obtained in the same manner as in Example 1 except that the blending amounts of the pigment and the derivative were changed.

<Evaluation of coloring composition>
Evaluation of the viscosity, sediment, coloring power, and contrast of the obtained colored compositions (YP-1 to 11) was performed by the following methods. Table 3 shows the evaluation results.

(Viscosity evaluation)
The viscosity of the coloring composition (YP-1 to 11) and the viscosity after standing at 40 ° C. for 7 days were measured using an E-type viscometer (“R110” manufactured by Toki Sangyo Co., Ltd.).
The viscosity was evaluated in the following four stages.
◎: Change rate is less than 10% ○: Change rate is 10% or more and less than 20% △: Change rate is 20% or more and less than 50% ×: Change rate is 50% or more

(Evaluation of sediment)
20 ml of the colored composition (YP-1 to 11) was collected in a screw tube, allowed to stand at room temperature for 3 days, and then visually checked for the presence or absence of a precipitate. The sediment was evaluated in the following four stages.
◎: No sediment ○: Very small amount of sediment △: Small amount of sediment ×: Large amount of sediment

(Evaluation of coloring power)
Using a spin coater, the coloring composition (YP-1 to 11) is placed on a glass substrate having a thickness of 100 mm × 100 mm and a thickness of 1.1 mm so that the chromaticity x (C) = 0.455 is the center value. A three-level coated substrate was produced by changing the rotation speed. Drying conditions were performed at 70 ° C. for 20 minutes after coating and further at 230 ° C. for 30 minutes. Furthermore, the contrast of the substrate and the chromaticity with the C light source were measured, and the film thickness at the chromaticity x (C) = 0.455 was obtained from the three points of data by the primary correlation method. The film thickness was evaluated in the following four stages.
◎: Less than 0.75μ ○: 0.75μ or more, less than 1μ △: 1μ or more, less than 1.25μ ×: 1.25μ or more

(Contrast evaluation)
Contrast measurement was performed using the substrate used in the coloring power measurement.
Contrast was evaluated in the following four stages. ◎: 1000 or more ○: 500 or more, less than 1000 Δ: 100 or more, less than 500 ×: Less than 100

  As shown in Table 2, Examples 1 to 5, which are coloring compositions having a by-product content in the range of 5% by weight or less, which is a feature of the present invention, have viscosity stability, sediment, and coloring power. There was no x evaluation for any of the contrast items, and the result was very good.

On the other hand, with respect to Comparative Examples 1 to 6 in which the content of the by-product exceeds 5% by weight, the sediment and the coloring power were significantly inferior to the examples of the present invention.

[Examples 6 to 10, Comparative Examples 7 to 12]
(Green photosensitive coloring composition (YR-1 to 11))
After stirring and mixing the mixture of the composition and blending amount (parts by weight) shown in Table 3 so as to be uniform, the mixture was filtered with a 1.0 μm filter to obtain photosensitive coloring compositions (YR-1 to 11). .
In addition, it was set as the green photosensitive coloring composition (YR-1 to 11) corresponding to the yellow coloring composition (YP-1 to 11), respectively.

<Evaluation of photosensitive coloring composition>
The obtained photosensitive coloring compositions (YR-1 to 11) were evaluated for viscosity, sediment, coloring power and contrast by the following methods. Table 4 shows the evaluation results.

(Viscosity evaluation)
The viscosity of the coloring composition (YR-1 to 11) and the viscosity after standing at 40 ° C. for 7 days were measured using an E-type viscometer (“R110” manufactured by Toki Sangyo Co., Ltd.).
The viscosity was evaluated in the following four stages.
◎: Change rate is less than 10% ○: Change rate is 10% or more and less than 20% △: Change rate is 20% or more and less than 50% ×: Change rate is 50% or more

(Evaluation of sediment)
20 ml of the colored composition (YR-1 to 11) was collected in a screw tube, allowed to stand at room temperature for 3 days, and then the presence or absence of sediment was confirmed by visual observation. The sediment was evaluated in the following four stages.
◎: No sediment ○: Very small amount of sediment △: Small amount of sediment ×: Large amount of sediment

(Evaluation of coloring power)
Using a spin coater, the coloring composition (YR-1 to 11) is placed on a glass substrate of 100 mm × 100 mm and 1.1 mm thickness so that the chromaticity x (C) = 0.455 becomes a center value. A three-level coated substrate was produced by changing the rotation speed. Drying conditions were performed at 70 ° C. for 20 minutes after coating and further at 230 ° C. for 30 minutes. Furthermore, the contrast of the substrate and the chromaticity with the C light source were measured, and the film thickness at the chromaticity x (C) = 0.455 was obtained from the three points of data by the primary correlation method. The film thickness was evaluated in the following four stages.
A: Film thickness of less than 2.2 μm B: Film thickness of 2.2 μm or more, less than 2.5 μm Δ: Film thickness of 2.5 μm or more, less than 2.8 μm ×: Film thickness of 2.8 μm or more

(Contrast evaluation)
Contrast measurement was performed using the substrate used in the coloring power measurement. The contrast was evaluated according to the following four levels.
◎: 1000 or more ○: 500 or more, less than 1000 △: 100 or more, less than 500 ×: less than 100

  As shown in Table 4, Examples 7 to 11 using colored compositions (YP1 to 5) having a by-product content of 5% by weight or less, which is a feature of the present invention, are viscosity stable. No evaluation was made for any of the items, sediment, coloring power and contrast, and the results were very good.

Claims (5)

A coloring composition for a color filter, comprising: an isoindoline pigment having a by-product content of 5% by weight or less; a dye derivative; a pigment dispersant; and a binder resin. A coloring composition for a color filter, wherein the product is a compound represented by the following general formula (1).

(In the formula, X represents O or NH. R _{1 to} R ₄ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. An alicyclic group which may have a group, an aralkyl group which may have a substituent, a heterocyclic group which may have a substituent, an alkoxy group which may have a substituent, and a substituent Aryloxy group which may have a substituent, alkylthio group which may have a substituent, arylthio group which may have a substituent, alkylamino group which may have a substituent, dialkyl which may have a substituent An amino group, an arylamino group which may have a substituent, a diarylamino group which may have a substituent, a halogen atom, a nitro group, a sulfonic acid group, a carboxyl group, a formyl group, or a substituent A good phthalimidomethyl group or an optionally substituted substituent It represents a Hon'amido group.) The coloring composition for a color filter according to claim 1, wherein the by-product / pigment derivative weight ratio is in the range of 0.05 to 0.6.
  The colored composition for a color filter according to claim 1 or 2, wherein the isoindoline pigment is C.I. Pigment Yellow 185 pigment.   Furthermore, the coloring composition for color filters of any one of Claims 1-3 containing a photoinitiator and / or a photoinitiator.   A color filter comprising a filter segment formed from the colored composition for a color filter according to claim 1.