JP2021054964A - Phthalocyanine pigment, coloring composition, photosensitive coloring composition, and color filter - Google Patents

Abstract

To provide a phthalocyanine pigment that gives a coloring composition having excellent brightness, contrast, voltage retention rates, and storage stability. when used in a color filter.SOLUTION: A phthalocyanine pigment is represented by the following formula (X and Y each denote a halogen atom; n is 4-16; m is 1-10).SELECTED DRAWING: None

Description

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to obtain a coloring composition which is excellent in brightness, contrast and voltage retention when used in a color filter, generates less foreign matter in a coating film, has low viscosity and is excellent in storage stability. The present invention relates to a phthalocyanine pigment, a coloring composition using the phthalocyanine pigment, a photosensitive coloring composition using the coloring composition, and a color filter.

In recent years, most display devices such as televisions, computer monitors, and smartphones are occupied by liquid crystal display devices. In the liquid crystal display device, the liquid crystal layer sandwiched between the two polarizing plates controls the degree of deflection of the light passing through the first polarizing plate, and controls the amount of light passing through the second polarizing plate. It is displayed by doing so. The liquid crystal display device can display colors by providing a color filter between the two polarizing plates.

The color filter consists of two or more fine band-shaped filter segments having different hues arranged in parallel or intersecting each other on the surface of a transparent substrate such as glass, or fine filter segments arranged in a constant vertical and horizontal arrangement. Consists of things. The filter segments are as fine as several microns to several hundreds of microns, and are arranged in a predetermined arrangement for each hue.

Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film is formed on the transparent electrode for orienting the liquid crystal in a certain direction. There is. In order to obtain sufficient performance of these transparent electrodes and alignment films, it is generally necessary to form them at a high temperature of 200 ° C. or higher. Therefore, organic pigments having excellent heat resistance and light resistance are mainly used as colorants in color filters.

The color filter has optical characteristics such as high brightness, which is the performance to make the display screen of the liquid crystal display device brighter, and high contrast, which is the performance to make the display screen more clearly visible. is necessary.

If a color filter with low brightness is used, the screen becomes dark with low light transmittance, and in order to obtain a bright screen, it is necessary to increase the number of backlights as light sources. Therefore, in recent years, with the viewpoint of low power consumption and the thinning of televisions and smartphones, further increase in brightness of color filters has been required.

In addition, if a color filter with low contrast is used, the degree of deflection controlled by the liquid crystal is disturbed, and the transmitted light leaks when the light must be blocked or transmitted when the light must be transmitted. The screen becomes blurry due to attenuation. Therefore, in recent years, with the increase in size of televisions, there is a demand for higher contrast of color filters.

For the above optical characteristics, an organic pigment having a primary particle size of several tens of nm is generally used. However, when the primary particle size of the organic pigment is reduced, the specific surface area is increased, so that the cohesive force between the organic pigment particles is increased and the secondary aggregation is likely to occur. Therefore, the coloring composition for a color filter using a finely divided organic pigment tends to have low dispersion stability, and a problem occurs in the color filter manufacturing process. Therefore, an organic pigment having high brightness and contrast as well as high dispersion stability is required.

Against the background as described above, regarding the increase in brightness of the green filter, for example, in Patent Document 1, the conventional C.I. I. A novel green pigment having a specific hue to replace Pigment Greens 7 and 36, zinc phthalocyanine brominated, is disclosed. However, the new green pigment is a conventional C.I. I. The brightness was improved as compared with Pigment Greens 7 and 36, but it was not sufficient. Further, since the new green pigment is ionized with phthalocyanine radicals by irradiation with light under low oxygen, there is a problem that the voltage retention rate (hereinafter, also referred to as VHR) is lowered and the drive of the liquid crystal display element is adversely affected. ..

Regarding increasing the contrast of the green filter, for example, Patent Document 2 discloses aluminum halide phthalocyanine in which aluminum, which is a novel green pigment, as a central metal and a specific acidic compound are bonded. However, the new green pigment is a conventional C.I. I. Compared with Pigment Greens 7 and 36, the contrast was improved, but it was not sufficient, and the brightness was also insufficient, which was a problem. Further, the novel green pigment has a problem that phthalocyanine is radically ionized by irradiation with light under low oxygen, so that VHR is lowered and the driving of the liquid crystal display element is adversely affected. Furthermore, depending on the acidic compound bonded to the central metal aluminum, the initial viscosity and the viscosity after storage over time become high, and there are problems such as deterioration of coatability and generation of foreign matter in the coating film after coating. It was.

Japanese Unexamined Patent Publication No. 2004-070342 Japanese Unexamined Patent Publication No. 2016-14534

The problem to be solved by the present invention is a coloring composition having excellent brightness, contrast, and voltage retention when used in a color filter, less generation of foreign matter in the coating film, low viscosity, and excellent storage stability. It is an object of the present invention to provide a phthalocyanine pigment capable of obtaining a product, a coloring composition using the phthalocyanine pigment, a photosensitive coloring composition using the coloring composition, and a color filter.

As a result of diligent studies to solve the above problems, the present inventors have conducted the following phthalocyanine pigments, coloring compositions using the phthalocyanine pigments, photosensitive coloring compositions using the coloring compositions, and color filters. It was found that the above-mentioned problems could be solved, and the present invention was completed.

（一般式（１）中のＸ、及びＹはハロゲン原子を表し、ｎは４〜１６、ｍは１〜１０を表す。） That is, the present invention relates to a phthalocyanine pigment represented by the following general formula (1).

General formula (1)

(X and Y in the general formula (1) represent halogen atoms, n represents 4 to 16, and m represents 1 to 10.)

The present invention also relates to the phthalocyanine pigment in which m in the general formula (1) is 1 to 4.

The present invention also relates to the phthalocyanine pigment having a distribution width of halogen atoms represented by Y in the general formula (1) of 2 to 6.

The present invention also relates to the phthalocyanine pigment in which X in the general formula (1) is a bromine atom and n is 6 to 10.

The present invention also relates to a coloring composition containing the phthalocyanine pigment and a dispersed resin as a coloring agent.

The present invention also relates to the coloring composition containing an acidic dispersion resin as the dispersion resin.

The present invention also relates to the coloring composition further containing a basic dispersion resin as the dispersion resin.

The present invention also relates to the coloring composition further containing a yellow pigment as the coloring agent.

Further, in the present invention, as the yellow pigment, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 150, C.I. I. It relates to the coloring composition which is at least one selected from the group consisting of Pigment Yellow 185 and the quinophthalone pigment represented by the following general formula (2).

（一般式（２）中、Ｒ^１〜Ｒ^１３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ルコキシル基または置換基を有しても良いアリール基を表す。ただし、Ｒ^１〜Ｒ^４のうち少なくとも１つの隣接した一組の基、及び／又は、Ｒ^１０〜Ｒ^１３のうち少なくとも１つの隣接した一組の基は、一体となって、置換基を有してもよい芳香環を形成する。） General formula (2)

(In the general formula (2), R ^{1 to} R ¹³ each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and an alkoxyl group or a substituent which may have a substituent. Represents an aryl group that may have, provided that ^{at least one adjacent set of groups from R 1 to} R ⁴ and / or at least one adjacent set of groups from R ^{10 to} R ¹³ , Together to form an aromatic ring that may have a substituent.)

The present invention also relates to a photosensitive coloring composition containing the coloring composition, a photopolymerizable compound, and a photopolymerization initiator.

The present invention also relates to a color filter including a filter segment formed of the photosensitive colored material on a substrate.

According to the present invention, a phthalocyanine capable of obtaining a coloring composition having excellent brightness, contrast, and voltage retention when used in a color filter, less generation of foreign matter in the coating film, low viscosity, and excellent storage stability can be obtained. It was possible to provide a pigment, a coloring composition using the phthalocyanine pigment, a photosensitive coloring composition using the coloring composition, and a color filter.

Hereinafter, embodiments for carrying out the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.

The terms used in this specification will be described. "(Meta) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" are "acryloyl and", respectively, unless otherwise specified. / Or metaacryloyl, "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or metaacrylamide". Further, "CI" means a color index.

<Parthalocyanine pigment>
The present invention will be described in detail. The phthalocyanine pigment of the present invention is represented by the following general formula (1).

General formula (1)

In the general formula (1), X and Y represent halogen atoms, n represents 4 to 16, and m represents 1 to 10.
When the general formula (1) contains a plurality of compounds having different numbers of halogen atoms represented by X and Y, n and m are average values of the plurality of compounds.

Examples of the halogen atom represented by X in the general formula (1) include fluorine, bromine, chlorine, and iodine, and two or more of them may be used in combination. From the viewpoint of storage stability, bromine and chlorine are preferable, and bromine is more preferable.

From the viewpoint of brightness, n in the general formula (1) is preferably 6 to 10, and more preferably 7 to 9.

Examples of the halogen atom represented by Y in the general formula (1) include fluorine, bromine, chlorine, and iodine, and two or more of them may be used in combination. From the viewpoint of brightness and voltage retention, bromine and chlorine are preferable, and from the viewpoint of low viscosity, storage stability, and suppression of foreign matter generation in the coating film, bromine is more preferable.

The m in the general formula (1) is preferably 1 to 4 from the viewpoint of low viscosity, storage stability, and suppression of foreign matter generation in the coating film, and further, brightness, contrast, and voltage retention. From the viewpoint of rate, it is more preferably 2 to 3.

The distribution width of the halogen atom represented by Y in the general formula (1) is preferably 2 to 6 from the viewpoint of storage stability, voltage retention, and suppression of foreign matter generation in the coating film.
Here, the "distribution width of halogen atoms" is the distribution of the number of halogen substituents substituted with the phosphorus compound of the phthalocyanine pigment represented by the general formula (1). The distribution width of the halogen atom represented by Y is obtained by calculating the area of the peak of the molecular weight corresponding to each component in the LC-MS mass spectrum of the phosphorus compound represented by the general formula (5) described later, and in the chromatogram. It was obtained by counting the number of peaks having a peak area ratio of 1% or more when the total area of the detected peaks was set to 100%. The distribution width of the halogen number occurs when a plurality of compounds having different numbers of substituents of the phosphorus compound represented by the general formula (5) described later are included, and the halogen atom in the phosphorus compound represented by the general formula (5) When only compounds having the same number of substituents are used, the distribution width is 1. Compounds having the same number of substituents but different substitution sites are regarded as one compound.

[Manufacturing method of phthalocyanine pigment]
The method for synthesizing the phthalocyanine pigment represented by the general formula (1) of the present invention is not particularly limited and can be synthesized by a known method. For example, the following method can be mentioned.

The phthalocyanine compound represented by the following general formula (3) is halogenated and then hydrolyzed to obtain the following general formula (4), which is then reacted with the phosphorus compound represented by the following general formula (5). A phthalocyanine pigment represented by the general formula (1) can be synthesized.
Note that X and n in the general formula (4) and Y and m in the general formula (5) are synonymous with X and n in the general formula (1), respectively.

The halogenation of the phthalocyanine compound represented by the general formula (3) can be carried out by, for example, the chlorosulphonic acid method, the dissolution method or the like described in The Phthalocyanines Volume II Manufacture and Applications (CRC Press, Inc., 1983) or the like. Can be synthesized by the method.

Examples of the chlorosulphonic acid method include dissolving a phthalocyanine compound represented by the general formula (3) in a sulfur oxide-based solvent such as chlorosulphonic acid and sulfuric acid, and adding a halogenating agent to the solvent to halogenate the phthalocyanine compound. .. The reaction temperature at this time is preferably 20 to 120 ° C., and the reaction time is preferably 1 to 10 hours.

Examples of the dissolution method include aluminum chloride, aluminum halide such as aluminum bromide, titanium halide such as titanium tetrachloride, sodium chloride, sodium bromide and the like, as described in JP-A-51-64534. 10 to 170 ° C. consisting of one or a mixture of two or more halogenating agents such as alkali metal halides or alkaline earth metal halides [hereinafter referred to as alkali (earth) metal halides] and thionyl chloride. A method of halogenating a phthalocyanine compound in a certain amount of melt can be mentioned.

The halogenating agent used for halogenation means a fluorinating agent, a chlorinating agent, a brominating agent and an iodizing agent. Examples include fluorite, N-fluorosulfonamide, diethylaminosulfatrifluoride, N-fluoropyridinium salt and the like.
Examples of the chlorinating agent include chlorine (Cl ₂ ), N-chlorosuccinimide, sulfyl chloride, trichloroisocyanuric acid, sodium dichloroisocyanurate, 2,3,4,5,6,6-hexachloro-2,4-cyclohexadienone. , 2,3,4,5,6-hexachloro-2,5-cyclohexadienone, N-chlorotriethylammonium chloride, benzeneselenenyl chloride and the like.
Examples of the brominating agent include bromine (Br ₂ ), N-bromosuccinimide, silver sulfate-bromine, tetramethylammonium tribromide, trifluoroacetyl hypobromite, dibromoisocyanuric acid, 2,4,4,6-tetrabromocyclohexy. Sa-2,5-dieneon, hydrogen bromide-dimethyl sulfoxide, N-bromosuccinimide-dimethylformamide, 2,4-diamino-1,3-thiazole hydrotribromide, 1,3-dibromo-5,5-dimethylhydantoin, etc. Can be mentioned.
Examples of the iodinating agent include iodine (I ₂ ), 1,3-diiodo-5,5-dimethylhydantoin, trifluoroacetyl hypoiodite, iodine-periodic acid, ethylene iodochloride, N-iodosuccinimide and the like. ..

The method for synthesizing the phosphorus compound represented by the general formula (5) is not particularly limited and can be synthesized by a known method. For example, it can be obtained by halogenating diphenyl phosphate by a method such as a chlorosulphonic acid method or a dissolution method as described above. It can also be obtained by using a pre-halogenated alcohol as a raw material.

Since the phthalocyanine compound represented by the general formula (4) has properties as a pigment, acid is previously used in advance of the reaction in order to improve the reaction efficiency with the phosphorus compound represented by the general formula (5). It is desirable to use a compound that has been miniaturized by a method such as a pacing method or a solvent salt milling method. By refining the phthalocyanine compound represented by the general formula (4) in advance, it becomes easy to obtain fine phthalocyanine pigments represented by the general formula (1) produced from the phthalocyanine compound. When used as an object, it has the effect of facilitating the acquisition of high contrast.

The reaction between the phthalocyanine compound represented by the general formula (4) and the phosphorus compound represented by the general formula (5) can be allowed to proceed, for example, by mixing and stirring in an organic solvent. Then, the phthalocyanine pigment represented by the general formula (1) can be obtained by removing the organic solvent.

Specific examples of the organic solvent used in the production of the phthalocyanine pigment represented by the general formula (1) include ethylene, a monovalent alcohol solvent typified by methanol, ethanol, isopropanol and t-butanol. For glycols, propylene glycols, diethylene glycols, polyethylene glycols, thiodiglycols, dithiodiglycols, 2-methyl-1,3-propanediols, 1,2,6-hexanetriols, acetylene glycol derivatives, glycerin, trimethylolpropane, etc. Representative polyhydric alcohol solvents, 1-methyl-2-pyrrolidinone, 1,3-dimethyl-2-imidazolidinone, 2-pyrrolidinone, ε-caprolactam, formamide, N-methylformamide, N, N-dimethylformamide , Acetamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpropanamide, hexamethylphosphoric triamide, urea, or amide-based solvents such as tetramethylurea, and other ethylene glycol monomethyl (or ethyl). ) Ether, diethylene glycol monomethyl (or ethyl) ether, or triethylene glycol monoethyl (or butyl) ether and other polyhydric alcohol lower monoalkyl ether solvents, ethylene glycol dimethyl ether (monoglyme), diethylene glycol dimethyl ether (diglime), or tri Polyether-based solvents such as ethylene glycol dimethyl ether (triglime), sulfur-containing solvents such as sulfolane, dimethyl sulfoxide, or 3-sulfolene, polyfunctional solvents such as diacetone alcohol and diethanolamine, acetic acid, maleic acid, docosahexaenoic acid, and trichloro. Examples thereof include carboxylic acid solvents such as acetic acid or trifluoroacetic acid, sulfonic acid solvents such as methanesulfonic acid or trifluorosulfonic acid, and aromatic hydrocarbon solvents such as benzene, toluene and xylene, but phosphoric acid. Due to the good dissolution of diphenyl, monovalent alcohol solvents such as methanol, ethanol and isopropyl alcohol, and aproton polar solvents such as dimethyl sulfoxide, N, N-dimethylformamide and 1-methyl-2-pyrrolidinone Is preferably used. These organic solvents may be used alone or in combination of two or more.

The method for removing the organic solvent after completion of the reaction is not particularly limited, and a known method can be used, but it is compatible with the organic solvent used after suction filtration or pressure filtration. It is desirable to wash with an organic solvent having a low boiling point and then dry and remove it. In the case of a water-soluble organic solvent, it is desirable to mix it with water and then remove it by washing with water.

(Miniaturization of phthalocyanine pigment)
The phthalocyanine pigment represented by the general formula (1) of the present invention and the pigment used in the coloring composition are preferably used in a finely divided form. The miniaturization method is not particularly limited, and a known method can be used. For example, wet grinding, dry grinding, and dissolution-precipitation method can all be used, and as illustrated in the present invention, salt milling treatment by the kneader method, which is a kind of wet grinding, can be performed to make the particles finer. The average primary particle size determined by the TEM (transmission electron microscope) of the pigment is preferably in the range of 5 to 90 nm. If it is smaller than 5 nm, it becomes difficult to disperse it in an organic solvent, and if it is larger than 90 nm, a sufficient contrast ratio may not be obtained. For this reason, the more preferable average primary particle size is in the range of 10 to 70 nm.

The solvent salt milling method is a method of heating a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, or a sand mill. After mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment particles are crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

As the water-soluble inorganic salt, sodium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride is preferably used from the viewpoint of price. From the viewpoint of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by weight, based on the total mass of the pigment.

The water-soluble organic solvent has a function of wetting 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 used. However, since the temperature rises during salt milling and the solvent easily evaporates, a high boiling point having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety. Such examples include, 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, etc. Is used. These water-soluble organic solvents are preferably used in an amount of 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass, based on the total mass of the pigment.

When the pigment is subjected to solvent salt milling treatment, a resin may be added if necessary. Here, the type of resin used is not particularly limited, and a natural resin, a modified natural resin, a synthetic resin, a synthetic resin modified with a natural resin, or the like can be used. The resin used is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in the water-soluble organic solvent. The amount of the resin used is preferably 5 to 200 parts by mass with respect to the total mass of the pigment.

The phthalocyanine pigment represented by the general formula (1) of the present invention may be used in combination with two or more kinds of phthalocyanine pigments represented by the general formula (1) according to the intended use. At this time, the phthalocyanine pigments produced separately may be mixed with each other, or two or more kinds of phthalocyanine pigments may be synthesized and miniaturized at the same time to be produced and used. Further, a phthalocyanine pigment other than the phthalocyanine pigment represented by the general formula (1) may be used in combination as long as the effect of the present invention is not impaired.

<Coloring composition>
One embodiment of the present invention relates to a coloring composition. The coloring composition contains a phthalocyanine pigment represented by the general formula (1) and a dispersed resin as a coloring agent.

Hereinafter, the components contained in or may be contained in the coloring composition of one embodiment will be described.

[Colorant]
The coloring composition in the present invention contains a phthalocyanine pigment represented by the general formula (1) as a coloring agent. In the present invention, the phthalocyanine pigment represented by the general formula (1) may be used alone or in combination of two or more.

(Other colorants)
In order to adjust the chromaticity, the coloring composition in the present invention may contain, in addition to the phthalocyanine pigment represented by the general formula (1), other coloring agents as long as the effects of the present invention are not impaired. .. The other colorants are not particularly limited, and known colorants can be used. For example, a green pigment or a yellow pigment can be mentioned.

The green pigment is not particularly limited, but generally includes a green pigment or a green dye. Specific examples of the green pigment include C.I. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 62, 63, Examples thereof include zinc phthalocyanine pigments described in JP-A-2008-19383, JP-A-2007-320986, JP-A-2004-070342, etc., and aluminum phthalocyanine pigments described in Japanese Patent No. 4893859. , Especially not limited to these.

Specific examples of the green dye include C.I. I. Solvent Green 1, 4, 5, 7, 34, 35, etc. I. Solvent dye, C.I. I. Acid Green 1, 3, 5, 9, 16, 50, 58, 63, 65, 80, 104, 105, 106, 109 and the like. I. Acid dye, C.I. I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82 and the like. I. Direct dye, C.I. I. Modant Green 1, 3, 4, 5, 10, 15, 26, 29, 33, 34, 35, 41, 43, 53, etc. I. Examples include modern dyes.

Above all, from the viewpoint of contrast and brightness, C.I. I. It is preferred to include at least one selected from the group consisting of Pigment Greens 7, 36, 58, 62 and 63.

The yellow pigment is not particularly limited, but generally includes a yellow pigment or a yellow dye. Specific examples of the yellow pigment 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, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214 and the like can be mentioned. In addition, quinophthalone pigments described in Japanese Patent Application Laid-Open No. 2012-226110 and Japanese Patent No. 6432077 can be mentioned.

Yellow dyes include azo dyes, azo metal complex salt dyes, anthraquinone dyes, indigo dyes, thioindigo dyes, phthalocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, thiazine dyes, cationic dyes, cyanine dyes, nitro dyes, and quinoline dyes. , Naftquinone dyes, oxazine dyes and the like. Specifically, C.I. I. Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9: 1, 10, 11, 11: 1, 12, 13, 14, 15, 16, 17, 17: 1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40: 1, 41, 42, 42: 1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, 66, 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191 and 192, 199 and the like can be mentioned.

In addition, C.I. I. Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44: 1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, 134 and the like.

In addition, C.I. I. Basic Yellow 1, 2, 5, 11, 13, 14, 15, 19, 21, 24, 25, 28, 29, 37, 40, 45, 49, 51, 57, 79, 87, 90, 96, 103, Examples include 105 and 106.

In addition, C.I. I. Solvent Yellow 2, 3, 4, 7, 8, 10, 11, 12, 13, 14, 15, 16, 18, 19, 21, 22, 25, 27, 28, 29, 30, 32, 33, 34, 40, 42, 43, 44, 45, 47, 48, 56, 62, 64, 68, 69, 71, 72, 73, 77, 79, 81, 82, 83, 85, 88, 89, 90, 93, 94, 98, 104, 107, 114, 116, 117, 124, 130, 131, 133, 135, 138, 141, 143, 145, 146, 147, 157, 160, 162, 163, 167, 172, 174, 175, 176, 177, 179, 181, 182, 183, 184, 185, 186, 187, 188, 190, 191 and 192, 194, 195 and the like.

In addition, C.I. I. Disperse Yellow 1, 2, 3, 5, 7, 8, 10, 11, 13, 13, 23, 27, 33, 34, 42, 45, 48, 51, 54, 56, 59, 60, 63, 64 , 67, 70, 77, 79, 82, 85, 88, 93, 99, 114, 118, 119, 122, 123, 124, 126, 163, 184, 184: 1, 202, 211, 229, 231, 232 , 233, 241, 245, 246, 247, 248, 249, 250, 251 and the like.

Among them, from the viewpoint of heat resistance, light resistance, and brightness of the filter segment, the yellow dye is C.I. I. Pigment Yellow 138, 150, 185, and preferably at least one selected from the group consisting of quinophthalone pigments represented by the following general formula (2).

（一般式（２）中、Ｒ^１〜Ｒ^１３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ルコキシル基または置換基を有しても良いアリール基を表す。ただし、Ｒ^１〜Ｒ^４のうち少なくとも１つの隣接した一組の基、及び／又は、Ｒ^１０〜Ｒ^１３のうち少なくとも１つの隣接した一組の基は、一体となって、置換基を有してもよい芳香環を形成する。） General formula (2)

(In the general formula (2), R ^{1 to} R ¹³ each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and an alkoxyl group or a substituent which may have a substituent. Represents an aryl group that may have, provided that ^{at least one adjacent set of groups from R 1 to} R ⁴ and / or at least one adjacent set of groups from R ^{10 to} R ¹³ , Together to form an aromatic ring that may have a substituent.)

When a yellow pigment is used in combination with the phthalocyanine pigment represented by the general formula (1), the mass ratio of the yellow pigment / the phthalocyanine pigment represented by the general formula (1) is 70/30 to 70/30 from the viewpoint of brightness and hue. The range of 10/90 is preferable, the range of 70/30 to 25/75 is more preferable, and the range of 65/35 to 35/65 is particularly preferable.

[Dispersed resin]
The coloring composition containing the phthalocyanine pigment represented by the general formula (1) in the present invention contains a dispersed resin from the viewpoints of low viscosity, storage stability, and contrast. The dispersion resin is not particularly limited, and known ones can be used.

Specifically, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, and lengths. Oil-based dispersants such as chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) with polyesters having free carboxyl groups, and salts thereof. , (Meta) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone and other water-soluble resins and highly water-soluble Examples thereof include molecular compounds, polyester-based compounds, modified polyacrylate-based compounds, ethylene oxide / propylene oxide-added compounds, and phosphoric acid ester-based compounds.

The structure of the dispersed resin is also not particularly limited, and examples thereof include a random structure, a block structure, a comb-shaped structure, and a star-shaped structure. Of these, a block structure or a comb-shaped structure is preferable from the viewpoint of dispersion stability.

The dispersed resin may be used alone or in combination of two or more.

From the viewpoint of dispersion stability, the content of the dispersed resin is preferably 0.01 to 100 parts by mass, more preferably 0.01 to 60 parts by mass, and 5 to 5 parts by mass with respect to 100 parts by mass of the colorant. 40 parts by mass is more preferable.

[Acid dispersion resin]
The dispersed resin preferably contains an acidic dispersed resin from the viewpoint of low viscosity and storage stability. The acidic dispersion resin is not particularly limited, and known ones can be used. Specifically, it is a dispersion resin having a carboxyl group, a phosphoric acid group, a sulfonic acid group, or the like as an acidic group. Above all, it is preferable to have a carboxyl group and a phosphoric acid group having high adsorptivity to pigments.

The weight average molecular weight of the acidic dispersion resin is preferably 2,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 2,000 to 20,000 from the viewpoint of viscosity and dispersion stability. ..

The acid value of the acidic dispersion resin is preferably 5 to 200 mgKOH / g, more preferably 10 to 150 mgKOH / g, and even more preferably 15 to 100 mgKOH / g from the viewpoint of viscosity and dispersion stability.

(Acid dispersion resin having a carboxyl group)
The acidic dispersion resin having a carboxyl group is selected from the group consisting of tetracarboxylic acid dianhydride and tricarboxylic acid anhydride because the position and number of carboxyl groups can be controlled and the dispersion stability can be improved. It is preferable to have a carboxyl group-containing polyester moiety obtained by reacting an acid anhydride group of an acid anhydride of more than one species with a hydroxyl group of a hydroxyl group-containing compound.

Further, the acidic dispersion resin having a carboxyl group is an ethylenically unsaturated single amount containing at least one thermally crosslinkable functional group selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, and a blocked isocyanate group. It is preferable to have a body and a vinyl polymer portion formed by radically polymerizing an ethylenically unsaturated monomer containing a carboxyl group.

By acting as the carboxyl group-containing polyester portion as an organic pigment adsorbing group and the vinyl polymer portion as an organic pigment carrier-affinitive group, aggregation of the pigment is suppressed and a coloring composition having excellent dispersion stability can be obtained. Since the vinyl polymer portion has a heat-crosslinkable group, a photosensitive coloring composition having excellent chemical resistance and solvent resistance after curing can be obtained.

Hereinafter, each component of the acidic dispersion resin having a carboxyl group will be described.
≪Acid anhydride constituting the carboxyl group-containing polyester portion in the acidic dispersion resin≫
The acid anhydride constituting the carboxyl group-containing polyester moiety in the acidic dispersion resin is one or more selected from the group consisting of tetracarboxylic dianhydride and tricarboxylic acid anhydride.
By reacting the two anhydride groups of the tetracarboxylic dianhydride with the hydroxyl groups of the hydroxyl group-containing compound, the carboxyl groups serving as the organic pigment adsorbing groups can be regularly arranged on the dispersion resin, resulting in dispersion stability. It is advantageous. When a tricarboxylic acid anhydride is used, it can react with a hydroxyl group to form an ester bond and leave a carboxyl group.

Examples of the tetracarboxylic acid dianhydride include 1,2,3,4-butanetetracarboxylic acid dianhydride, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, and 1,3-dimethyl-1,2. , 3,4-Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic hydride, 2,3,5-tricarboxycyclopentylacetic hydride, 3,5,6- Tricarboxynorbornan-2-acetate dianhydride, 2,3,4,5-tetracarboxylic acid dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1, 2-Dicarboxylic acid dianhydride, aliphatic tetracarboxylic acid dianhydride such as bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride, pyromerit Acid dianhydride, ethylene glycol dianhydride trimellitic acid ester, propylene glycol dianhydride trimellitic acid ester, butylene glycol dianhydride trimellitic acid ester, 3,3', 4,4'-benzophenone tetracarboxylic acid dianhydride, 3,3', 4,4'-biphenylsulfonetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride , 3,3', 4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3', 4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3', 4,4'- Tetraphenylsilane Tetracarboxylic acid dianhydride, 1,2,3,4-furtetracarboxylic acid dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylsulfide dianhydride, 4,4 '-Bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4'-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3', 4,4'-per Fluoroisopropyridene diphthalic hydride, 3,3', 4,4'-biphenyltetracarboxylic hydride, bis (phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) ) Dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4'-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4' −Diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) Fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] Fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinate Examples thereof include acid dianhydrides and aromatic tetracarboxylic dianhydrides such as 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride. The tetracarboxylic dianhydride is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic acid anhydride groups. These may be used alone or in combination. Among them, the aromatic carboxylic acid has a higher affinity for organic pigments than the aliphatic carboxylic acid, and the aromatic tetracarboxylic dianhydride is preferable from the viewpoint of dispersion stability.

Examples of the tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydrous, and cis-propen-1,2,3-tricarboxylic acid-1,2-. Anhydrous, 1,3,4-cyclopentanetricarboxylic acid anhydride, benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzenetricarboxylic acid anhydride] Things], etc.), Naphthalenetricarboxylic acid anhydride (1,2,4-naphthalentricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalentricarboxylic acid anhydride, 1,2 , 8-Naphthalene tricarboxylic acid anhydride, etc.), 3,4,4'-benzophenone tricarboxylic acid anhydride, 3,4,4'-biphenyl ether tricarboxylic acid anhydride, 3,4,4'-biphenyl tricarboxylic acid anhydride , 2,3,2'-biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, 3,4,4'-biphenylsulfonetricarboxylic acid anhydride and the like. Of these, aromatic tricarboxylic acid anhydrides are preferable from the viewpoint of affinity for organic pigments.

The ratio of the acid anhydride group in one or more acid anhydrides selected from tetracarboxylic acid dianhydride and tricarboxylic acid anhydride to the hydroxyl group in the hydroxyl group-containing compound is 0.5 for the acid anhydride group / hydroxyl group. It is preferably ~ 1.5. If it is smaller than 0.5 or larger than 1.5, there are many parts that do not react, and the desired dispersed resin is often not obtained.

As the acid anhydride, a tetracarboxylic acid dianhydride and a dicarboxylic acid anhydride which is a polycarboxylic acid anhydride other than the tricarboxylic acid anhydride, and an anhydride of a compound having 5 or more carboxylic acids can also be used in combination. ..

<< Hydroxy group-containing compound constituting the carboxyl group-containing polyester portion in the acidic dispersion resin >>
Examples of the hydroxyl group-containing compound include a compound having two hydroxyl groups and one thiol group in the molecule, a one-terminal hydroxyl group-containing vinyl polymer, and other polyols.

Compounds having two hydroxyl groups and one thiol group in the molecule include, for example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-. Propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1- Examples thereof include mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol and the like.

The details of the method for synthesizing the acidic dispersion resin having a carboxyl group will be described later, but the method of first synthesizing the polyester portion and then the vinyl polymer portion and the method of synthesizing the vinyl polymer portion first are followed. There is a method of synthesizing a polyester part. When the polyester moiety is synthesized first, the acid anhydride is reacted with a hydroxyl group-containing compound containing at least a compound having two hydroxyl groups and one thiol group in the above-mentioned molecule. On the other hand, when the vinyl polymer portion is synthesized first, the ethylenically unsaturated monomer is polymerized in the presence of the compound having two hydroxyl groups and one thiol group in the above-mentioned molecule, and 2 in the molecule. A vinyl polymer moiety is obtained in which a hydroxyl group derived from a compound having one hydroxyl group and one thiol group is introduced at the terminal. Therefore, it is the terminal hydroxyl group of the vinyl polymer moiety that reacts with the acid anhydride when synthesizing the next polyester moiety. That is, when the vinyl polymer portion is synthesized first, the vinyl polymer in which a hydroxyl group derived from a compound having two hydroxyl groups and one thiol group in the molecule is introduced into the hydroxyl group-containing compound constituting the polyester portion at the end. A moiety (one-terminal hydroxyl group-containing vinyl polymer) is also included.

Other polyols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, and 1,6-hexanediol. , 1,4-bis (Hydroxymethyl) cyclohesane, bisphenol A, hydrogenated bisphenol A, hydroxypivalyl hydroxypivalate, trimethylolethane, trimethylolpropane, 2,2,4-trimethyl-1,3-pentanediol, Polyhydric alcohols such as glycerin or hexanetriol;
Various polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, polyoxypropylene polyoxytetramethylene glycol, or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol;
Ring-opening of the various polyhydric alcohols described above and (cyclic) ether bond-containing compounds such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, or allyl glycidyl ether. Modified polyether polyols obtained by ring polymerization;
Polyester polyols obtained by co-condensation of one or more of the above-mentioned various polyvalent alcohols with polyvalent carboxylic acids, wherein the polyvalent carboxylic acids are succinic acid, adipic acid, sebacic acid, azelaic acid, and the like. Phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid, glutaconic acid, 1,2,5-hexanetricarboxylic acid, 1,4-cyclohexanehicarboxylic acid, 1,2, A polyol obtained by using a particularly representative one such as 4-benzenetricarboxylic acid, 1,2,5-benzenetricarboxylic acid, 1,2,4-cyclohexatricarboxylic acid, or 2,5,7-naphthalene tricarboxylic acid. Kind;
A lactone-based polyester polyol obtained by a polycondensation reaction between one or more of the various polyhydric alcohols described above and various lactones such as ε-caprolactone, δ-valerolactone, or 3-methyl-δ-valerolactone. Or lactone-modified polyester polyols obtained by a polycondensation reaction of the above-mentioned various polyhydric alcohols, polyvalent carboxylic acids, and various lactones;
Epoxy compounds such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monovalent and / or polyhydric alcohols, or glycidyl esters of monobasic acids and / or polybasic acids are used as polyester polyols. Epoxy-modified polyester polyols obtained in combination with one or more at the time of synthesis;
Others such as polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol, castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative, hydroxyl group-containing acrylic copolymer, hydroxyl group-containing fluorine-containing compound, or hydroxyl group-containing silicon resin. Examples thereof include polymer polyols of.

Of course, these other polyols may be used alone or in combination of two or more, but the weight average molecular weight thereof is preferably 40 to 10,000 from the viewpoint of compatibility and dispersion stability. It is preferably 100 to 2,000, and more preferably 100 to 1,000. When the weight average molecular weight is less than 40, the effect of improving compatibility and dispersion stability is small, and when the weight average molecular weight is 10,000 or more, the compatibility may be worsened.

The number of hydroxyl groups in one molecule of the other polyol is preferably a diol from the viewpoint of design, such as for adjusting the molecular weight of the acidic dispersion resin and adjusting the viscosity of the coloring composition. In particular, by reacting with the tetracarboxylic dianhydride, the carboxyl groups serving as the organic pigment adsorbing groups can be regularly arranged, which is advantageous for dispersion stability. If a large amount of a polyol having more than two hydroxyl groups is used, the main chain of the polyester may be branched to become complicated and bulky, and it may be difficult to obtain dispersion stability.

<< Ethylene unsaturated monomer constituting the vinyl polymer portion in the acidic dispersion resin >>
The vinyl polymer moiety has an ethylenically unsaturated monomer having at least one thermally crosslinkable functional group selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, and a blocked isocyanate group, and a carboxyl group. It is obtained by radical polymerization with an ethylenically unsaturated monomer.

The ethylenically unsaturated monomer having a hydroxyl group may be any monomer having a hydroxyl group and having an ethylenically unsaturated double bond, but specifically, it has a hydroxyl group. (Meta) acrylate-based monomers such as 2-hydroxyethyl (meth) acrylate, 2 (or 3) -hydroxypropyl (meth) acrylate, 2 (or 3 or 4) -hydroxybutyl (meth) acrylate and cyclohexanedi Hydroxyalkyl (meth) acrylates such as methanol mono (meth) acrylate and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate, or (meth) acrylamide-based monomers having a hydroxyl group, such as N- N- (hydroxyalkyl) (meth) acrylamide such as (2-hydroxyethyl) (meth) acrylamide, N- (2-hydroxypropyl) (meth) acrylamide, N- (2-hydroxybutyl) (meth) acrylamide, or , A vinyl ether-based monomer having a hydroxyl group, for example, a hydroxyalkyl vinyl ether such as 2-hydroxyethyl vinyl ether, 2- (or 3-) hydroxypropyl vinyl ether, 2- (or 3- or 4-) hydroxybutyl vinyl ether, or a hydroxyl group. Hydroxyalkylallyl ethers such as 2-hydroxyethylallyl ether, 2- (or 3-) hydroxypropylallyl ether, 2-(or 3- or 4-) hydroxybutylallyl ether, etc. Can be mentioned.

Further, obtained by adding an alkylene oxide and / or a lactone to the above-mentioned hydroxyalkyl (meth) acrylate, alkyl-α-hydroxyalkyl acrylate, N- (hydroxyalkyl) (meth) acrylamide, hydroxyalkyl vinyl ether or hydroxyalkyl allyl ether. The ethylenically unsaturated monomer obtained can also be used as the ethylenically unsaturated monomer having a hydroxyl group. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination system of two or more of these are used. When two or more kinds of alkylene oxides are used in combination, the binding form may be either random and / or block. As the lactone to be added, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these are used. Both alkylene oxide and lactone may be added.

Examples of the ethylenically unsaturated monomer having an oxetane group include (vinyloxyalkyl) alkyloxetane, (meth) acryloyloxyalkyl oxetane, and [(meth) acryloyloxyalkyl] alkyl oxetane. Of these, methyl methacrylate (3-ethyloxetane-3-yl) methyl and the like can be preferably mentioned. Examples of commercially available products include ETERNALCOLL OXMA (methyl methacrylate (3-ethyloxetane-3-yl)) (manufactured by Ube Industries, Ltd.).

Examples of the ethylenically unsaturated monomer having a t-butyl group include t-butyl methacrylate and t-butyl acrylate.

Examples of the ethylenically unsaturated monomer having a blocked isocyanate group include 2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate and 2-[(3,5-dimethylpyrazolyl) carbonylamino]. Ethyl methacrylate and the like can be mentioned.
Commercially available products include, for example, Karenz (registered trademark) MOI-BM (2- (0- [1'-methylpropylideneamino] carboxyamino) ethyl methacrylate) (Showa Denko), Karenz (registered trademark) MOI- BP (2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate) (manufactured by Showa Denko) and the like can be mentioned.

Examples of the ethylenically unsaturated monomer having a carboxyl group include (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, and cinnamic acid. Of these, (meth) acrylic acid is preferable because of its copolymerizability and easy availability.

Ethylene unsaturated monomer with hydroxyl group, ethylenically unsaturated monomer with oxetane group, ethylenically unsaturated monomer with t-butyl group, and ethylenically unsaturated monomer with blocked isocyanate group The content of is preferably 5 to 90% by mass in the whole ethylenically unsaturated monomer, and particularly preferably 20 to 60% by mass. If it is 5% by mass or more, it is possible to obtain a photosensitive coloring composition having excellent resistance due to the effect of crosslinking, and if it is 90% by mass or less, the dispersion stability is also good, which is preferable.

The vinyl polymer portion in the acidic dispersion resin having a carboxyl group has an ethylenically unsaturated monomer having a thermally crosslinkable functional group and other ethylenically unsaturated monomers other than the ethylenically unsaturated monomer having a carboxyl group. The saturated monomer may be radically polymerized.
Examples of other ethylenically unsaturated monomers include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, and isopropyl (meth), in addition to the above-mentioned ethylenically unsaturated monomer. Acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, isobornyl Alkyl (meth) acrylates such as (meth) acrylate;
Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate;
Heterocyclic (meth) acrylates such as tetrahydroflufreel (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate;
N-substituted (meth) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloyl morpholine, etc. Acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;
And nitriles such as (meth) acrylonitrile can be mentioned. Here, the (meth) acrylate indicates methacrylate or acrylate, and the (meth) acrylamide indicates methacrylamide or acrylamide.

Further, as a monomer that can be used in combination with the above acrylic monomer, styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether, etc. Examples thereof include fatty acid vinyls such as vinyl acetate and vinyl propionate.

The weight average molecular weight of the vinyl polymer portion is preferably 1,000 to 20,000, more preferably 2,000 to 15,000, even more preferably 2,000 to 12,000, and 3,000 to 8,000. Is particularly preferable. The vinyl polymer portion serves as an affinity portion for the solvent which is the dispersion medium. If the weight average molecular weight of the vinyl polymer portion is less than 1,000, the effect of steric repulsion by the solvent-affinitive portion is reduced, it becomes difficult to prevent the agglutination of the pigment, and the dispersion stability may be insufficient. On the other hand, if it exceeds 20,000, the absolute amount of the solvent-affinitive portion increases, and the dispersibility effect itself may decrease. Furthermore, the viscosity of the dispersion may increase.

The method for synthesizing the acidic dispersion resin having a carboxyl group is not particularly limited, and a known method is used. For example, the following synthesis method can be mentioned.

As a method for synthesizing the acidic dispersion resin having a carboxyl group, an ethylenically unsaturated monomer having an oxetane group and a t-butyl group are used in the presence of a compound having two hydroxyl groups and one thiol group in the molecule. A piece obtained by radically polymerizing an ethylenically unsaturated monomer containing at least one selected from the group consisting of an ethylenically unsaturated monomer having an ethylenically unsaturated monomer and an ethylenically unsaturated monomer having a blocked isocyanate group. Carboxyl by reacting a hydroxyl group in a vinyl polymer having two hydroxyl groups in the terminal region with an acid anhydride group in one or more acid anhydrides selected from tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides. An acidic dispersion resin having a group is obtained.

Further, as another synthesis method, a group consisting of a hydroxyl group in a hydroxyl group-containing compound constituting the polyester portion (however, a vinyl polymer containing one terminal hydroxyl group is not included), tetracarboxylic acid anhydride, and tricarboxylic acid anhydride. Ethylene unsaturated monomer having a hydroxyl group and ethylenically unsaturated having an oxetane group in the presence of a compound produced by reacting an acid anhydride group in one or more kinds of acid anhydrides selected from the above. An ethylenically unsaturated monocell containing at least one selected from the group consisting of a monomer, an ethylenically unsaturated monomer having a t-butyl group, and an ethylenically unsaturated monomer having a blocked isocyanate group. By radically polymerizing the weight, an acidic dispersion resin having a carboxyl group can be obtained.

When radical polymerization is carried out using an ethylenically unsaturated monomer having a hydroxyl group, it is preferable to synthesize using the synthesis method 1. When the synthesis method 2 is used, the acid anhydride group in the acid anhydride also reacts with the hydroxyl group derived from the ethylenically unsaturated monomer constituting the vinyl polymer portion, so that one end of the vinyl polymer portion is used. The purpose of reacting with a hydroxyl group may not be achieved, and the desired structure may not be obtained.

It can be obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the tetracarboxylic acid anhydride in the acidic dispersion resin having a carboxyl group and a tricarboxylic acid anhydride with a hydroxyl group in a hydroxyl group-containing compound. The method for synthesizing the carboxyl group-containing polyester moiety is not particularly limited, and a known method is used.

The method for synthesizing the vinyl polymer portion in the acidic dispersion resin having a carboxyl group is not particularly limited, and a known method is used.

As the acidic dispersant having a carboxyl group, a known technique described in JP-A-2009-155406 can be used.

(Acid dispersion resin having a phosphoric acid group)
The acidic dispersion resin having a phosphoric acid group means a resin having a phosphoric acid bond [(−O ₃ P = O] in the molecule.
For example, examples of the acidic dispersion resin having a phosphoric acid group include a resin represented by the following general formula (6).

（一般式（１）中、Ｒ₁は数平均分子量３００〜１０，０００のポリエステル残基、nは１または２を表す。） General formula (6)

(In the general formula (1), R ₁ represents a polyester residue having a number average molecular weight of 300 to 10,000, and n represents 1 or 2.)

The dispersion resin having a phosphoric acid group represented by the general formula (6) is, for example, a phosphoric acid esterification (second step) after ring-opening addition (first step) of a cyclic ester using monoalcohol as an initiator. It is preferable to carry out the above step).

The monoalcohol is not particularly limited as long as it has one hydroxyl group in the molecule, and any primary, secondary or tertiary alcohol can be used. For example, methanol, ethanol, propanol, isopropanol, butanol, sec-butanol, t-butanol, pentanol, amyl alcohol, hexanol, heptanol, octanol, 2-ethylhexyl alcohol, nonanol, decanol, lauryl alcohol, myristyl alcohol, cetyl alcohol, Stearyl alcohol, oleyl alcohol, hexadecyl alcohol and the like, and mixtures thereof are used. In particular, lauryl alcohol, N-hexanol, and hexadecyl alcohol are preferred.

A polyester residue having a hydroxyl group at one end can be obtained by ring-opening addition polymerization of ε-caprolactone or the like using monoalcohol as an initiator. The addition reaction of ε-caprolactone can be carried out by a known method, for example, by charging a reactor connected with a dehydration tube and a condenser with monoalcohol, ε-caprolactone and a polymerization catalyst, and carrying out the addition reaction under a nitrogen stream. When a low boiling point monoalcohol is used, it can be reacted under pressure using an autoclave. Solvent-free or a suitable dehydrating solvent such as toluene or xylene can also be used for the reaction. After the reaction is completed, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a part of the product.

The reaction temperature in the first step is 120 ° C. to 220 ° C., preferably 160 ° C. to 210 ° C. If the reaction temperature is less than 120 ° C, the reaction rate is extremely slow, and if it exceeds 220 ° C, side reactions other than the addition reaction of ε-caprolactone, for example, decomposition of the ε-caprolactone adduct into ε-caprolactone monomer, cyclic ε-caprolactone dimer Is likely to occur.
The number of moles of ε-caprolactone added per mole of monoalcohol is 1 to 50 moles, preferably 3 to 20 moles. If the number of added moles is less than 1 mol, it becomes difficult to obtain the effect as a dispersant, and if it is larger than 50 mol, the molecular weight of the reactant becomes too large, which tends to cause deterioration of dispersibility and fluidity.

Examples of the polymerization catalyst include tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodo, tetrabutylammonium iodo, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, and benzyltrimethylammonium. Quartular ammonium salts such as iodo, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodine, tetrabutylphosphonium bromide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethyl In addition to quaternary phosphonium salts such as phosphonium iodine, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, and tetraphenylphosphonium iodine, phosphorus compounds such as triphenylphosphine, and organic substances such as potassium acetate, sodium acetate, potassium benzoate, and sodium benzoate. In addition to alkali metal alcoholates such as carboxylates, sodium alcoholates, and potassium alcoholates, tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds, and zinc compounds such as zinc chloride can be mentioned. The amount of the catalyst used is 0.1 ppm to 3,000 ppm, preferably 1 ppm to 1,000 ppm. If the amount of catalyst exceeds 3,000 ppm, the resin will be heavily colored, which will adversely affect the stability of the product. On the contrary, if the amount of the catalyst used is less than 0.1 ppm, the ring-opening addition polymerization rate of the cyclic ester becomes extremely slow, which is not preferable.

Polyester residues having a hydroxyl group at one end can be phosphorylated by reacting with one or a combination of two or more phosphoric acid esterifying agents such as phosphorus pentoxide, polyphosphoric acid, orthophosphoric acid, and phosphorus oxychloride. It can be carried out. Of these, one or more phosphoric acid esterifying agents selected from the group consisting of orthophosphoric acid, polyphosphoric acid and phosphorus pentoxide are preferable because they do not have by-products such as hydrochloric acid gas and do not require special equipment. Of these, polyphosphoric acid having an orthophosphoric acid equivalent content of 116% by mass is preferable.

As for the charging ratio of the phosphoric acid esterifying agent, the molar ratio of the phosphorus atom in the phosphoric acid esterifying agent to the hydroxyl group of the polyester residue having a hydroxyl group at one end is preferably 0.5 to 1.5. It is more preferably 0 to 1.3, and most preferably 1.05 to 1.2. If the molar ratio of phosphorus atom to epoxy group is less than 0.5, phosphoric acid esterification to hydroxyl group tends to be insufficient or the amount of by-product of phosphoric acid diester tends to increase, and if it exceeds 1.5, it tends to increase. , There is a tendency that an increase effect commensurate with the amount added cannot be obtained.

The reaction temperature in the second step is not particularly limited, but is preferably 40 ° C. to 130 ° C., more preferably 50 ° C. to 110 ° C., and most preferably 60 ° C. to 100 ° C. If the reaction temperature is lower than these ranges, the esterification reaction may be insufficient and the phosphate esterifying agent may remain, and if it is higher than these ranges, by-products are likely to be formed and the ester is esterified. Decomposition of the chemical reaction product tends to occur easily.

In the general formula (6), when the molar ratio of the phosphoric acid ester of n = 1 to the phosphoric acid ester of n = 2 is 100: 0 to 100:30, the pigment dispersibility is good, which is preferable.

Further, in the general formula (6), _{it is preferable that R 1} has a structure represented by the following general formula (6-1).

（一般式（６−１）中、Ｒ_２はラクトン残基、Ｒ_３はモノアルコール残基、ｍは１〜５０の整数を表す。） General formula (6-1)

(In the general formula (6-1), R ₂ represents a lactone residue, R ₃ represents a monoalcohol residue, and m represents an integer of 1 to 50.)

_{For example, when R 1} in the general formula (6) is a polycaprolactone residue, pigment dispersibility and dry solubility are improved, which is preferable. In particular, polycaprolactone residues having a number average molecular weight of 300 to 10,000 are more preferable.

Examples of the acidic dispersion resin having a phosphoric acid group include a dispersion resin which is a copolymer of an ethylenically unsaturated monomer having a phosphoric acid group and another ethylenically unsaturated monomer. Specifically, it is described in JP-A-2003-253878 and JP-A-2008-161737.

As the acidic dispersion resin, an acidic dispersion resin having a carboxyl group and an acid dispersion resin having a phosphoric acid group may be used alone or in combination.

[Basic dispersion resin]
The coloring composition of the present invention preferably further contains a basic dispersion resin as the dispersion resin from the viewpoint of low viscosity and storage stability. The basic dispersion resin is not particularly limited, and known ones can be used. Specifically, it is a dispersion resin having a functional group containing a nitrogen atom such as a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonia base, and a nitrogen-containing heterocycle as a basic group.

Above all, from the viewpoint of dispersion stability, the basic group may have at least one structural unit selected from the groups represented by the following general formulas (7), general formulas (8), and general formulas (9). preferable.

(In the general formula (7), R _{1 to} R ₃ represent a chain or cyclic hydrocarbon group which may have a hydrogen atom or a substituent independently of each other, and R _{1 to} R ₃ Two or more of them may be bonded to each other to form a cyclic structure. R ₄ represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y ⁻ represents a counter anion.)

(In the general formula (8), R ₅ and R ₆ represent a chain or cyclic hydrocarbon group which may have a hydrogen atom or a substituent independently of each other, and R ₅ and R ₆ are They may be bonded to each other to form a cyclic structure. R ₄ represents a hydrogen atom or a methyl group, and X represents a divalent linking group.)

(In the general formula (9), R ₇ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxyradical group, or OR. represents _{12, R 12} represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group or an acyl group, having 7 to 12 carbon _atoms, R _{8, R} 9, R ₁₀ and R ₁₁ independently represent a methyl group, an ethyl group, or a phenyl group. R ₄ represents a hydrogen atom or a methyl group, and X represents a divalent linking group.)

_{As R 1 to} R ₃ in the general formula (7), an alkyl group having 1 to 4 carbon atoms which may have a substituent and an aralkyl group having 7 to 16 carbon atoms which may have a substituent may be used. More preferably, a methyl group, an ethyl group, a propyl group, a butyl group and a benzyl group are particularly preferable.

_{As R 5} and R ₆ in the general formula (8), an alkyl group having 1 to 4 carbon atoms which may have a substituent is more preferable, and a methyl group, an ethyl group, a propyl group and a butyl group are particularly preferable.

_{In R 7} of the general formula (9), examples of the alkyl group having 1 to 18 carbon atoms include linear, branched and cyclic alkyl groups, and specifically, a methyl group, an ethyl group and a normal propyl group. , Isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group and the like.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like.
Examples of the aralkyl group having 7 to 12 carbon atoms include a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms, and specifically, a benzyl group, a phenethyl group, and an α. -Methylbenzyl group, 2-phenylpropan-2-yl group and the like can be mentioned.
Examples of the acyl group include an alkanoyl group having 2 to 8 carbon atoms and an aroyl group, and specific examples thereof include an acetyl group and a benzoyl group.
Among these, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an oxy radical group are particularly preferable, a hydrogen atom and a methyl group are more preferable, and a methyl group is most preferable.

In the general formulas (7), (8), and (9), the divalent linking group X includes, for example, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, -CONH-R ₁₃ -,-. COO-R _{1 14} - _{(where, R 13} and _{R 14} is a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxy group)) and the like the recited, preferably -COO-R _{1 4} - a. Further, in the above formula (3), examples ^{of the counter anion Y −} include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , and PF ₆ ^−.

Specific examples of the ethylenically unsaturated monomer having a quaternary ammonium base, which is a precursor / partial structure of the general formula (7), include (meth) acryloyloxyethyltrimethylammonium chloride and (meth) acryloyloxy. Alkyl (meth) acrylate-based quaternary ammonium salts such as ethyltriethylammonium chloride, (meth) acryloyloxyethyldimethylbenzylammonium chloride, (meth) acryloyloxyethylmethylmorpholinoammonium chloride, (meth) acryloylaminopropyltrimethylammonium chloride, Examples thereof include alkyl (meth) acryloylamide-based quaternary ammonium salts such as (meth) acryloylaminoethyltriethylammonium chloride, (meth) acryloylaminoethyldimethylbenzylammonium chloride, dimethyldialylammonium methylsulfate, and trimethylvinylphenylammonium chloride. ..

Specific examples of the ethylenically unsaturated monomer having a tertiary amine group, which is the precursor / partial structure of the general formula (8), include N, N-dimethylaminoethyl (meth) acrylate, N, N. (Meta) acrylates having a tertiary amino group such as -diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N, N-diethylaminopropyl (meth) acrylate;
Tertiary such as N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, and N, N-diethylaminopropyl (meth) acrylamide. (Meta) acrylamides with amino groups;
And so on.

Specific examples of the ethylenically unsaturated monomer having a precursor / partial structure of the general formula (9) include compounds represented by the following general formulas (9-1) to (9-11). Can be mentioned.

In the general formulas (9-1) to (9-11), R ₄ represents a hydrogen or methyl group.

Of these, 2,2,6,6-tetramethylpiperidyl methacrylate ( _{a compound in which R 4} is a methyl group in the above general formula (9-1)), 1,2,2,6,6-pentamethylpiperidyl _{Methacrylate (a compound in which R 4} is a methyl group in the above general formula (9-2)) is preferable, and 1,2,2,6,6-pentamethylpiperidyl methacrylate is particularly preferable.

The structural units represented by the general formulas (7), (8), and (9) may be contained alone or in combination of two or more, and may be in any of random copolymerization, block copolymerization, and graft copolymerization. It may be contained.

The structural unit other than the structural unit represented by the general formulas (7), (8), and (9) is not particularly limited as long as it has a structure obtained by copolymerizing a copolymerizable monomer, and is used for any purpose. It can be appropriately selected accordingly. The copolymerizable monomers are shown below.

For example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate, isoamyl (meth) acrylate. , Octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate , Isomiristyl (meth) acrylates, stearyl (meth) acrylates, and linear or branched alkyl (meth) acrylates such as isostearyl (meth) acrylates;
Cyclic alkyl (meth) acrylates such as cyclohexyl (meth) acrylate, tertiary butylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and isobornyl (meth) acrylate;
(Meta) acrylates having a heterocycle such as tetrahydrofurfuryl (meth) acrylate and 3-methyl-3-oxetanyl (meth) acrylate;
(Meta) acrylates having an aromatic ring of benzyl (meth) acrylate and phenoxyethyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2-methoxypropyl (meth) acrylate , Diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, triethylene glycol monomethyl ether (meth) acrylate, Triethylene glycol monoethyl ether (meth) acrylate, tripropylene glycol monomethyl ether (meth) acrylate, tetraethylene glycol monomethyl ether (meth) acrylate, polyethylene glycol monomethyl ether (meth) acrylate, polypropylene glycol monomethyl ether (meth) acrylate, polyethylene (Poly) alkylene glycol monoalkyl ether (meth) acrylates such as glycol monolauryl ether (meth) acrylate, polyethylene glycol monostearyl ether (meth) acrylate, and octoxypolyethylene glycol-polypropylene glycol (meth) acrylate;
Phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, phenoxyhexaethylene glycol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, parac Milphenoxyethylene glycol (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, and nonylphenoxypoly (ethylene glycol-propylene glycol) (meth) ) (Poly) alkylene glycol (meth) acrylates having an aromatic ring such as acrylate;
Alkyloxy such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane (Meta) acrylates having a silyl group;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctyl ethyl (meth) acrylate, and tetrafluoropropyl (meth) acrylate; (meth) acryloxy-modified polydimethyl Siloxane (silicone macromer);
N-substituted (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholin; In addition, nitriles such as (meth) acrylonitrile can be mentioned.
In addition, styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acids such as vinyl acetate and vinyl propionate. Examples include vinyls.

Further, a carboxyl group-containing ethylenically unsaturated monomer can also be used in combination. Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth) acrylic acid, (meth) acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2- (meth) acryloyloxyethyl phthalate, and 2 -(Meta) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth) acrylate, and ω-carboxypoly Examples thereof include caprolactone (meth) acrylate.

Further, as long as the effect of the present invention is not impaired, an ethylenically unsaturated monomer containing an amino group other than the structural units represented by the general formulas (7), (8) and (9) is used in combination. May be good.

The weight average molecular weight of the basic dispersion resin is preferably 1,000 to 100,000 from the viewpoint of viscosity and dispersion stability.

(Dispersion aid)
From the viewpoint of dispersion stability, the coloring composition in the present invention may contain a dispersion aid such as a dye derivative in addition to the dispersion resin.

As the dye derivative, a known dye derivative having an acidic group, a basic group, a neutral group or the like in the organic dye residue can be used. For example, compounds having acidic substituents such as sulfo group, carboxy group and phosphoric acid group and amine salts thereof, compounds having basic substituent such as sulfonamide group and tertiary amino group at the terminal, phenyl group and phthalimide. Examples thereof include compounds having a neutral substituent such as an alkyl group.
Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, and benzo. Indole pigments such as isoindole, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, azo pigments such as azo, disazo, polyazo, etc. Be done.

Specifically, as the diketopyrrolopyrrole dye derivative, JP-A-2001-22520, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, JP-A-2017-156397, phthalocyanine. Examples of the dye derivative are JP-A-2007-226161, WO2016 / 163351, JP-A-2017-165820, Patent No. 5735266, and as an anthraquinone-based dye derivative, JP-A-63-264674. Japanese Patent Application Laid-Open No. 09-272812, Japanese Patent Application Laid-Open No. 10-245501, Japanese Patent Application Laid-Open No. 10-265697, Japanese Patent Application Laid-Open No. 2007-079094, WO2009 / 025325 pamphlet, as a quinacridone-based dye derivative, JP-A-48- 54128, 03-9961 and 2000-273383, the dioxazine dye derivative is 2011-162662, and the thiazineindigo dye derivative is 2007-314785. Examples of JP, Triazine-based dye derivatives include JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, and JP-A-2004-217842. JP-A-2007-314681, JP-A-2009-57478 as a benzoisoindole-based dye derivative, JP-A-2003-167112, JP-A-2006-291194, and JP-A as quinophthalone-based dye derivatives. 2008-31281, 2012-226110, naphthol dye derivatives are 2012-208329, 2014-5439, and azo dye derivatives are 2001-172520. Japanese Unexamined Patent Publication No. 2012-172092, JP-A-2004-307854 as acidic substituents, JP-A-2002-201377, JP-A-2003-171594, JP-A-2005 as basic substituents. Examples thereof include known dye derivatives described in Japanese Patent Application Laid-Open No. -181383, Japanese Patent Application Laid-Open No. 2005-213404, and the like. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group, a basic group, and the like. A compound having a substituent such as a sex group is synonymous with a dye derivative.

The dye derivative may be used alone or in combination of two or more.

From the viewpoint of dispersion stability, the content of the dye derivative is preferably 0.5 to 40 parts by mass, more preferably 1 to 35 parts by mass, based on the total mass of the colorant. It is particularly preferable that the amount is ~ 35 parts by mass.

When the pigment derivative is added to the pigment and pigmentation treatment such as acid pacing, acid slurry, dry milling, salt milling, solvent salt milling is performed, the pigment derivative is adsorbed on the pigment surface, and the pigment derivative is not added. The primary particles of the pigment can be made finer as compared with the above.

By adding a pigment derivative to the pigment and performing a dispersion treatment such as wet dispersion using two rolls, three rolls, and beads, the pigment derivative is adsorbed on the pigment surface and the pigment surface has polarity, and the pigment surface becomes polar, and the pigment is different from the dispersed resin. Adsorption is promoted, compatibility with pigments, dye derivatives, dispersion resins, solvents, and other additives is improved, and dispersion stability when made into a coloring composition or a photosensitive coloring composition is improved. Further, by improving the compatibility, the coating film is excellent in stability over time when the photosensitive coloring composition is applied to a glass substrate or the like, and the waiting time from application to exposure of the photosensitive coloring composition (PCD: Post Coating). The stability / characteristic dependence such as the pattern shape with respect to the delay) and the waiting time (PED: Post Exposure Day) from exposure to heat treatment, and the line width sensitivity stability are improved.
Further, by adsorbing and coating the pigment surface with the pigment derivative and the dispersed resin, it is possible to suppress crystal precipitation due to aggregation and sublimation of the pigment when the coating film is heated and fired. Further, variation in development time and development residue are suppressed.

(Binder resin)
The coloring composition in the present invention can contain a binder resin from the viewpoint of dispersibility, film forming property, and coating film resistance. The binder resin is not particularly limited, and known binder resins can be used.

The binder resin includes a thermoplastic resin, a thermosetting resin, an active energy ray-curable resin having an ethylenically unsaturated double bond and the like when classified according to the main curing method, and the active energy ray-curable resin is heat. It may be a plastic resin or one having a thermosetting function, and is preferably an alkali-soluble resin from the viewpoint of developability.

The binder resin preferably has 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.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 10,000 to 80,000 from the viewpoint of dispersion stability.

Examples of the thermoplastic resin that can be used as the binder resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, and vinyl chloride-vinyl acetate copolymer. , Polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin And so on.

Examples of the thermosetting resin that can be used as the binder resin include epoxy resin, cardo resin, and melamine resin. Moreover, not only high molecular weight compounds such as resins, but also low molecules such as epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, cardo compounds, and phenol compounds. It may be a compound, and the present invention is not limited thereto. Of these, epoxy compounds and oxetane compounds are preferable. By including such a thermosetting compound, it reacts at the time of firing the filter segment, and the crosslink density of the coating film is increased, so that the heat resistance is improved and the pigment aggregation at the time of firing the filter segment is suppressed.

Examples of the epoxy compound include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, etc.). Polycondensate of alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthoaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) , Phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadien, vinylnorbornene, tetrahydroinden, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) Polycondensate with ketones (acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'-benzenedimethanol, biphenyl Polycondensate with dimethanol, α, α, α', α'-biphenyldimethanol, etc., and the weight of phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.) Condensates, polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylizing alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, glycidyl Examples thereof include ester-based epoxy resins, but the epoxy compounds that are usually used are not limited thereto. These may be used alone or two or more kinds may be used.

As the oxetane compound, a known compound having an oxetane group can be used without particular limitation. Examples of the oxetane compound include those in which the oxetane group is monofunctional, those in which the oxetane group is bifunctional, and those in which the oxetane group is bifunctional or higher. Specifically, examples of monofunctional oxetane groups include (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methyl methacrylate, and 3-ethyl-3-hydroxymethyloxetane. , 3-Ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3-ethyl-3-3 {[3- (Triethoxysilyl) propoxy] methyl} oxetane and the like can be mentioned. Examples of bifunctional oxetane groups include 4,4'-bis [(3-ethyl-3-oxetanyl) methoxymethyl] biphenyl) and 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl]. Ethylene, 1,4-bis {[(3-ethyl-3-oxetanyl) methoxy] methyl} benzene, di [1-ethyl (3-oxetanyl)] methyl ether, di [1-ethyl (3-oxetanyl)] methyl Ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (2-phenoxymethyl) oxetane, 3,7-bis (3-bis) Oxetanyl) -5-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene Glycosbis (3-ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis (3-Ethylene-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, polyethylene glycol bis ( 3-Ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) -modified bisphenol A-bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) -modified bisphenol A-bis (3-ethyl-3-oxetanylmethyl) Ether, EO-modified hydrogenated bisphenol A-bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A-bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3) -Oxetanylmethyl) ether and the like can be mentioned. Examples of those having a bifunctional or higher oxetane group include pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol hexa (3-ethyl). -3-oxetanylmethyl) ether, dipentaerythritol pentax (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-3-oxetanylmethyl) ether Ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentax (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrax (3-ethyl-3-oxetanylmethyl) ether, resin containing oxetane group And so on.

The binder resin is preferably an alkali-soluble resin from the viewpoint of developability, heat resistance, and transparency. It is for imparting development solubility in the alkaline development step at the time of producing a color filter, and has an acid group and / or a hydroxyl group.

The weight average molecular weight of the alkali-soluble resin is 2,000 to 40,000, preferably 3,000 to 30,000, and 4,000 to 20,000 in order to impart alkali development solubility. Is more preferable. If the weight average molecular weight is less than 2,000, the adhesion to the substrate is lowered and the exposure pattern is less likely to remain. If it exceeds 40,000, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated.

The acid value of the alkali-soluble resin is 50 to 200 (KOHmg / g), preferably 70 to 180, and more preferably 90 to 170 in order to impart alkali development solubility. If the acid value is less than 50, the alkali development solubility is lowered, a residue is generated, and the linearity of the pattern is deteriorated. If it exceeds 200, the adhesion to the substrate is lowered and the exposure pattern is less likely to remain.

Examples of the alkali-soluble resin include an alkali-soluble resin having no ethylenically unsaturated double bond and an alkali-soluble resin having an ethylenically unsaturated double bond that improves the photosensitivity of the composition. It can be used alone or in combination.

An alkali-soluble resin having no ethylenically unsaturated double bond is synthesized by using at least one carboxyl group-containing ethylenically unsaturated monomer and one or more of the other ethylenically unsaturated monomers. , Can be obtained by not imparting an ethylenically unsaturated bond to the side chain.

As the alkali-soluble resin having an ethylenically unsaturated double bond, for example, a resin into which an ethylenically unsaturated double bond has been introduced can be obtained by the methods (i) and (ii) shown below.

(Method (i))
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers is used. , The carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added and reacted, and the generated hydroxyl group is further reacted with a polybasic acid anhydride to form an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce it.

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

Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyls, halogens, nitros, and cyano-substituted products. Examples include monocarboxylic acid.

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

As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with one or more other monomers. There is a method of introducing an ethylenically unsaturated double bond and a carboxyl group by adding an ethylenically unsaturated monomer having an epoxy group to a part of the carboxyl group.

(Method (ii))
As the method (ii), an ethylenically unsaturated 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 the side chain hydroxyl group of the obtained copolymer with the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group.

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

Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate and 1,1-bis [(meth) acryloyloxy] ethyl isocyanate.

Examples of the monomer constituting the alkali-soluble resin include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and 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, methoxypolypropylene glycol (meth) acrylate, or (meth) acrylate such as ethoxypolyethylene glycol (meth) acrylate. ,
Alternatively, (meth) such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloylmorpholin. Acrylamides styrenes, styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ethers, n-propyl vinyl ethers, isopropyl vinyl ethers, n-butyl vinyl ethers, or isobutyl vinyl ethers, vinyl acetates, and fatty acid vinyls such as vinyl propionate. And so on.
Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide. Kumarin, 4,4'-bismaleimidediphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedimaleimide, N, N'-1,4- Phenylened maleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-Bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimide N-substituted maleimides such as hexanoate, N- [4- (2-benzoimidazolyl) phenyl] maleimide, 9-maleimide acrydin, etc.
Alternatively, EO-modified cresol acrylate, n-nonylphenoloxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO) -modified (meth) acrylate of phenol, EO or propylene oxide (PO) -modified (PO) of paracumylphenol ( Examples thereof include meth) acrylate, EO-modified (meth) acrylate of nonylphenol, and PO-modified (meth) acrylate of nonylphenol.

Alternatively, a carboxyl group-containing ethylenically unsaturated monomer can also be used. Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

Alternatively, a hydroxyl group-containing ethylenically unsaturated monomer can also be used. Examples of the hydroxyl group-containing ethylenically unsaturated monomer include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, or cyclohexane. Examples thereof include hydroxyalkyl (meth) acrylates such as dimethanol mono (meth) acrylate. Further, a polyether mono (meth) acrylate obtained by addition-polymerizing the above hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, (poly) γ-valerolactone, and (poly) ε-caprolactone. , And / or (poly) ester mono (meth) acrylate to which (poly) 12-hydroxystearic acid or the like is added.

Alternatively, a phosphoric acid ester group-containing ethylenically unsaturated monomer can also be used. The phosphoric acid ester group-containing ethylenically unsaturated monomer can be obtained, for example, by reacting the hydroxyl group of the hydroxyl group-containing ethylenically unsaturated monomer with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid. Can be mentioned.

The binder resin may be used alone or in combination of two or more at any ratio.

The content of the binder resin is preferably 20 to 1000 parts by mass, more preferably 20 to 400 parts by mass, based on the total mass of the colorant, from the viewpoint of film forming property and various resistances. More preferably, it is 50 to 250 parts by mass.

(Organic solvent)
The coloring composition in the present invention can contain an organic solvent from the viewpoint of dispersibility of the colorant and solubility of the binder resin. The organic solvent is not particularly limited, and known ones can be used.

Specific examples of the organic solvent include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, and 1,3-butylene. Glycoldiacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, Ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate , 4-Heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methyl Pyrrolidone, 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 monotersial butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether , Ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl Ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate Dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate. , Propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl Examples thereof include alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate and dibasic acid ester. Among them, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate are considered from the viewpoint of dispersibility of colorants and solubility of binder resin. , Alcohols such as benzyl alcohol and diacetone alcohol and ketones such as cyclohexanone are preferably used. These organic solvents may be used alone or in combination of two or more at any ratio.

[Method for producing coloring composition]
In the coloring composition of the present invention, the phthalocyanine pigment represented by the general formula (1) and the dispersion resin are added to an organic solvent, and if necessary, together with a binder resin and a dispersion aid, a kneader is used. It is produced by finely dispersing using various dispersion means such as a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual bead mill, or an attritor.

Further, the coloring composition in the present invention can be prepared by dispersing the phthalocyanine pigment represented by the general formula (1) and other colorants together, or by mixing the separately dispersed ones. You can also do it.

The coloring composition in the present invention is mixed with coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, by means of centrifugation, sintering filter, membrane filter or the like. It is preferable to remove the dust. As described above, the coloring composition preferably contains substantially no particles of 0.5 μm or more, and more preferably 0.3 μm or less.

<Photosensitive coloring composition>
One embodiment of the present invention relates to a photosensitive coloring composition. The photosensitive coloring composition includes the coloring composition, a photopolymerizable compound, and a photopolymerization initiator.

Hereinafter, components contained in or may be contained in the photosensitive coloring composition of one embodiment will be described.

[Photopolymerizable compound]
The photosensitive coloring composition in the present invention contains a photopolymerizable compound. The photopolymerizable compound is not particularly limited, and known compounds can be used.
The photopolymerizable compound contains a monomer or oligomer that is cured by ultraviolet rays, heat, or the like.

Specific examples of monomers and oligomers that are cured by ultraviolet rays or heat include polyethylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, epoxy (meth) acrylate, and EO. Modified bisphenol A di (meth) acrylate, 1,4-butanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyester (Meta) Acrylate, Trimethylol Propanetri (Meta) Acrylate, Tris (Acryloxyethyl) Isocyanurate, Tris (methacryloxyethyl) Isocyanurate, Dipentaerythritol Penta (Meta) Acrylate, Dipentaerythritol Hexa (Meta) Acrylate, Various acrylic acids and methacrylates such as caprolactone-modified dipentaerythritol hexaacrylate, ditrimethylolpropanetetra (meth) acrylate, epoxy acrylate, pentaerythritol tetra (meth) acrylate, (meth) acrylic acid, styrene, vinyl acetate, hydroxy Examples thereof include ethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, N-vinylformamide, and acrylonitrile.

Moreover, the photopolymerizable compound may contain an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphoric acid group.

Examples of the photopolymerizable compound containing an acid group include an esterified product of a free hydroxyl group-containing poly (meth) acrylate of a polyhydric alcohol and (meth) acrylic acid and a dicarboxylic acid; a polyvalent carboxylic acid and a mono. Examples thereof include esterified products with hydroxyalkyl (meth) acrylates. Specifically, monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropanedimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. Free carboxyl group-containing monoesteride with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and terephthalic acid; propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4 -Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 2-hydroxyethyl acrylate, 2- Examples thereof include monohydroxymonoacrylates such as hydroxyethyl methacrylate, 2-hydroxypropyl acrylate and 2-hydroxypropyl methacrylate, and oligoesterides containing a free carboxyl group with monohydroxymonomethacrylates.

Moreover, the photopolymerizable compound may contain a urethane bond. For example, a polyfunctional urethane acrylate obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting with a (meth) acrylate having a hydroxyl group. Urethane acrylate and the like can be mentioned.

Examples of the (meth) acrylate having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, trimethylolpropandi (meth) acrylate, pentaerythritol tri (meth) acrylate, and ditrimethylol propanetri (meth). Meta) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol ethylene oxide-modified penta (meth) acrylate, dipentaerythritol propylene oxide-modified penta (meth) acrylate, dipentaerythritol caprolactone-modified penta (meth) acrylate, glycerol acrylate Examples thereof include methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy (meth) acrylate, and a hydroxyl group-containing polyol polyacrylate.
Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

The photopolymerizable compound may be used alone or in combination of two or more at any ratio.

The content of the photopolymerizable compound is preferably 1 to 50 parts by mass, preferably 2 to 40 parts by mass, based on the total solid content of the photosensitive coloring composition from the viewpoint of photocurability and developability. More preferably.

[Photopolymerization initiator]
The photosensitive coloring composition in the present invention contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited, and known photopolymerization initiators can be used.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one. , 1-Hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl ] -1- [4- (4-morpholinyl) phenyl] -1-butanone, or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butane-1-one and other acetophenone compounds; Benzophenones such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl Benzophenone compounds such as -4'-methyldiphenylsulfide or 3,3', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, Thioxanthone compounds such as 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -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 (trichloromethyl) -S-triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2 , 4-Trichloromethyl- (4'-methoxystyryl) -6-triazine and other triazine compounds; 1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O) -Benzoyl oxime)], or oxime ester compounds such as etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole-3-yl]-, 1- (O-acetyloxime); Phosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinones such as 9,10-phenanthrene quinone, camphorquinone and ethylanthraquinone. Examples thereof include a system compound; a borate compound; a carbazole compound; an imidazole compound; and a titanosen compound.

The photopolymerization initiator may be used alone or in combination of two or more at any ratio.

From the viewpoint of photocurability, the content of the photopolymerization initiator is preferably 5 to 200 parts by mass, more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the colorant.

(Sensitizer)
In the photosensitive coloring composition of the present invention, a sensitizer can be further used from the viewpoint of improving the photocurability. The sensitizer is not particularly limited, and known sensitizers can be used.

Examples of the sensitizer include becalcon derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone derivatives. Polymethine dyes such as anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonoal derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, Indoline derivative, azulene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinoporphyrazine derivative, phthalocyanine derivative, tetraazaporphyrazine derivative, tetraquinoxalylo Porphyrazine derivative, naphthalocyanine derivative, subphthalocyanine derivative, pyrylium derivative, thiopyrylium derivative, tetraphyllin derivative, anurene derivative, spiropirane derivative, spiroxazine derivative, thiospiropirane derivative, metal arene complex, organic ruthenium complex, or Michler ketone derivative, α- Achilloxyester, acylphosphine oxide, methylphenylglioxylate, benzyl, 9,10-phenanthrene quinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalofenone, 3,3'or 4, Examples thereof include 4'-tetra (t-butylperoxycarbonyl) benzophenone and 4,4'-bis (diethylamino) benzophenone. Of these, thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives are preferable from the viewpoint of improving photocurability.

The sensitizer may be used alone or in combination of two or more at any ratio.

From the viewpoint of photocurability, the content of the sensitizer is preferably 3 to 60 parts by mass and more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the photopolymerization initiator.

(Binder resin)
The above-mentioned binder resin can be further added to the photosensitive coloring composition in the present invention from the viewpoint of coating film resistance.

(Organic solvent)
Further, from the viewpoint of coatability, the above-mentioned organic solvent can be added to the photosensitive coloring composition in the present invention.

(Chain transfer agent)
The photosensitive coloring composition in the present invention may contain a chain transfer agent from the viewpoint of suppressing polymerization inhibition by oxygen. The chain transfer agent is not particularly limited, and known ones can be used.

Examples of the chain transfer agent include thiol compounds. Of these, a polyfunctional thiol compound having two or more thiol groups is preferable, and specifically, hexanedithiol, decandithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, etc. Ethylene Glycol Bisthioglycolate, Ethylene Glycol Bisthiopropionate, Trimethylol Propanetristhioglycolate, Trimethylol Propanetristhiopropionate, Trimethylol Propantris (5-Mercaptobutyrate), Pentaerythritol Tetraxthioglycolate , Pentaerythritol tetraxthiopropionate, tris (2-hydroxyethyl) trimercaptopropionate, isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N) -Dibutylamino) -4,6-dimercapto-s-triazine and the like.

The polyfunctional thiol compound may be used alone or in combination of two or more at any ratio.

The content of the polyfunctional thiol is preferably 0.1 to 20 parts by mass, more preferably 2 to 10 parts by mass, based on the total solid content of the photosensitive coloring composition.

(Leveling agent)
The photosensitive coloring composition in the present invention may contain a leveling agent from the viewpoint of coatability. The leveling agent is not particularly limited, and known ones can be used.

As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray, BYK (registered trademark) 333 manufactured by Big Chemie, and the like. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK (registered trademark) 310 and BYK (registered trademark) 370 manufactured by Big Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination.

A particularly preferable leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, which has a hydrophilic group but has low solubility in water and is added to a coloring composition. , It has a feature of low surface tension lowering ability, and it is useful to have good wettability to the glass plate despite its low surface tension lowering ability, and addition that does not cause defects in the coating film due to foaming. Those capable of sufficiently suppressing chargeability in terms of amount can be preferably used. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes 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 polyalkylene oxide unit is bonded to the terminal of dimethylpolysiloxane, and dimethylpolysiloxane. It may be any of the linear block copolymer types that are alternately and repeatedly bonded. Didimethylpolysiloxane 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 to these.

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

Examples of the chaotic surfactant added as a supplement to the leveling agent include alkyl quaternary ammonium salts and ethylene oxide adducts thereof. Nonionic surfactants to be added as a supplement to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, and polyoxyethylene sorbitan monostearate. , Polyethylene glycol monolaurate and the like. Examples of the amphoteric tenside agent supplementarily added to the leveling agent include an alkyl betaine such as alkyldimethylaminoacetic acid betaine and an amphoteric tenside agent such as alkyl imidazoline.

The content of the leveling agent is preferably 0.001 to 2.0 parts by mass, more preferably 0.005 to 1.0 parts by mass, based on the total solid content of the photosensitive coloring composition. preferable.

(UV absorber, polymerization inhibitor)
The photosensitive coloring composition in the present invention may contain an ultraviolet absorber or a polymerization inhibitor. By containing an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled.

Examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3- (dodecyl and tridecyl) oxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethyl). Phenyl) -1,3,5-triazine, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine Hydroxyphenyltriazines such as 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) Phenol, benzotriazoles such as 2- (3-t butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, 2, Benzopenone type such as 2', 4,4'-tetrahydroxybenzophenone, phenyl salicylate, salicylate type such as p-tert-butylphenyl salicylate, ethyl-2-cyano-3,3'-diphenylacrylate and the like. Cyanoacrylate-based, 2,2,6,6, -tetramethylpiperidin-1-oxyl (triacetone-amine-N-oxyl), bis (2,2,6,6-tetramethyl-4-piperidyl) -sevacate , Poly [[6-[(1,1,3,3-tetrabutyl) amino] -1,3,5-triazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-diyl] Examples thereof include hindered amines such as piperidinyl) imino].
The ultraviolet absorber may be used alone or in admixture of two or more at an arbitrary ratio as required.

Examples of the polymerization inhibitor include methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, t-butylcatechol and the like. Hydroquinone derivatives and phenol compounds, phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, amine compounds such as 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, manganese diphenyldithiocarbamate, etc. Examples thereof include nitroso compounds such as copper and manganese salt compounds, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine, and ammonium salts or aluminum salts thereof.
The polymerization inhibitor may be used alone or in admixture of two or more at any ratio as required.

The ultraviolet absorber and the polymerization inhibitor can be used in an amount of 0.01 to 20 parts by mass, preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the colorant in the coloring composition.
Better resolution can be obtained by using 0.01 part by mass or more of the ultraviolet absorber or the polymerization inhibitor.

(Antioxidant)
The photosensitive coloring composition in the present invention may contain an antioxidant from the viewpoint of improving the transmittance of the coating film. The antioxidant can increase the transmittance of the coating film because it prevents the photopolymerization initiator contained in the photosensitive coloring composition from being oxidized and yellowed by the thermal process at the time of thermosetting or ITO annealing. .. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high transmittance of the coating film can be obtained.

Preferred examples of the antioxidant include a hindered phenol-based antioxidant, a hindered amine-based antioxidant, a phosphorus-based antioxidant, a sulfide-based antioxidant, and the like. Further, more preferably, it is a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant.
The antioxidant may be used alone or in admixture of two or more at any ratio as required.

Examples of the hindered phenolic antioxidant include 2,4-bis [(laurylthio) methyl] -o-cresol and 1,3,5-tris (3,5-di-t-butyl-4-hydroxybenzyl). , 1,3,5-Tris (4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), and 2,4-bis- (n-octylthio) -6- (4-hydroxy-3,5) -Di-t-butylanilino) -1,3,5-triazine, pentaerythritol tetrakis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and the like can be mentioned.

Among the hindered amine-based antioxidants, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (N-methyl-2,2,6,6-tetramethyl-4-piperidyl) sebacate, N, N'-bis (2,2,6,6-tetramethyl-4-piperidyl) -1,6-hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4) -Piperidyl) Amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) (1,2,3) 4-butanetetracarboxylate, poly [{6- (1,1,3,3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6) -Tetramethyl-4-piperidyl) imino} Hexamethyl {(2,2,6,6-tetramethyl-4-piperidyl) imino}], poly [(6-morpholino-1,3,5-triazin-2,4) -Diyl) {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethine {(2,2,6,6-tetramethyl-4-piperidyl) imino}], dimethyl succinate and 1- (2-Hydroxyethyl) -4-hydroxy-2,2,6,6-polycondensate with tetramethylpiperidine, N, N'-4,7-tetrakis [4,6-bis {N-butyl-N -(1,2,2,6,6-pentamethyl-4-piperidyl) amino} -1,3,5-triazine-2-yl] -4,7-diazadecan-1,10-diamine and the like.

Examples of the phosphorus-based antioxidant include tris [2-[[2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine. -6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetra-tert-butyldibenzo [d, f] [1,3,2] dioxaphosfepin-2] -Il) oxy] ethyl] amine, ethylbis phosphite (2,4-ditert-butyl-6-methylphenyl) can be mentioned.

Examples of the sulfide-based antioxidant include 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] and 2,4-bis [(octylthio) methyl]. Examples thereof include -o-cresol and 2,4-bis [(laurylthio) methyl] -o-cresol.

The content of the antioxidant is preferably 0.1 to 5% by mass based on 100% by mass of the total solid content of the photosensitive coloring composition.
When the amount of the antioxidant is less than 0.1% by mass, the effect of increasing the transmittance is small, and when it is more than 5% by mass, the hardness is greatly reduced and the sensitivity of the coloring composition for a color filter is greatly reduced.

(Other ingredients)
The photosensitive coloring composition in the present invention contains an adhesion improver such as a silane coupling agent or an amine compound having a function of reducing dissolved oxygen in order to enhance the adhesion to a transparent substrate. Can be done.

Examples of the silane coupling agent include vinylsilanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, and β-. (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as (epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N- β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysisilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl- Examples thereof include aminosilanes such as γ-aminopropyltrimethoxysilane and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane.

The silane coupling agent can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant in the coloring composition.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, and the like. Examples thereof include 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethylparatoluidine and the like.

<Color filter>
One embodiment of the present invention relates to a color filter. The color filter includes a filter segment formed from the photosensitive coloring composition on a substrate.

Hereinafter, the color filter of one embodiment will be described.

[Manufacturing method of color filter]
The color filter of the present invention can be manufactured by a printing method or a photolithography method. The formation of the filter segment by the printing method can be patterned only by repeating printing and drying of the coloring composition prepared as the printing ink, and therefore, as a manufacturing method of the color filter, it is excellent in mass productivity at low cost. Further, with the development of printing technology, it is possible to print a fine pattern having high dimensional accuracy and smoothness. In order to perform printing, it is preferable that the composition is such that the ink does not dry or solidify on the printing plate or on the blanket. It is also important to control the fluidity of the ink on the printing machine, and the viscosity of the ink can be adjusted with a dispersant or an extender pigment.

When forming a filter segment by a photolithography method, a method of applying a photosensitive coloring composition prepared as an organic solvent development type or an alkali development type on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. Therefore, the coating is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays through a mask having a predetermined pattern provided in contact with or without contact with the film. After that, after immersing in an organic solvent or an alkaline developer or spraying the developer with a spray to remove the uncured part to form a desired pattern, the same operation is repeated for other colors to apply a color filter. Can be manufactured. Further, in order to promote the polymerization of the photosensitive coloring composition, heating can be applied if necessary. According to the photolithography method, a color filter having higher accuracy than the above-mentioned printing method can be manufactured.

At the time of development, an aqueous solution of sodium carbonate, sodium hydroxide or the like is used as the alkaline developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. The developer may also contain an antifoaming agent or a surfactant.
In order to increase the exposure sensitivity, a photosensitive coloring composition is applied and dried, and then a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. After that, ultraviolet exposure can be performed.

The color filter of the present invention can be produced by an electrodeposition method, a transfer method, an inkjet method or the like in addition to the above-mentioned methods, and the photosensitive coloring composition of the present invention can be used in any of the methods. The electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles using the transparent conductive film formed on the substrate. .. 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 the filter segment is transferred to a desired substrate.

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

The dry film thickness of the filter segment and the black matrix is preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a vacuum dryer, a convection oven, an IR oven, a hot plate or the like may be used.

The color filter is bonded to the opposite substrate using a sealing agent, liquid crystal is injected from the injection port provided in the sealing portion, the injection port is sealed, and a polarizing film or a retardation film is placed on the outside of the substrate as necessary. A liquid crystal display panel is manufactured by laminating.

Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optical convencend bend (OCB). It can be used in the liquid crystal display mode in which colorization is performed using a color filter such as.

As the transparent substrate, a glass plate such as soda-lime glass, low-alkali borosilicate glass, or non-alkali aluminum borosilicate glass, or a resin plate such as polycarbonate, polymethylmethacrylate, or polyethylene terephthalate is used. Further, on the surface of the glass plate or the resin plate, a transparent electrode made of indium oxide, tin oxide or the like may be formed for driving the liquid crystal after the panelization.

Examples and comparative examples are shown below, and the present invention will be described in more detail. However, the present invention is not limited thereto. In the examples and comparative examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

The identification of the phthalocyanine pigment represented by the general formula (1) and the phthalocyanine compound represented by the general formula (4) in the present invention is carried out by a time-of-flight mass spectrometer (autoflexIII (TOF-MS)), Bruker Daltonics. Match the molecular ion peak of the mass spectrum obtained by using (manufactured by) and the mass number obtained by calculation, and carbon obtained by using an elemental analyzer (2400CHN elemental analyzer, manufactured by Perkin Elmer). This was done by matching the ratio of hydrogen and nitrogen with the theoretical value.

The LC-MS spectrum was used for the identification of the phosphorus compound represented by the general formula (5) used in the present invention and the distribution width of halogen atoms. The measurement of the LC-MS spectrum was performed under the following conditions.

Equipment: UPLC H-Class / XevoTQD manufactured by Japan Waters Corp.
Column: Symmetry C185 micron (Japan Waters Corp.)
Eluent:
(A) H ₂ O
(B) DMF
Eluent conditions: (A): (B) = 10:90 (volume ratio)
Flow velocity: 0.400 ml / min Injection volume: 1 μl
Column temperature: 40 ° C
Measurement wavelength: 300 nm

The obtained compound was identified based on the agreement between the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation.
The distribution width of halogen atoms is the peak area ratio when the area of the peak of the molecular weight corresponding to each component is calculated in the obtained mass spectrum and the total area of the detected peaks in the chromatogram is set to 100%. Was calculated by counting the number of peaks of 1% or more.

The number of substitutions of the halogen atom represented by n in the general formula (4) was obtained by burning the phthalocyanine compound represented by the general formula (4) by an oxygen combustion flask method and absorbing the combusted product in water. The liquid was obtained by quantifying the amount of halogen by an ion chromatograph (ICS-2000 ion chromatography, manufactured by DIONEX) and converting it into the number of substitutions of halogen atoms.
By the same method, the number of substitutions of the halogen atom represented by m in the general formula (5) was obtained.

The weight average molecular weights of the dispersed resin and the binder resin in the present invention were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, two separation columns are connected in series, and "TSK-GEL SUPER HZM-N" is connected in two for both fillers, and the oven temperature is 40. The measurement was carried out at a flow rate of 0.35 ml / min using a THF solution as an eluent at ° C. The sample was dissolved in a solvent consisting of 1 wt% of the above eluate and injected in 20 microliters. All molecular weights are polystyrene-equivalent values.

The acid value (mgKOH / g) in the present invention was measured as follows.
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of the sample solution and stirred to uniformly dissolve the sample solution. Using a 0.1 mol / L KOH aqueous solution as a titrator, an automatic titrator ("COM-555" Hiranuma Sangyo) The acid value (mgKOH / g) of the sample solution was measured by titration using (manufactured by). Then, the acid value per solid content of the sample was calculated from the acid value of the sample solution and the solid content concentration of the sample solution.

The amine value (mgKOH / g) in the present invention is a value obtained by converting the measured total amine value (mgKOH / g) into a solid content according to the method of ASTM D 2074.

<Synthesis of phosphorus compounds>
First, a method for synthesizing a phosphorus compound used for synthesizing a phthalocyanine pigment of Examples and Comparative Examples will be described.

(Synthesis of phosphorus compound (d-1))
In the reaction vessel, 150 parts of diphenyl phosphate was added to 1,500 parts of concentrated sulfuric acid under an ice bath. Then, 173 parts of 1,3-dibromo-5,5-dimethylhydantoin was added, and the mixture was stirred at 15 ° C. for 4 hours. Subsequently, this sulfuric acid solution was injected into 9,000 parts of cold water at 3 ° C., and the formed precipitate was treated in the order of filtration, washing with water, washing with 1% aqueous sodium hydroxide solution, and washing with water, and dried to 157 parts. The phosphorus compound (d-1) represented by the general formula (5) was obtained. The obtained phosphorus compound (d-1) had Y = bromine, m = 2, and a halogen atom distribution width of 3.

(Synthesis of phosphorus compound (d-2))
In the synthesis of the phosphorus compound (d-1), the phosphorus compound (d-1) was prepared except that 173 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 160 parts of the phosphorus compound N-chlorosuccinimide. The phosphorus compound (d-2) was obtained in the same manner as in the synthesis of. The obtained phosphorus compound (d-2) had Y = chlorine, m = 2, and a halogen atom distribution width of 3.

(Synthesis of phosphorus compound (d-3))
In the reaction vessel, 150 parts of diphenyl phosphate was added to 1,500 parts of concentrated sulfuric acid under an ice bath. Then, 80 parts of N-chlorosuccinimide was added, and the mixture was stirred at 15 ° C. for 2 hours. Subsequently, 88 parts of 1,3-dibromo-5,5-dimethylhydantoin was added, and the mixture was further stirred at 15 ° C. for 2 hours. This sulfuric acid solution is injected into 9000 parts of cold water at 3 ° C., and the generated precipitate is treated in the order of filtration, washing with water, washing with 1% aqueous sodium hydroxide solution, and washing with water, and dried to dry out the above general formula (157 parts). The phosphorus compound (d-3) represented by 5) was obtained. The obtained phosphorus compound (d-3) had Y = chlorine, bromine, m = 2 (chlorine was 1, bromine was 1), and the distribution width of halogen atoms was 3.

(Synthesis of phosphorus compounds (d-4) to (d-7))
In the synthesis of the phosphorus compound (d-1), the same operations as those for the phosphorus compound (d-1) were carried out except that the amount of the halogenating agent charged was changed to the conditions shown in Table 1, respectively. d-4) to (d-7) were obtained. Table 1 shows the distribution widths of Y, m, and halogen atoms of the obtained phosphorus compounds (d-4) to (d-7).

(Synthesis of phosphorus compound (d-8))
In the synthesis of the phosphorus compound (d-1), the phosphorus compound (d-8) was similar to the synthesis of the phosphorus compound (d-1) except that 150 parts of diphenyl phosphate was changed to diphenylphosphinic acid. Got The obtained phosphorus compound (d-8) had a bromine number of 2 and a halogen atom distribution width of 3.

Next, a method for synthesizing the phthalocyanine compound represented by the general formula (4) used for synthesizing the phthalocyanine pigments of Examples and Comparative Examples will be described.

(Synthesis of phthalocyanine compound (p-1))
In the reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were mixed and stirred with 1,250 parts of n-amyl alcohol. To this, 266 parts of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene) was added, the temperature was raised, and the mixture was refluxed at 136 ° C. for 5 hours. The reaction solution cooled to 30 ° C. with stirring was poured into a mixed solvent consisting of 5,000 parts of methanol and 10,000 parts of water with stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2,000 parts of methanol and 4,000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine represented by the above general formula (3). Elemental analysis of the obtained chloroaluminum phthalocyanine revealed that the measured values (C) 66.85%, (H) 2.80%, and (N) 19.49% were measured. It was 7%, (H) 3.0%, and (N) 19.2%, and it was identified as the target compound.
Then, in the reaction vessel, 100 parts of the above chloroaluminum phthalocyanine was added to 1500 parts of concentrated sulfuric acid under an ice bath. Then, 225 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 20 ° C. for 8 hours. Subsequently, this sulfuric acid solution was injected into 9,000 parts of cold water at 3 ° C., and the formed precipitate was treated in the order of filtration, washing with water, washing with 1% aqueous sodium hydroxide solution, and washing with water, and dried to 159 parts. The phthalocyanine compound (p-1) represented by the general formula (4) was obtained. The obtained phthalocyanine compound (p-1) was X = bromine and n = 8.

(Synthesis of phthalocyanine compound (p-2))
In the synthesis of the phthalocyanine compound (p-1), phthalocyanine was obtained in the same manner as in the synthesis of the phthalocyanine compound (p-1), except that 215 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 175 parts. Compound (p-2) was obtained. The obtained phthalocyanine compound (p-2) was X = bromine and n = 6.

(Synthesis of phthalocyanine compound (p-3))
In the synthesis of the phthalocyanine compound (p-1), 215 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 296 parts in the same manner as in the synthesis of the phthalocyanine compound (p-1). A phthalocyanine compound (p-3) was obtained. The obtained phthalocyanine compound (p-3) was X = bromine and n = 10.

(Synthesis of phthalocyanine compound (p-4))
In the synthesis of the phthalocyanine compound (p-1), 215 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 358 parts in the same manner as in the synthesis of the phthalocyanine compound (p-1). A phthalocyanine compound (p-4) was obtained. The obtained phthalocyanine compound (p-4) was X = bromine and n = 12.

(Synthesis of phthalocyanine compound (p-5))
In the synthesis of the phthalocyanine compound (p-1), except that 215 parts of 1,3-dibromo-5,5-dimethylhydantoin was changed to 122 parts of trichloroisocyanuric acid, the synthesis of the phthalocyanine compound (p-1) Similarly, a phthalocyanine compound (p-5) was obtained. The obtained phthalocyanine compound (p-5) was X = chlorine and n = 8.

(Synthesis of phthalocyanine compound (p-6))
In the reaction vessel, 100 parts of the above chloroaluminum phthalocyanine was added to 1,500 parts of concentrated sulfuric acid under an ice bath. Then, 60 parts of trichloroisocyanuric acid was gradually added, and the mixture was stirred at 20 ° C. for 3 hours. Subsequently, 136 parts of 1,3-dibromo-5,5-dimethylhydantoin was gradually added, and the mixture was stirred at 25 ° C. for 4 hours. Subsequently, this sulfuric acid solution was injected into 9,000 parts of cold water at 3 ° C., and the formed precipitate was treated in the order of filtration, washing with water, washing with 1% aqueous sodium hydroxide solution, and washing with water, and dried to 159 parts. The phthalocyanine compound (p-6) represented by the general formula (3) was obtained. The obtained phthalocyanine compound (p-6) was X = bromine and chlorine, n = 8 (4 for bromine and 4 for chlorine).

<Synthesis of phthalocyanine pigment represented by general formula (1)>
[Example 1]
(Synthesis of phthalocyanine pigment (GP-1))
To the reaction vessel, 1,000 parts of 1-methyl-2-pyrrolidinone, 100 parts of a phthalocyanine compound (p-1), and 50 parts of a phosphorus compound (d-1) were added. After reacting at 85 ° C. for 3 hours, the solution was injected into 8,000 parts of water. The reaction product was filtered, washed with 16,000 parts of water, and dried under reduced pressure at 60 ° C. for 24 hours to obtain 112 parts of the product. Then, the obtained product was added to 600 parts of propylene glycol monomethyl ether acetate, and the mixture was heated at 120 ° C. for 2 hours. The product was filtered and dried under reduced pressure at 60 ° C. for 24 hours to obtain 106 parts of a phthalocyanine pigment (GP-1).

[Examples 2 to 12]
(Synthesis of phthalocyanine pigments (GP-2-12))
In the synthesis of the phthalocyanine pigment (GP-1), the phthalocyanine pigment and the phosphorus compound as raw materials were changed to the compositions and blending ratios shown in Table 2, respectively, in the same manner as in Example 1. (GP-2 to 12) were obtained.

[Example 13]
(Synthesis of phthalocyanine pigment (GP-13))
In the synthesis of the phthalocyanine pigment (GP-1), 50 parts of the phosphorus compound (d-1) was changed to 50 parts of bis (4-bromophenyl) phosphate having a distribution width of 1 halogen atom. A phthalocyanine pigment (GP-13) was obtained in the same manner as in Example 1.

[Example 14]
(Synthesis of phthalocyanine pigment (GP-14))
In the synthesis of the phthalocyanine pigment (GP-1), 50 parts of the phosphorus compound (d-1) was changed to 72 parts of bis (3,5-dibromophenyl) phosphate having a distribution width of 1 halogen atom. , A phthalocyanine pigment (GP-14) was obtained in the same manner as in Example 1.

[Comparative Example 1]
(Synthesis of Comparative Phthalocyanine Pigment (CP-1))
In the synthesis of the phthalocyanine compound (GP-1), the comparative phthalocyanine pigment (CP-1) was obtained in the same manner as in Example 1 except that 50 parts of the phosphorus compound (d-1) was changed to 32 parts of diphenyl phosphate. Got

[Comparative Example 2]
(Synthesis of Comparative Phthalocyanine Pigment (CP-2))
In the synthesis of the phthalocyanine compound (GP-1), comparative phthalocyanine was compared in the same manner as in Example 1 except that 50 parts of the phosphorus compound (d-1) was changed to 44 parts of bis (p-nitrophenyl) phosphate. A pigment (CP-2) was obtained.

[Comparative Example 3]
(Synthesis of Comparative Phthalocyanine Pigment (CP-3))
In the synthesis of the phthalocyanine compound (GP-1), a comparative phthalocyanine pigment (CP-3) was obtained in the same manner as in Example 1 except that 50 parts of the phosphorus compound (d-1) was changed to 47 parts of 2-dynaphthyl phosphate. ) Was obtained.

[Comparative Example 4]
(Synthesis of Comparative Phthalocyanine Pigment (CP-4))
In the synthesis of the phthalocyanine compound (GP-1), a comparative phthalocyanine pigment (CP-) was obtained in the same manner as in Example 1 except that 50 parts of the phosphorus compound (d-1) was changed to 48 parts of (d-8). 4) was obtained.

<Preparation of coloring composition>
The pigment, the dispersion resin, and the binder resin used in the coloring composition of the present invention will be described.

(Synthesis of Acidic Dispersion Resin S1 with Carboxyl Group)
In a reaction vessel equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer, 4 parts of trimellitic anhydride, 2 parts of 3-mercapto-1,2-propanediol, and propylene glycol monomethyl ether acetate (hereinafter, also referred to as PGMAc). ) 50 parts and 0.1 part of dimethylbenzylamine were charged. After replacement with nitrogen gas, the inside of the reaction vessel was heated to 120 ° C. and reacted at 120 ° C. for 4 hours, and then reacted at 80 ° C. for 2 hours. Furthermore, 30 parts of tertiary butyl acrylate, 20 parts of methyl methacrylate (3-ethyloxetane-3-yl) methyl (“ETERNACOLL® OXMA” manufactured by Ube Kosan Co., Ltd.), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and propylene glycol. 10 parts of monomethyl ether acetate was charged, and 0.2 part of 2,2'-azobisisobutyronitrile was added every 30 minutes in 15 portions while keeping the inside of the reaction vessel at 80 ° C. The non-volatile content was measured 1 hour after the final addition, and it was confirmed that 95% of the monomers had reacted. PGMAc was added so as to have a non-volatile content of 40% by mass in the non-volatile content measurement, and a solution of an acidic dispersion resin S1 having a carboxyl group having an acid value of 55 mgKOH / g per non-volatile content and a weight average molecular weight of 15,000 was obtained.

(Synthesis of acidic dispersant S2 having a phosphoric acid group)
186 g of lauryl alcohol, 571 g of ε-caprolactone monomer, and 0.6 g of tetrabutyl titanate were charged in a reaction vessel equipped with a gas introduction tube, a condenser, and a stirrer, replaced with nitrogen gas, and then heated and stirred at 120 ° C. for 3 hours. The disappearance of the caprolactone monomer was confirmed by a GPC (gel permeation chromatography) RI detector using tetrahydrofuran as an eluent. After cooling to 40 ° C. or lower, the mixture is mixed with 84.5 g of polyphosphoric acid having an orthophosphoric acid equivalent content of 116%, gradually heated, and heated at 80 ° C. for 6 hours with stirring. An acidic dispersant S2 having a number average molecular weight of R ₁ and a phosphoric acid group having an abundance ratio of n = 1 and 2 of 100:12 was obtained. PGMAc was added so as to have a non-volatile content of 40% by mass in the measurement of the non-volatile content, and an acidic dispersant S2 solution having an acid value of 166 mgKOH / g per non-volatile content was obtained.

(Synthesis of basic dispersion resin B1)
A reactor equipped with a gas introduction tube, a condenser, a stirrer, and a thermometer was charged with 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst, and charged at 50 ° C. while flowing nitrogen. Was stirred for 1 hour, and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate was charged as an initiator, 5.6 parts of cuprous chloride and 133 parts of PGMAc were charged as a catalyst, and the temperature was raised to 110 ° C. under a nitrogen stream to initiate polymerization of the first block portion. .. After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content. Next, 61 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate and 10 parts of methacryloyloxyethylene benzyldimethylammonium chloride as the monomer of the second block part were added to this reactor, and the reaction was continued by stirring at 110 ° C. in a nitrogen atmosphere. did. After 2 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate of the second block portion was 98% or more in terms of the non-volatile content, and the reaction solution was cooled to room temperature for polymerization. It stopped. After cooling to room temperature, PGMAc was added so that the reaction solution had a non-volatile content of 40% by mass to obtain a basic dispersion resin B1 having a weight average molecular weight of 20,000 and an amine value of 169.8 mgKOH / g.

(Synthesis of binder resin 1)
196 parts of PGMAc was charged into a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirrer, the temperature was raised to 80 ° C. while stirring, nitrogen was replaced in the reaction vessel, and then the dropping pipe was used. , N-Butyl methacrylate 37.2 parts, 2-hydroxyethyl methacrylate 12.9 parts, methacrylic acid 12.0 parts, paracumylphenol ethylene oxide-modified acrylate (“Aronix (registered trademark) M110” manufactured by Toa Synthetic Co., Ltd.) 20. A mixture of 7 parts and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. A solution of the binder resin 1 was obtained. The weight average molecular weight was 26,000.

(Synthesis of binder resin 2)
The inside of the flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube was made into a nitrogen atmosphere, 210 parts of PGMAc was added, and the temperature was raised to 100 ° C. while stirring. Next, 106 parts of benzyl methacrylate, 22 parts of acrylic acid, and 22 parts of dicyclopentanyl methacrylate (“Funkril (registered trademark) FA-513M” manufactured by Hitachi Chemical Co., Ltd.) were dissolved in 215 parts of PGMAc, and further 2,2 ′-. A solution prepared by dissolving 3.6 parts of azobisisobutyronitrile was added dropwise to a flask, and the mixture was continuously stirred at 100 ° C. for 5 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. A solution of the binder resin 2 was obtained. The weight average molecular weight was 10,000.

[Example 101]
(Preparation of coloring composition (GM-1))
The following components are mixed and stirred so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm for 3 hours, and then having a pore diameter of 1 The mixture was filtered through a 0.0 μm filter to prepare a green coloring composition (GM-1) having a non-volatile component of 20% by mass.

Phthalocyanin pigment (GP-1) finely divided by the method described above: 14.0 parts Solution of acidic dispersion resin S1: 1.5 parts Solution of basic dispersion resin B1: 1.5 parts Solution of binder resin 1: 12 .0 parts Solution of binder resin 2: 12.0 parts propylene glycol monomethyl ether acetate (PGMAc): 59.0 parts

[Examples 102 to 118, Comparative Examples 101 to 104]
Examples 102 to 118 and Comparative Examples 101 to 104 were prepared in the same manner as in Example 101 except that the raw materials and amounts shown in Table 3 were changed.

<Evaluation of coloring composition>
The evaluation of the viscosity, storage stability, and contrast of the coloring compositions of Examples 101 to 118 and Comparative Examples 101 to 104 was carried out by the following methods. The results are shown in Table 3.

(viscosity)
The viscosity of the coloring composition was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd .: ELD-type viscometer) under the conditions of a temperature of 25 ° C. and a rotation speed of 50 rpm. 3 or more was set as a practical level.

5: 4.0 or more, less than 8.0 4: 8.0 or more, less than 12.0 3: 12.0 or more, less than 16.0 2: 16.0 or more, less than 20.0 1: 20.0 or more

(Evaluation of storage stability)
Based on the initial viscosity on the day of preparation of the coloring composition and the viscosity measured after storage in a constant temperature chamber at 40 ° C for 7 days, the viscosity change rate (%) (= (viscosity after storage at 40 ° C for 7 days-initial viscosity) / initial Viscosity x 100) was calculated and storage stability was evaluated according to the following criteria. 3 or more was set as a practical level.
Both the initial viscosity and the viscosity after storage were measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd .: ELD-type viscometer) under the conditions of a temperature of 25 ° C. and a rotation speed of 50 rpm.

5: Viscosity change rate is less than 2% 4: Viscosity change rate is 2% or more and less than 5%
3: Viscosity change rate is 5% or more and less than 10% 2: Viscosity change rate is 10% or more and less than 15% 1: Viscosity change rate is 15% or more

(Evaluation of contrast ratio)
The coloring composition was applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so as to have a film thickness of 1.5 μm, then dried at 70 ° C. for 20 minutes, and then further 230 ° C. The coating film substrate was prepared by heating and allowing to cool for 30 minutes.
The light emitted from the backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a coating film of a coloring composition coated on a glass substrate, and reaches the other polarizing plate. At this time, if the polarizing plate and the polarizing planes of the polarizing plate are parallel, the light passes through the polarizing plate, but if the polarizing planes are orthogonal to each other, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the coloring composition, scattering or the like occurs due to the colorant particles, and if a part of the polarizing surface is displaced, the light is transmitted when the polarizing plates are parallel. When the amount of light emitted is reduced and the polarizing plates are orthogonal, part of the light is transmitted. This transmitted light was measured as the brightness on the polarizing plate, and the ratio of the brightness when the polarizing plates were parallel to the brightness when the polarizing plates were orthogonal was calculated as a contrast ratio.

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

Therefore, when scattering occurs due to the colorant in the coating film, the brightness when parallel is reduced and the brightness when orthogonal is increased, so that the contrast ratio is lowered.
Using the prepared coating film substrate, a color luminance meter (“BM-5A” manufactured by Topcon Co., Ltd.) was used as a luminance meter, and a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used as a polarizing plate. The measurement was carried out through a black mask having a 1 cm square hole in the measurement portion. 3 or more was set as a practical level.

5: 9,000 or more 4: 7,000 or more, less than 9,000 3: 5,000 or more, less than 7,000 2: 3,000 or more, less than 5,000 less than 1: 3,000

In Examples 101 to 118 of the present invention, the results were excellent in viscosity, storage stability, and contrast. Among them, a coloring composition using a phthalocyanine pigment in which Y is bromine, m is 2 to 3, the distribution width of halogen atoms is 2 to 6, and X is bromine is particularly excellent in viscosity, storage stability, and contrast. Was there.
Further, as can be seen from Examples 101, 117 and 118, the coloring composition in which the acidic dispersion resin and the basic dispersion resin are used in combination as the dispersion resin has excellent viscosity and storage stability. ..
On the other hand, the coloring composition using the phthalocyanine pigment having m of 0 in the general formula (1) as in Comparative Example 101 resulted in inferior contrast. Further, the coloring compositions using the phthalocyanine pigment in which the acidic compound does not have the structure specific to the present application as in Comparative Examples 102 to 104 were inferior in viscous storage stability and contrast.

<Preparation of coloring composition containing yellow pigment>
The yellow pigment used in the coloring composition containing the yellow pigment of the present invention will be described.

(Production of miniaturized PY138)
C. I. Pigment Yellow 138 (BASF's "Pariotor® Yellow L 0960HD") 200 parts, sodium chloride 1,400 parts, and diethylene glycol 360 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) at 80 ° C. Kneaded for 6 hours. Next, this kneaded product was put into 8 liters of warm water and stirred for 2 hours while heating at 80 ° C. to form a slurry. This slurry was filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. for 24 hours to obtain a refined PY138.

(Making miniaturized PY150)
C. I. Pigment Yellow 138 200 copies by C.I. I. Pigment Yellow 150 (“YELLOW PIGMENT E4GN” manufactured by LANXESS Co., Ltd.) was changed to 200 parts, and the miniaturized PY150 was obtained by the same method as the miniaturized PY138.

(Making miniaturized PY150)
C. I. Pigment Yellow 138 200 copies by C.I. I. Pigment Yellow 185 (“Pariotor® Yellow L1155” manufactured by BASF) was changed to 200 parts, and a refined PY185 was obtained in the same manner as the refined yellow pigment (PY138-1).

(Preparation of miniaturized quinophthalone pigment (A) represented by the general formula (2))
A quinophthalone pigment (A) represented by the following formula (2-1) was obtained according to the synthesis method described in JP-A-2012-226110.

Equation (2-1)

Subsequently, 100 parts of the obtained quinophthalone pigment (A), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C. for 8 hours. Next, this kneaded product was put into warm water and stirred for 1 hour while heating at about 70 ° C. to form a slurry, which was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. A refined quinophthalone pigment (A) was obtained.

(Preparation of miniaturized quinophthalone pigment (B) represented by the general formula (2))
A quinophthalone pigment (B) represented by the following formula (2-2) was obtained according to the synthesis method described in Japanese Patent No. 6432077.

Equation (2-2)

Subsequently, 100 parts of the obtained quinophthalone pigment (B), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 120 ° C. for 8 hours. Next, this kneaded product was put into 5 liters of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. Then, a finely divided quinophthalone pigment (B) was obtained.

(Preparation of coloring composition (YM-1))
The following components are mixed and stirred so as to be uniform, and then dispersed for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using zirconia beads having a diameter of 0.5 mm, and then the pore diameter is 1. A colored composition (YM-1) having a non-volatile component content of 20% by mass was prepared by filtering with a 0.0 μm filter.

Miniaturization PY138: 14 parts Acid dispersion resin S1 solution: 3.0 parts Binder resin 1 solution: 12.0 parts Binder resin 2 solution: 12.0 parts Propylene glycol monomethyl ether acetate (PGMAc): 59.0 parts

YM-2 to YM-5 were prepared in the same manner as the coloring composition (YM-1) except that the pigments shown in Table 4 were changed.

[Examples 201-205, Comparative Examples 201-204]
The components shown in Table 5 were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to prepare a colored composition containing the yellow pigments of Examples 201-205 and Comparative Examples 201-204. The blending ratio of the green coloring composition and the yellow coloring composition was such that the chromaticity after the substrate was prepared was (x = 0.297, y = 0.570) with the C light source.

<Evaluation of coloring composition>
The viscosity, storage stability, brightness, and contrast of the coloring compositions of Examples 201-205 and Comparative Examples 201-204 were evaluated by the following methods. The evaluation method of viscosity and storage stability was carried out in the same manner as the evaluation of the coloring compositions of Examples 101 to 118 and Comparative Examples 101 to 104. The results are shown in Table 5.

(Evaluation of brightness)
The coloring composition is applied onto a glass 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, then heated at 230 ° C. for 30 minutes and allowed to cool to form a coating film. A substrate was prepared.
The brightness (Y) of the obtained coating film substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.) and evaluated according to the following criteria. 3 or more was set as a practical level.
After the heat treatment at 230 ° C., the coating film substrate was adjusted to the chromaticity of x = 0.297 and y = 0.570 with a C light source.

5: 66.5 or more 4: 65.9 or more, less than 66.5 3: 65.3 or more, less than 65.9 2: 64.9 or more, less than 65.3
1: Less than 64.9

(Evaluation of contrast ratio)
The light emitted from the backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a coating film of a coloring composition coated on a glass substrate, and reaches the other polarizing plate. At this time, if the polarizing plate and the polarizing planes of the polarizing plate are parallel, the light passes through the polarizing plate, but if the polarizing planes are orthogonal to each other, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the coloring composition, scattering or the like occurs due to the colorant particles, and if a part of the polarizing surface is displaced, the light is transmitted when the polarizing plates are parallel. When the amount of light emitted is reduced and the polarizing plates are orthogonal, part of the light is transmitted. This transmitted light was measured as the brightness on the polarizing plate, and the ratio of the brightness when the polarizing plates were parallel to the brightness when the polarizing plates were orthogonal was calculated as a contrast ratio.

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

Therefore, when scattering occurs due to the colorant in the coating film, the brightness when parallel is reduced and the brightness when orthogonal is increased, so that the contrast ratio is lowered.
Use the same coating film as the one for which the brightness was evaluated, and use a color luminance meter ("BM-5A" manufactured by Topcon) as the luminance meter and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) as the polarizing plate. There was. The measurement was carried out through a black mask having a 1 cm square hole in the measurement portion. 3 or more was set as a practical level.

5: 13,000 or more 4: 13,000 or more, less than 11,000 3: 9,000 or more, less than 11,000 2: 7,000 or more, less than 9,000 less than 1: 7,000

<Preparation of photosensitive coloring composition>
The binder resin used in the photosensitive coloring composition of the present invention will be described.

(Synthesis of binder resin 3)
207 parts of propylene glycol monomethyl ether acetate was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, and the temperature was raised to 80 ° C. to replace the inside of the reaction vessel with nitrogen. After that, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (“Aronix (registered trademark) M110” manufactured by Toa Synthetic Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate from the dropping tube. A mixture of parts and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, for the entire amount of the obtained copolymer solution, nitrogen gas was stopped, dry air was injected for 1 hour, and the mixture was stirred, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko). A mixture of 6.5 parts of Karenz (registered trademark) MOI, 0.08 part of dibutyltin laurate and 26 parts of propylene glycol monomethyl ether acetate was added dropwise at 70 ° C. over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl is added to the previously synthesized resin solution so that the non-volatile content is 20% by mass. Ether acetate was added to obtain a solution of binder resin 3. The weight average molecular weight was 18,000.

(Synthesis of binder resin 4)
333 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, the atmosphere inside the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. 70.5 g (0.40 mol) of benzyl methacrylate, 71.1 g (0.50 mol) of glycidyl methacrylate, 22.0 g of dicyclopentanyl methacrylate (“Fankril (registered trademark) FA-513M” manufactured by Hitachi Chemical Co., Ltd.) A solution prepared by adding 3.6 g of azobisisobutyronitrile to a mixture consisting of 0.10 mol) and 164 g of propylene glycol monomethyl ether acetate was added dropwise to the flask over 2 hours from the dropping funnel, and the mixture was further stirred at 100 ° C. for 5 hours. Continued to do. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 g of methacrylic acid [0.5 mol, (100 mol% with respect to the glycidyl group of glycidyl methacrylate used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g of hydroquinone were put into a flask, and the reaction was continued at 110 ° C. for 6 hours, and the reaction was terminated when the non-volatile acid value reached 1 mgKOH / g. Next, 60.9 g (0.40 mol) of tetrahydrophthalic anhydride and 0.8 g of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a photosensitive transparent resin solution having an acid value of 80 mgKOH / g. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and the non-volatile content becomes 20% by mass in the previously synthesized photosensitive transparent resin solution. As described above, propylene glycol monomethyl ether acetate was added to obtain a solution of the binder resin 4. The weight average molecular weight was 12,000.

(Synthesis of binder resin 5)
182 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen introduction tube, the atmosphere inside the flask was changed from air to nitrogen, and then the temperature was raised to 100 ° C. 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g of dicyclopentanyl methacrylate (“Fankril (registered trademark) FA-513M” manufactured by Hitachi Kasei Co., Ltd.) A solution prepared by adding 3.6 g of azobisisobutyronitrile to a mixture consisting of (0.10 mol) and 136 g of propylene glycol monomethyl ether acetate was added dropwise to a flask over 2 hours from a dropping funnel, and the mixture was further stirred at 100 ° C. for 5 hours. Continued. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 g of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9 g and 0.145 g of hydroquinone were put into a flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a photosensitive transparent resin solution having an acid value of 79 mgKOH / g. After cooling to room temperature, about 2 g of the photosensitive transparent resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and the non-volatile content becomes 20% by mass in the previously synthesized photosensitive transparent resin solution. As described above, propylene glycol monomethyl ether acetate was added to obtain a solution of the binder resin 5. The weight average molecular weight was 13,000.

(Synthesis of binder resin 6)
A separable flask with a cooling tube was prepared as a reaction tank, while 40 parts of dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, 40 parts of methacrylic acid, and methacrylic acid were prepared as a monomer dropping tank. Prepare a well-stirred mixture of 120 parts of methyl, 4 parts of t-butylperoxy-2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Oil & Fats Co., Ltd.), and 40 parts of propylene glycol monomethyl ether acetate, and prepare a chain transfer agent dropping tank. A well-stirred mixture of 8 parts of n-dodecanethiol and 32 parts of propylene glycol monomethyl ether acetate was prepared.
395 parts of propylene glycol monomethyl ether acetate was charged into the reaction vessel, replaced with nitrogen, and then heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90 ° C. After the temperature of the reaction tank became stable at 90 ° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was carried out over 135 minutes while keeping the temperature at 90 ° C. 60 minutes after the dropping was completed, the temperature was raised to 110 ° C. After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (volume ratio) mixed gas was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis (4-methyl-6-t-butylphenol) and 0.8 parts of triethylamine were charged in the reaction vessel, and the mixture was allowed to react at 110 ° C. for 12 hours. It was. After that, 150 parts of propylene glycol monomethyl ether acetate was added and cooled to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and the non-volatile content was added to the previously synthesized resin solution. Propylene glycol monomethyl ether acetate was added so as to have a concentration of 20% by mass to obtain a solution of the binder resin 6. The weight average molecular weight was 18,000 and the acid value per non-volatile component was 2 mgKOH / g.

[Example 301]
(Preparation of Photosensitive Coloring Composition (GR-1))
The following components were mixed and stirred so as to be uniform, and then filtered through a filter having a pore size of 1.0 μm to prepare a photosensitive coloring composition (GR-1).

Coloring composition (GM-1): 19.5 parts Coloring composition (YM-1): 30.5 parts Solution of binder resin 3: 3.75 parts Solution of binder resin 4: 3.75 parts of binder resin 5 Solution: 3.75 parts Solution of binder resin 6: 3.75 parts Epoxy compound ("EHPE (registered trademark) 3150" manufactured by Daicel Co., Ltd.): 0.16 parts Photopolymerizable compound (Aronix (registered trademark) manufactured by Toa Synthetic Co., Ltd. ) M402 "): 1.10 parts photopolymerizable compound ("Aronix (registered trademark) M350" manufactured by Toa Synthetic Co., Ltd.): 1.45 parts photopolymerization initiator ("Irgacure (registered trademark) OXE02" manufactured by BASF): 0.15 part photopolymerization initiator (IGM Resins BV "OMNIRAD (registered trademark) 369"): 0.30 part sensitizer (Nippon Kayakusha "KAYACURE (registered trademark) DETX-S" ): 0.05 part thiol compound (pentaerythritol tetrakisthiopropionate): 0.20 part leveling agent ("BYK (registered trademark) 330" manufactured by Big Chemie): 0.05 part antioxidant (BASF "" IRGANOX® 1010 "): 0.10 parts Propropylene glycol monomethyl ether acetate: 21.44 parts Ethyl 3-ethoxypropionate: 10.00 parts

[Examples 302 to 322, Comparative Examples 301 to 304]
Examples 302 to 322 and Comparative Examples 301 to 304 were prepared in the same manner as in Example 301 except that the coloring compositions shown in Table 6 and their amounts were changed.

<Evaluation of photosensitive coloring composition>
The viscosity, storage stability, brightness, contrast, voltage retention rate, and foreign matter of the coating film of the photosensitive coloring compositions of Examples 301-222 and Comparative Examples 301-304 were evaluated by the following methods.
The results are shown in Table 6.

(viscosity)
The viscosity of the photosensitive coloring composition was measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd .: ELD-type viscometer) under the conditions of a temperature of 25 ° C. and a rotation speed of 50 rpm. 3 or more was set as a practical level.

5: 2.0 or more and less than 4.0 4: 4.0 or more, less than 6.0 3: 6.0 or more, less than 8.0 2: 8.0 or more and less than 10.0 1: 10.0 or more

(Evaluation of storage stability)
From the initial viscosity on the day of preparation of the photosensitive coloring composition and the viscosity measured after storage in a constant temperature room at 40 ° C. for 7 days, the viscosity change rate (%) (= (viscosity after storage at 40 ° C. for 7 days-initial viscosity) / Initial viscosity x 100) was calculated and the storage stability was evaluated according to the following criteria. 3 or more was set as a practical level.
Both the initial viscosity and the viscosity after storage were measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd .: ELD-type viscometer) under the conditions of a temperature of 25 ° C. and a rotation speed of 50 rpm.

5: Viscosity change rate is less than 2% 4: Viscosity change rate is 2% or more and less than 5%
3: Viscosity change rate is 5% or more and less than 10% 2: Viscosity change rate is 10% or more and less than 15% 1: Viscosity change rate is 15% or more

(Evaluation of brightness)
The photosensitive coloring composition was applied onto a glass 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 an integrated light amount of 200 mJ was used using an ultra-high pressure mercury lamp. Ultraviolet exposure was performed at / cm2 and development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Then, after heating and allowing to cool at 230 ° C. for 60 minutes, the brightness (Y) of the obtained coating film substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.) and evaluated according to the following criteria. 3 or more was set as a practical level.
After the heat treatment at 230 ° C., the coating film substrate was adjusted to the chromaticity of x = 0.297 and y = 0.570 with a C light source. As an alkaline developer, from 1.5% by mass of sodium carbonate, 0.5% by mass of sodium hydrogen carbonate, 8.0% by mass of an anionic surfactant ("Perirex NBL" manufactured by Kao Corporation), and 90% by mass of water. Was used.

5: 66.5 or more 4: 65.9 or more, less than 66.5 3: 65.3 or more, less than 65.9 2: 64.9 or more, less than 65.3
1: Less than 64.9

(Evaluation of contrast ratio)
The light emitted from the backlight unit for a liquid crystal display passes through a polarizing plate, is polarized, passes through a coating film of a photosensitive coloring composition coated on a glass substrate, and reaches the other polarizing plate. At this time, if the polarizing plate and the polarizing planes of the polarizing plate are parallel, the light passes through the polarizing plate, but if the polarizing planes are orthogonal to each other, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the coating film of the coloring composition, scattering or the like occurs due to the colorant particles, and if a part of the polarizing surface is displaced, the light is transmitted when the polarizing plates are parallel. When the amount of light emitted is reduced and the polarizing plates are orthogonal, part of the light is transmitted. This transmitted light was measured as the brightness on the polarizing plate, and the ratio of the brightness when the polarizing plates were parallel to the brightness when the polarizing plates were orthogonal was calculated as a contrast ratio.

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

Therefore, when scattering occurs due to the colorant in the coating film, the brightness when parallel is reduced and the brightness when orthogonal is increased, so that the contrast ratio is lowered.
Using the same coating film as the one whose brightness was evaluated, the luminance meter was a color luminance meter ("BM-5A" manufactured by Topcon), and the polarizing plate was a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation). Was used. At the time of measurement, the measurement was carried out through a black mask having a 1 cm square hole in the measurement portion and evaluated according to the following criteria. 3 or more was set as a practical level.

5: 13,000 or more 4: 11,000 or more, less than 13,000 3: 9,000 or more, less than 11,000 2: 7,000 or more, less than 9,000 less than 1: 7,000

(Evaluation of voltage retention rate change rate ΔVHR)
The photosensitive coloring composition is applied onto a glass substrate having an ITO transparent electrode having an effective electrode size of 10 mm × 10 mm using a spin coater so that the thickness of the dry film is 3.2 μm, and the coating film on the electrode portion is coated. Was wiped off with a solvent, and then exposed to ultraviolet rays at an integrated light amount of 50 mJ / cm ² , and developed with an alkaline developer at 23 ° C. to obtain a coated substrate. Then, after heating at 230 ° C. for 20 minutes and allowing to cool, two sample-coated substrates for measurement were prepared.
The two sample-coated glass substrates were placed facing each other so that the ITO transparent electrode surfaces faced each other, and a small cell was prepared using a sealant so that the cell gap was 9 μm. A liquid crystal liquid is injected into this small cell between the cell gaps, a voltage is applied at a voltage of 5 V for 60 μsec at 50 ° C., and the cell voltage [V1] after 16.67 msec after the voltage is released is set to VHR manufactured by Toyo Corporation. Measured at -1S. The measured cell voltage was averaged, and the obtained cell voltage was used to obtain the initial VHR (%) from the following formula.

VHR (voltage retention rate) (%) = ([V1] / 5) x 100

The above initial VHR measured cell sample is irradiated with LED illumination of 150,000 nits for 3 hours, and the VHR (%) after irradiation is measured again. evaluated. 3 or more was set as a practical level.

ΔVHR = | Initial VHR-VHR after exposure |

Less than 5: 2% 4: 2% or more and less than 5% 3: 5% or more and less than 10% 2:10% or more, less than 15% 1: 15% or more

(Foreign matter on the coating film)
The photosensitive coloring composition was rotationally coated on a glass substrate using a spin coater so that the dry film thickness was 1.2 μm, and prebaked at 120 ° C. for 120 seconds to prepare a test sample substrate. The evaluation was carried out by observing the surface using a metallurgical microscope "BX60" manufactured by Olympus System Corporation. The magnification is set to 500 times, and the number of particles that can be observed in any five fields of view by transmission is counted. 3 or more was set as a practical level.

5: Foreign matter less than 20 4: Foreign matter 20 or more, less than 50 3: Foreign matter 50 or more and less than 100 2: Foreign matter 100 or more 1: Foreign matter 100 or more, uneven coating surface

Examples 301-222 of the present invention were excellent in brightness, contrast, ΔVHR, and foreign matter in the coating film, and were also excellent in viscosity and storage stability. Among them, the photosensitive coloring composition using a phthalocyanine pigment in which Y is bromine, m is 2 to 3, the distribution width of halogen atoms is 2 to 6, and X is bromine and n is 7 to 9, has brightness and ΔVHR. , And the foreign matter in the coating film was particularly excellent, and the results were also particularly excellent in viscosity and storage stability.
Further, as can be seen from Examples 301, 317, and 318, the photosensitive coloring composition in which the acidic dispersion resin and the basic dispersion resin are used in combination as the dispersion resin has excellent viscosity and storage stability. became.
Further, as can be seen from Examples 301 and 319 to 322, C.I. I. The photosensitive coloring composition using Pigment Yellow 138 was excellent in brightness and contrast.
On the other hand, the photosensitive coloring composition using the phthalocyanine pigment having m of 0 in the general formula (1) as in Comparative Example 301 was inferior in brightness, contrast, and ΔVHR. Further, the photosensitive coloring composition using a phthalocyanine pigment in which the acidic compound does not have the structure specific to the present application as in Comparative Examples 302 to 304 is inferior in brightness, contrast, ΔVHR, and foreign matter in the coating film, and is also inferior in storage stability. Met.

<Making color filters>
The photosensitive coloring composition (GR-1) is applied onto a glass substrate on which a black matrix is formed using a slit die coater, and then prebaked on a hot plate at 90 ° C. for 2 minutes to form a coating film. did. Next, after cooling the substrate on which the coating film was formed to room temperature, using a high-pressure mercury lamp, the coating film was irradiated with radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at 1,000 J / m via a striped photomask. ^It was exposed with an exposure amount of 2.
After performing alkaline development, the cells were washed with ultrapure water and post-baked at 230 ° C. for 20 minutes to form green striped pixels on the substrate.
Next, a protective film was formed on the pixel using the photocurable resin composition. In this way, it was possible to produce a color filter having excellent brightness, contrast, and voltage retention, and having less foreign matter on the coating film.

Claims (11)

A phthalocyanine pigment represented by the following general formula (1).

General formula (1)

(X and Y in the general formula (1) represent halogen atoms, n represents 4 to 16, and m represents 1 to 10.)
The phthalocyanine pigment according to claim 1, wherein m in the general formula (1) is 1 to 4. The phthalocyanine pigment according to any one of claims 1 or 2, wherein the halogen atom represented by Y in the general formula (1) has a distribution width of 2 to 6. The phthalocyanine pigment according to any one of claims 1 to 3, wherein X in the general formula (1) is a bromine atom and n is 6 to 10. A coloring composition containing the phthalocyanine pigment according to any one of claims 1 to 4 and a dispersion resin as a colorant. The coloring composition according to claim 5, which contains an acidic dispersion resin as the dispersion resin. The coloring composition according to claim 5 or 6, which comprises a basic dispersion resin as the dispersion resin. The coloring composition according to any one of claims 5 to 7, which contains a yellow pigment as the coloring agent. As the yellow pigment, C.I. I. Pigment Yellow 138, C.I. I. Pigment Yellow 150, C.I. I. The coloring composition according to claim 8, which comprises at least one selected from the group consisting of Pigment Yellow 185 and a quinophthalone pigment represented by the following general formula (2).

General formula (2)

(In the general formula (2), R ^{1 to} R ¹³ each independently have a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, and an alkoxyl group or a substituent which may have a substituent. Represents an aryl group that may have, provided that ^{at least one adjacent set of groups from R 1 to} R ⁴ and / or at least one adjacent set of groups from R ^{10 to} R ¹³ , Together to form an aromatic ring that may have a substituent.) A photosensitive coloring composition containing the coloring composition according to any one of claims 5 to 9, a photopolymerizable compound, and a photopolymerization initiator. A color filter comprising a filter segment formed of the photosensitive coloring composition according to claim 10 on a substrate.