JP2008138037A - Ink-jet ink and ink-jet color filter using the same - Google Patents

Abstract

Disclosed is an inkjet ink that is excellent in light resistance, heat resistance, and transparency and that can be stably ejected by an inkjet method.
The present invention relates to a dye monomer containing, as ink jet inks, a coloring material and a thermosetting resin as main components, a specific anion as an essential component, and a specific cation as an optional component as the coloring material. Or a coloring composition containing at least one of a polymer obtained by polymerizing the dye monomer, or a copolymer obtained by copolymerizing the monomer with another monomer can do. Moreover, this invention can provide the color filter by the inkjet method using the said coloring composition.
[Selection] Figure 1

Description

  The present invention relates to an ink-jet ink for the purpose of producing an optical color filter mainly used in a color liquid crystal display, and an ink-jet color filter using this ink. More specifically, the present invention relates to an inkjet ink for forming a colored pattern portion generally referred to as a pixel portion of a stripe filter or a matrix filter, and an inkjet color filter using the same.

  In recent years, with the development of personal computers, especially portable personal computers, the demand for liquid crystal displays, particularly color liquid crystal displays, has been increasing. However, cost reduction is necessary for further dissemination, and there is an increasing demand for cost reduction of color filters that have a particularly high cost ratio.

  Various methods for reducing the cost of color filters have been proposed. Among them, as a promising method, a method of adopting an inkjet method for forming a pixel portion of a color filter, that is, a colored light-transmitting portion, has attracted attention. (For example, Patent Documents 1, 2, and 3).

  The ink jet method is a method in which ink is ejected as droplets from an ink ejection port and is attached to a colored portion for coloring, and has the advantage that a fine array of fine pixels can be formed accurately and at high speed. Have. In addition, each colored layer can be formed at the same time, and it is only necessary to deposit ink only on the pixel formation portion, and ink is not wasted. Therefore, productivity can be greatly improved and cost can be reduced. it can.

  In particular, the method for forming a color filter by directly applying a curable ink on a substrate is more resistant to heat and solvent than the conventional method for forming a color filter by applying ink to an ink receiving layer. Since it is not necessary to consider the process restrictions in the ITO formation process and the alignment film formation process, which occur due to low properties, a more reliable liquid crystal element can be configured.

  In the inkjet method, due to the nature of ejecting ink from fine nozzles, nozzle clogging is likely to occur if there are particles in the ink. Since the pigment does not dissolve in the solvent or resin of the ink, it exists as particles in the ink. For this reason, when a pigment is used as a coloring material for ink-jet ink, there are significant restrictions on the particle diameter and the amount of pigment added. On the other hand, when a dye is used as the coloring material, the dye is generally soluble in a solvent or a polymer and is stable without causing aggregation in the ink. However, ordinary dyes have problems such as inferior heat resistance, light resistance and chemical resistance.

Prior art documents are shown below.
JP 59-75205 A JP-A 63-235901 JP-A-1-217302

The present invention has been made to solve the above-described problems, and provides an ink for a color filter by an ink jet method, which has excellent light resistance, heat resistance, and transparency and can be stably ejected by an ink jet method. The issue is to provide.

  In the present invention, as a result of repeated studies to solve the above-mentioned problems, a specific dye monomer that is easily synthesized by a conventionally known synthesis method, a polymer obtained by polymerizing the monomer, or another single monomer. The object can be achieved by using a colored polymer comprising a copolymer obtained by copolymerization with a monomer, and using an ink-jet ink comprising the colored polymer, a thermosetting resin, and a solvent. I found it.

That is, the present invention includes the following items.
[1] In an inkjet ink comprising a coloring material, a thermosetting resin, and a solvent, the coloring material has an absorption maximum containing a quaternary ammonium cation having a terminal double bond represented by the following general formula (1). A polymerizable dye monomer having a wavelength of 400 to 450 nm, a polymer obtained by polymerizing the dye monomer, or a coloring material that is a copolymer obtained by copolymerizing with another monomer is used. Inkjet ink

(In the formula, X represents —CH ₂ —, —COO—, —CONH—, R ₁ represents a hydrogen atom or a methyl group, and R ₂ , R ₃ and R ₄ each independently represent 1 to 10 carbon atoms. An alkyl group or a benzyl group, and n represents a number of 0 to 8.)
[2] The ink-jet ink according to claim 1, wherein the coloring material in the general formula (1) is such that X is —COO— and n is 2.
[3] The ink-jet ink according to claim 1, wherein the coloring material in the general formula (1) is such that X is —CONH— and n is 3.
[4] The inkjet ink according to any one of [1] to [3], wherein the dye anion obtained by removing a cation from a dye monomer having an absorption maximum at 400 to 450 nm is a pyrazolone dye anion. .
[5] The inkjet ink according to [4], wherein the pyrazolone dye anion is represented by the following chemical formula (2) or chemical formula (3).

[6] The ink-jet ink according to any one of [1] to [5], wherein the coloring material has a viscosity at 25 ° C. of 1 to 20 mPa · s.
[7] In the case where a partition made of a black matrix material is formed on a transparent substrate, and ink is filled into the pixels partitioned by the partition by an ink jet method to form a color filter, the ink is any one of claims 1 to 7. A color filter, which is the ink-jet ink according to any one of 6 above.

  Since this invention is the above structure, there exists an effect as shown below. That is, a polymerized pigment is used as a coloring material instead of a dye or pigment. As a result, first of all, it is soluble in the color characteristic part of the dye and the solvent, so that it has good transparency and no polarization property, and since no particles are formed, the ink is applied to an inkjet nozzle or the like. It is possible to provide a coloring material having discharge stability that does not cause clogging. Secondly, since the polymerized dye is further thermally cured, it is possible to provide an ink-jet ink having the same heat resistance and light resistance as the pigment has.

  In the present invention, the coloring performance of the color filter is determined by the polymerizable dye monomer containing a quaternary ammonium cation having a terminal double bond represented by the general formula (1) and having an absorption maximum at 400 to 450 nm, or The coloring material obtained by copolymerizing with the polymer obtained by polymerizing the dye monomer or with another monomer is guaranteed. Unlike the dye, this coloring material has excellent heat resistance and light resistance, so it is exposed to light for a long time in long-term use of a liquid crystal display or a color video camera, or heated during the manufacturing process of a color filter. Also, the initial coloring performance can be maintained.

  The coloring material is sprayed from a nozzle to a predetermined position on the substrate as a coloring liquid (hereinafter referred to as ink) containing a thermosetting resin and a solvent, and the ink is dried on the filter substrate to form a colored layer. However, they are uniformly present in the coatings formed on these substrates, and therefore do not constitute particles and do not cause portions having different refractive indexes in the composition or coating. The light incident on the coating is not scattered. In addition, viscosity increase due to aggregation between particles is unlikely to occur, and it is suitable as an inkjet ink.

  The coloring material can polymerize only the monomer, and can also be a copolymer of the monomer and a conventionally known monomer. Moreover, in order to adjust a hue, it can also be set as the copolymer which combined 2 or more types of the polymerizable pigment | dye monomer of this invention. Production of the polymer of the present invention can be easily carried out in water, in an organic solvent or in the absence of a solvent using a conventionally known polymerization catalyst as one used for addition polymerization.

  As the polymerizable dye monomer of the present invention, as representative examples of the cationic monomer represented by the general formula (1), the following compound No. 1-No. 7 is mentioned.

  Specific examples of the dye anion obtained by removing the cation from the polymerizable dye monomer having an absorption maximum of 400 to 450 nm according to the present invention include the following compound Nos. 8-Compound No. 24.

  In the present invention, as a combination with the cation component represented by the general formula (1), among the dye anions, in particular, the compound No. 23, Compound No. Pyrazolone dye anions exemplified by 24 etc. are preferably used.

  The coloring material of the present invention is the above-described polymerizable dye monomer, a polymer obtained by polymerizing the dye monomer, or a copolymer obtained by copolymerization with another monomer. In other words, the polymer of the present invention can be obtained by polymerizing only the monomer to give a colored polymer, and the copolymer of the monomer and a conventionally known low and / or high molecular weight monomer. A colored polymer can be formed as the polymer. The colored polymer can be converted into a polymer monomer having a dye structure by introducing a group having a double bond as required. Furthermore, the colored polymer or the polymer monomer having a dye structure can be polymerized to give a colored polymer in addition to other low-molecular or high-molecular monomers.

  The polymer of the present invention can be easily produced in water, in an organic solvent or in the absence of a solvent using a conventionally known polymerization catalyst.

  Known low molecular weight monomers used for synthesizing the above-mentioned copolymer which is the coloring material of the present invention include styrene compounds and α, β-unsaturated mono-polycarboxylic acids and esters, amides and imides thereof. For example, the former includes styrene, α-methylstyrene, hydroxystyrene, and the like, and the latter includes acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid, Examples include 1-butyne-2,3,4-tricarboxylic acid, and examples of the ester include methyl, ethyl, 2-hydroxyethyl, propyl, butyl, octyl, dodecyl, and 2 of the above α, β-unsaturated carboxylic acid. , 2,6,6-tetramethyl-4-piperidyl, 1,2,2,6,6-pentamethyl-4-piperidyl, 2- [3- (2- Benzotriazolyl) -4-hydroxyphenyl] ethyl and the like. Examples of the amide include methyl amide, dimethyl amide, ethyl amide, diethyl amide, propyl amide, dipropyl amide of the above α, β-unsaturated carboxylic acid, Examples include butyramide, dibutylamide, hexylamide, octylamide, and phenylamide. Examples of the imide include maleimide, itaconimide, N-butylmaleimide, N-octylmaleimide, and N-phenylmaleimide.

Moreover, as a well-known polymer monomer, a resin having a number average molecular weight of 5,000 to 100,000 having at least one ethylenically unsaturated double bond is suitably used. In particular, when an ink having a number average molecular weight of 5,000 to 30,000 is used, the viscosity is preferably low. Specifically, a linear polymer having a reactive functional group such as a hydroxyl group, a carboxyl group, or an amino group is bonded to a (meta) group via an isocyanate group, an aldehyde group, an epoxy group, or the like that can react with the reactive functional group. ) A resin or the like in which an ethylenically unsaturated double bond is introduced by reacting an acrylic compound or cinnamic acid is used.

  When a copolymer is formed using the dye monomer of the present invention and a known low or high molecular weight monomer, the amount of the known monomer used is appropriately selected according to the application. Usually, it is in the range of 5 to 100000 parts by mass with respect to 100 parts by mass of the dye monomer of the present invention.

  The total mass of the coloring material in the ink is preferably 0.1 to 30% by mass, particularly preferably 1 to 20% by mass, based on the total mass of the ink. In this range, the optical characteristics satisfying the pixel are obtained. It is preferable that the ink characteristics are not changed so as to deviate from the range that can be ejected accurately by the ink jet recording method.

  The thermosetting resin in the ink is appropriately selected from known color filter materials in relation to the pigment. Specifically, casein, gelatin, polyvinyl alcohol, carboxymethyl acetal, polyimide resin, acrylic resin, epoxy resin, melamine resin, or the like can be used. In particular, an acrylic resin is preferably used when manufacturing a color filter that requires heat resistance and light resistance.

  The solvent in the ink is selected depending on the printability of the ink jet apparatus, and it is particularly preferable to use a material having a surface tension range of less than 35 mN / m and a boiling point of 130 ° C. or higher. When the surface tension is 35 mN / m or more, the dot shape stability at the time of inkjet discharge is significantly adversely affected. Further, when the boiling point is less than 130 ° C., the drying property in the vicinity of the nozzle is remarkably increased. As a result, the occurrence of defects such as nozzle clogging is caused, which is not preferable. Further, the solvent is appropriately selected depending on the thermosetting temperature of the thermosetting resin of the ink. When a solvent having a remarkably low boiling point is used as compared with the thermosetting temperature of the thermosetting resin, there is a concern that the shape of the colored layer is adversely affected.

  As a solvent satisfying these conditions, specifically, diethylene glycol-n-butyl ether, tetraethylene glycol dimethyl ether, pentaethylene glycol dimethyl ether, tripropylene glycol methyl ether, dipropylene glycol-n-propyl ether, dipropylene glycol-n- Examples thereof include butyl ether, tripropylene glycol-n-butyl ether, and propylene glycol phenyl ether. In addition, in order to further increase the boiling point of the solvent, 2-methoxyethanol, 2-ethoxyethanol, 2-butoxyethanol, 2-ethoxyethyl acetate, 2-butoxyethyl acetate, 2-methoxyethyl acetate, 2 -Ethoxyethyl ether, 2- (2-ethoxyethoxy) ethanol, 2- (2-butoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethyl acetate, 2- (2-butoxyethoxy) ethyl acetate, 2-phenoxyethanol Diethylene glycol dimethyl ether or the like can be used. Moreover, what was mixed and adjusted so that two or more types of solvent may meet the said conditions as needed can be used.

  Furthermore, a dispersant may be used as appropriate for the ink. In this case, it is used for improving the dispersion of the pigment in the resin. As the dispersant, an ionic or nonionic surfactant can be used. Specific examples include sodium alkylbenzene sulfonate, poly fatty acid salts, fatty acid salt alkyl phosphates, tetraalkyl ammonium salts, polyoxyethylene alkyl ethers, and other organic pigment derivatives and polyesters. One type of dispersant may be used alone, or two or more types of dispersants may be mixed and used.

  Next, a method for manufacturing a color filter using the above-described ink will be described. FIG. 1 is an explanatory view of a method for producing a color filter for liquid crystal according to an embodiment of the present invention.

  As shown in FIG. 1, in general, a color filter is provided with a black matrix 2 for improving contrast on a transparent substrate 1, and then a colored layer 3 of red (R), green (G), blue (B) or the like. And a protective layer 4 is provided thereon. When this is used as a liquid crystal display device, a transparent conductive layer and an alignment film layer are sequentially stacked. For example, an LCD is configured through a liquid crystal layer facing a counter substrate on which an electrode such as a thin film transistor is formed. To do. In the following, a transparent substrate, a color filter combining this black matrix and colored pixel layers of red, green and blue is used.

  In the case of forming a colored layer of a color filter by the ink jet method, a partition wall is often provided in order to prevent the discharged ink from staying in a predetermined position range and spreading to a portion outside the predetermined position. The partition is usually made of a photosensitive black matrix material, and the black matrix 2 also serves as the partition in the present invention.

  As an apparatus used for inkjet, there are a piezo system and a thermal system depending on a difference in an ink ejection method, but it is desirable to use a piezo system apparatus. Further, it is desirable that the ink particleization frequency of the piezo-type ink jet apparatus is about 5 to 100 kHz. Further, the nozzle diameter of the ink jet apparatus is desirably about 5 to 80 μm. In addition, it is preferable to use an inkjet apparatus in which a plurality of heads are arranged and about 60 to 500 nozzles are incorporated in one head.

  As the transparent substrate 1, a known transparent substrate material such as a glass substrate, a quartz substrate, or a plastic substrate can be used. Among them, the glass substrate is excellent in transparency, strength, heat resistance, and weather resistance.

  The black matrix 2 of the color filter of the present invention contains an ink repellent, but is composed of other black pigments, resins, photoinitiators, additives and the like. It is desirable that these are ink-coated with a solvent applied on a transparent substrate and formed by photolithography or printing. As a result, a color filter having excellent light shielding properties can be obtained. Further, the addition of the ink repellent agent can prevent the color ink from flowing out to adjacent pixels of different colors, thereby preventing color mixing.

  The ink repellent agent described in the present invention has a role of repelling color ink when filled with color ink and preventing entry of color ink into adjacent pixels. The material is not particularly limited, but it is preferable to use a silicone-based or fluorine-based material because the ink repellent effect is excellent. Specific examples of the ink repellent agent include those having an organic silicone or alkyl fluoro group in the main chain or side chain, and a silicone resin or silicone rubber containing a siloxane component, in addition to vinylidene fluoride, vinyl fluoride, Examples thereof include, but are not limited to, ethylene trifluoride and the like, and fluororesins such as copolymers thereof.

  When an ink repellent agent is used, it may bleed out during heating in the production process. Due to the bleed-out of the ink repellent agent, the ink repellent agent adheres to the transparent substrate in the opening, and color loss or the like occurs when the color ink is filled. In order to prevent bleeding out, it is particularly preferable to use a fluorine-containing compound as the ink repellent agent. Furthermore, it can prevent more effectively by using an oligomer type thing rather than a low molecular weight thing.

  As the black pigment, a general pigment such as an organic black pigment or an inorganic black pigment can be used. For example, organic pigments, carbon black, aniline black, graphite, titanium oxide, iron black and the like can be used alone or in combination.

The colored layer 3 is provided in the opening of the black matrix 2 and usually has a red pixel pattern (
R), a pixel pattern composed of three primary colors, a green pixel pattern (G) and a blue pixel pattern (B), is arranged in a desired shape. Examples of the general forming method include a pigment dispersion method, a dye method, an electrodeposition method, a printing method, a transfer method, and an ink jet method. In the present invention, the ink is patterned by an ink jet apparatus, and then the colored layer 3 is formed through a heating process described later.

  As a heating condition of the formed colored layer 3, it is desirable to carry out at 180 to 240 ° C. for 10 to 60 minutes. If the heating temperature is too low or the heating time is too short, there is a problem that the drying of the solvent does not proceed. There is a concern that will become. As a heating method, a hot plate, a hot air furnace, a far-infrared furnace, or the like can be used. Therefore, in the present invention, it is desirable to use a hot plate that heats from the bottom of the substrate.

  The protective layer 4 is provided to improve the smoothness and weather resistance of the color filter surface. The protective layer 4 is, for example, a solution obtained by dissolving a compound having a carboxyl group and a compound having an epoxy group in a solvent or the like using an appropriate coating method such as a spin coating method or a die coating method, and then crosslinking by heating. Let it form. The compound which has this carboxyl group should just be a compound which has a carboxyl group which can perform a crosslinking reaction with an epoxy group by heating.

  By the way, since a carboxyl group and an epoxy group have high reactivity, a problem may arise in a manufacturing process. For this reason, it is desirable to use a compound having a carboxyl group blocked with an alkyl vinyl ether as the compound having a carboxyl group. Specifically, 1-isopropoxyethyl (meth) acrylate, 1-ethoxyethyl (meth) acrylate, 1-t-butoxyethyl (meth) acrylate, 1- (1-methylhexyloxy) ethyl (meth) acrylate, 1 -(1,1-dimethylpropoxy) ethyl (meth) acrylate, 1-isopropoxyethyl (meth) acrylamide, 1-ethoxyethyl (meth) acrylamide, 1-t-butoxyethyl (meth) acrylamide, 1- (1- Methylhexyloxy) ethyl (meth) acrylamide, 1- (1,1-dimethylpropoxy) ethyl (meth) acrylamide, 1,2,4-benzenetricarboxylic acid-2,4-bis (propoxyethyl) -1-(( An example is a monomer or copolymer such as (meth) acryloxyethyl) ester And the like Te. Examples of the compound having an epoxy group include monomers or copolymers such as glycidyl (meth) acrylate, glycidyl itaconate, glycidyl fumarate, and 3,4-epoxycyclohexyl (meth) acrylate. In particular, when an acrylic resin is used for the compound having an epoxy group, a protective layer excellent in transparency and weather resistance can be obtained.

Examples of the present invention are shown below, but the present invention is not limited to these examples.
<Example 1>
(Create black matrix)
10 parts by weight of polyimide precursor (Toray Industries, Inc .: Semicofine SP-510), 7.5 parts by weight of carbon black, 130 parts by weight of NMP, 5 parts by weight of a dispersant (copper phthalocyanine derivative), initiator (Ciba Specialty) 5 parts by mass of Chemicals: Irgacure 907) and 0.1 parts by mass of perfluoroalkyl group-containing oligomer (manufactured by Neos: FTX-720C) were dispersed for 3 hours while cooling with a bead mill disperser to obtain a black matrix composition Adjusted. This black matrix composition was formed on a non-alkali glass substrate (manufactured by Corning, product number 1737) with a spin coater to a coating thickness of about 2.0 μm. Then, after prebaking at 100 ° C. for 20 minutes, a black matrix was formed by performing post-baking at 230 ° C. for 60 minutes through exposure and development processes. When the contact angle with respect to the ink (surface tension 30 mN / m) on the top of the black matrix was measured, it was 35 °, and it was confirmed that the top of the black matrix had ink repellency with respect to the colored ink.

(Method for producing colored polymer)
As the colored polymer of the present invention, compound No. 1 is used as a cation component. 4 and compound no. 30 g of the dye monomer obtained by the combination of 23, 13 g of 2-acrylamido-2-methylpropanesulfonic acid, 46 g of 2-hydroxyethyl methacrylate, 11 g of methacrylic acid, and 4 g of 28% aqueous ammonia, and further, azobis as a polymerization catalyst. 5 g of isobutyronitrile was added, and the reaction was carried out at 95 ° C. for 5 hours using methyl solosolve as a solvent. The solvent was distilled off to obtain a copolymer (hereinafter referred to as polymer A).

  2.7 g of dipentaerythritol hexaacrylate, acrylic resin ((a) 5.0 g of methacrylic acid, (b) with respect to 30.6 g of diethylene glycol monoethyl ether acetate solution of polymer A (solid content concentration 20 mass%) Hydroxyethyl methacrylate 3.7 g, (c) methyl methacrylate 2.5 g, and (d) butyl methacrylate 13.7 g were dissolved in ethyl cellosolve 74.8 g, and 0.3 g of azoisobutyronitrile was added under a nitrogen atmosphere to add 70 g. Binder resin obtained by reaction at 5 ° C. for 5 hours) and 63.5 g of diethylene glycol monobutyl ether acetate were added and stirred well to obtain ink A.

(Production of color filter)
The ink A is used in the opening of the black matrix 2 on the glass substrate 1 and is filled in a pattern surrounded by each partition wall by an inkjet printing apparatus equipped with a 12 pl, 180 dpi head (manufactured by Seiko Instruments Inc.). did. Then, the coloring layer 3 was formed through the thermosetting process for 30 minutes at 230 degreeC after the drying process for 3 minutes at 130 degreeC with a hotplate.

As a material for the protective layer 4, a material obtained by dissolving 5 parts by mass of 1-ethoxyethyl methacrylate monomer, 3 parts by mass of glycidyl methacrylate monomer, and 0.5 parts by mass of an acid catalyst in a solvent is used. The layer coating solution is applied with a spin coater so that the dry film thickness on the black matrix is 1 μm, heated on a 90 ° C. hot plate for 3 minutes, then dried in a 230 ° C. oven for 30 minutes and thermally cured to form a protective layer 4 was formed.
As a heat resistance test, spectral transmittance was measured using Olympus OSP-SP200: OLYMPUS. Table 1 shows the color difference (ΔEab) before and after post-baking. As a light resistance test, Table 1 shows the color difference before and after irradiation for 24 hours with a xenon fade meter.

<Example 2>
Resin solution (18.8 g of hydroxyethyl methacrylate, 12.5 g of methyl methacrylate, 68.8 g of butyl methacrylate) is dissolved in 300 g of ethyl cellosolve with respect to 30 g of diethylene glycol monoethyl ether acetate solution of polymer A (solid content concentration 20 mass%). Then, 0.75 g of azoisobutyronitrile was added under a nitrogen atmosphere and 10.205 g of a 20% solution of a binder resin obtained by reaction at 70 ° C. for 5 hours), alkylated melamine resin MW-30M (Sanwa Chemical ( Ltd.)) 2.392 g and diethylene glycol monobutyl ether acetate 57.403 g were added and stirred well to obtain ink B. Next, samples were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 3>
As the cationic component, Compound No. 4 and compound no. Pigment monomer 3.2g obtained by the combination of 23, acrylic resin ((a) methacrylic acid 5.0g, (b) hydroxyethyl methacrylate 3.7g, (c) methyl methacrylate 2.5g, (d) 13.7 g of butyl methacrylate was dissolved in 74.8 g of ethyl cellosolve, 0.3 g of azoisobutyronitrile was added under a nitrogen atmosphere, and binder resin obtained by reaction at 70 ° C. for 5 hours) to 6.5 g of diethylene glycol monobutyl ether 68.7 g of acetate was added and stirred well to obtain ink C. Next, samples were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Example 4>
As the cationic component, Compound No. 4 and compound no. 3.8 g of the dye monomer obtained by the combination of No. 23, a resin solution (18.8 g of hydroxyethyl methacrylate, 12.5 g of methyl methacrylate, and 68.8 g of butyl methacrylate were dissolved in 300 g of ethyl cellosolve, (Binder resin 20% solution obtained by adding 0.75 g of butyronitrile at 70 ° C. for 5 hours) 13.25 g, alkylated melamine resin MW-30M (Sanwa Chemical Co., Ltd.) 3.12 g, diethylene glycol 72.83 g of monobutyl ether acetate was added and stirred well to obtain ink D. Next, samples were prepared and evaluated in the same manner as in Example 1. The results are shown in Table 1.

<Comparative Example 1>
(Method for producing colored polymer)
As the colored polymer, compound No. 1 as an anionic component is used. The cation component is represented by the following comparative compound No. 23. 30 g of the dye monomer represented by 1; 13 g of 2-acrylamido-2-methylpropanesulfonic acid; 46 g of 2-hydroxyethyl methacrylate; 11 g of methacrylic acid; and 4 g of 28% by weight ammonia water; and azobisisobutyrate as a polymerization catalyst. 5 g of ronitrile was added, and the reaction was carried out at 95 ° C. for 5 hours using methyl cellosolve as a solvent. The solvent was distilled off to obtain a copolymer (hereinafter referred to as polymer B).

(Ink preparation)
20.6 g of diethylene glycol monoethyl ether acetate solution of polymer B (solid content concentration 20% by mass), 2.7 g of dipentaerythritol hexaacrylate, acrylic resin ((a) 5.0 g of methacrylic acid, (b) Hydroxyethyl methacrylate 3.7 g, (c) methyl methacrylate 2.5 g, and (d) butyl methacrylate 13.7 g were dissolved in ethyl cellosolve 74.8 g, and 0.3 g of azoisobutyronitrile was added under a nitrogen atmosphere to add 70 g. Binder resin obtained by reaction at 5 ° C. for 5 hours) and 73.5 g of diethylene glycol monobutyl ether acetate were added and stirred well to obtain ink E. A sample was prepared and evaluated for the obtained ink E in the same manner as in Example 1. The evaluation results are shown in Table 1.

<Comparative example 2>
As a cation component, tetrabutylammonium ion represented in Comparative Compound No. 1 and as anion component, 3.0 g of a dye monomer in combination with Compound No. 23, acrylic resin ((a) 5.0 g of methacrylic acid, (b ) Hydroxyethyl methacrylate 3.7g, (c) Methyl methacrylate 2.5g, (d) Butyl methacrylate 13.7g was dissolved in ethyl cellosolve 74.8g, and 0.3g azoisobutyronitrile was added under nitrogen atmosphere. Ink F was obtained by adding 72.8 g of diethylene glycol monobutyl ether acetate to 5.2 g of binder resin obtained by reaction at 70 ° C. for 5 hours). The obtained ink was subjected to the same operations and evaluation as in Example 1. The results are shown in Table 1.

Table 1 shows the color difference before and after post-baking as the heat resistance evaluation and the light resistance evaluation, and the color difference (ΔEab) before and after irradiation with the Xe fade meter 24h as the light resistance.

It is explanatory drawing of the cross section of the color filter in this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Transparent substrate 2 ... Black matrix 3 ... Colored layer 4 ... Protective layer

Claims (7)

In an inkjet ink composed of at least a coloring material, a thermosetting resin, and a solvent, the coloring material has an absorption maximum of 400 containing a quaternary ammonium cation having a terminal double bond represented by the following general formula (1). Ink-jet ink, characterized by being a polymerizable dye monomer having a wavelength of ˜450 nm, a polymer obtained by polymerizing the dye monomer, or a copolymer obtained by copolymerizing with another monomer .
(In the formula, X represents —CH ₂ —, —COO—, —CONH—, R ₁ represents a hydrogen atom or a methyl group, and R ₂ , R ₃ and R ₄ each independently represent 1 to 10 carbon atoms. An alkyl group or a benzyl group, and n represents a number of 0 to 8.)   2. The ink-jet ink according to claim 1, wherein the coloring material is X in the general formula (1), and n is 2.   The ink for inkjet according to claim 1, wherein the coloring material is X in the general formula (1), wherein x is -CONH- and n is 3.   The inkjet ink according to any one of claims 1 to 3, wherein a dye anion obtained by removing a cation from a dye monomer having an absorption maximum at 400 to 450 nm is a pyrazolone dye anion. The inkjet ink according to claim 4, wherein the pyrazolone dye monomer anion is represented by the following chemical formula (2) or (3).
  The ink-jet ink according to any one of claims 1 to 5, wherein the viscosity of the ink at 25 ° C is in the range of 1 to 20 mPa · s.   A partition made of a black matrix material is formed on a transparent substrate, and ink is filled in the pixels partitioned by the partition by an ink jet method to form a color filter, wherein the ink is any one of claims 1 to 6. A color filter, which is an ink-jet ink according to claim 1.