JP2010026468A - Ink composition for inkjet color filter superior in storage stability, and cured film of inkjet color filter and color filter obtained by using the ink composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an ink composition for a color filter superior in storage stability to be used for an inkjet method. <P>SOLUTION: The ink composition for a color filter to be used for forming a color filter by an inkjet method is characterized in that the percentage of a pigment amount in a solid component excluding a solvent to a resin amount (pigment/resin amount) in the ink composition ranges from 20 to 60 wt.%, and that the percentage of the amount of a dispersant into which the pigment is dispersed, to the pigment amount (dispersant/pigment) ranges from 35 to 120 wt.%. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an ink composition for a color filter excellent in storage stability suitable for producing a color filter by an inkjet method, a color filter cured film obtained by using this ink composition, and a color filter.

  Conventional methods for producing color filters used in color liquid crystal display devices include photopolymerization initiators, various additives, and red (R), green (G), and blue (B) colorants for photosensitive resins. In general, a color resist prepared with a solvent is applied, dried, and then a pixel pattern is formed by a photolithographic method through a series of steps. However, with the recent increase in size of mother glass, technical problems have begun to occur in each process such as the coating process in the conventional color filter manufacturing method using the photolithography method.

  For example, coating methods using spin coating have been mainly used so far, but as the mother glass as the base becomes larger, it becomes technically difficult to apply by spin coating, and instead a slit coater is used. The coating method used is employed. However, even with a coating method using a slit coater, it is difficult to form a uniform coating film on the entire surface due to further enlargement of the mother glass, and this problem becomes even more pronounced with super large mother glasses such as 8G and 10G classes. Become. In addition, since the photolithographic method requires coating, drying, exposure, development, and curing processes for every three colors, there is a problem that the number of steps increases and the cost is high. Another pixel forming means is desired.

  Therefore, as a color filter manufacturing method replacing the photolithography method, for example, image formation using an offset printing method as disclosed in Patent Document 1 has been proposed and implemented. However, with respect to the offset printing method, it is difficult to form a stable pixel on a sufficiently large mother glass, and its practical application is delayed. On the other hand, it is a well-known fact that the pixel forming method by the ink jet method has been attracting attention and implemented in recent years and has a certain track record. And several patents are shown about the ink used in the inkjet method (for example, refer patent documents 2-4).

By the way, in order to realize a good image that can be used for television applications with a liquid crystal display device, a great technical improvement is required for the liquid crystal display device itself and the circuit. One of the requirements is to achieve good display specifications such as contrast. For that purpose, it is necessary to contain more pigments in the ink composition for color filters. However, when the pigment content in the ink composition is increased, a problem is relatively likely to occur with respect to the storage stability of the ink. In particular, in the case of an ink suitable for the photolithography method, in order to ensure developability, it is necessary to select a composition that lowers the dispersion material to the limit and sacrifices the stability to some extent.
JP-A-11-58921 Japanese Patent Laid-Open No. 2004-213033 JP 2004-220036 A JP 2008-50456 A

The present invention is suitable for forming a pixel pattern on a glass substrate whose size is increasing in the manufacture of a color filter, and for curing an ink composition used in an inkjet method capable of reducing cost and mass production. Ink composition for color filter that is excellent in viscosity, has excellent viscosity stability even if it contains a high concentration of pigment to achieve a large NTSC ratio, and can maintain a stable viscosity even at room temperature storage, and this ink composition An object of the present invention is to provide a color filter cured film and a color filter obtained as described above.

  As a result of intensive studies on an ink composition that has excellent viscosity stability and can maintain a stable viscosity even at room temperature storage, the present inventors have used raw materials to be used even if the pigment is contained at a high concentration to achieve a large NTSC ratio. By adjusting the ratio of the pigment to the dispersant in the pigment dispersion, which is one of the above, to an ink composition, the viscosity is stable even at room temperature and suitable for inkjet methods with excellent inkjet ejection properties. The inventors have found that an ink composition for a color filter can be obtained and completed the present invention.

  That is, the present invention relates to a ratio of a pigment amount and a resin amount in a solid component excluding a solvent in a color filter ink composition used for preparing a color filter by an inkjet method (pigment / Resin amount) is in the range of 20-60 wt%, and the ratio (dispersant / pigment) between the pigment amount and the amount of the dispersant for dispersing the pigment is in the range of 35-120 wt%. It is an ink composition for color filters.

The ink composition for an ink jet color filter comprises an unsaturated compound (A) represented by the following general formula (1), a polyfunctional acrylate compound (B) having at least 4 functions, a pigment (D), and a solvent (H). It is a preferable embodiment in the present invention that it is contained and the ratio (A) / (B) of the weight of the component (A) to the component (B) is in the range of 10/90 to 90/10. .
[Wherein, R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ represents a hydrogen atom or a methyl group. . A is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9 , 9-fluorenyl group or a direct bond, X represents a tetravalent carboxylic acid residue, Y ₁ and Y ₂ independently represent a hydrogen atom or -OC-Z- (COOH) _m Represents an acid residue, m represents a number of 1 to 3, and n represents a number of 1 to 200. ]

  In the ink composition for inkjet color filter, a polyfunctional epoxy compound (C) having two or more functions is added to the sum of the components (A) and (B) [(A) + (B)]. In a more preferred embodiment, 0 to 20% by weight is added.

Here, the dispersant is an additive that adsorbs or adheres to the pigment surface and inhibits aggregation of the pigments. In general, the basic structure of the dispersant is an adsorbing part that adsorbs on the pigment surface and the pigments. It has a steric repulsion part that inhibits the aggregation of. Usually, the adsorbing part has a structure having a charge opposite to that of the pigment surface. For example, when the pigment surface has been subjected to an acid treatment, the adsorbing part has Na ⁺ , amine or imino structure. There are many cases. On the other hand, the three-dimensional repulsion part is connected with a long hydrocarbon chain, acrylic, ester, ether or the like. Thus, the dispersant is a kind of surfactant because it has a charge on one side and a hydrocarbon structure on the other. Examples of such dispersants that are commercially available include BYPER Chemie's Disperbyk-160, 161, 162, 163, 164, 165, 166, 169, 182, 183, 184, 185, 2000, 2001. 2020, 2050, 2070, 2150 ", Efka CHEMICALS" EFKA-4046, 4047, 4048, 4050, 4055, 4400, 4401, 4402 ", Nippon Lubrizol" SOLPERSE24000SC, 24000GR, 31845 ", Enomoto Kasei Co., Ltd. DA703-50, DA-705, DA-725 ", Ajinomoto Fine Techno Co., Ltd." Ajisper PB711, 821, 822, 824, 827 ".

  The pigment (D) may be an organic pigment or an inorganic pigment. Among these, organic pigments include, for example, azo lake, insoluble azo (PY-150), phthalocyanine (PG-7, PG-36 & PB-15.6) cyanine, quinophthalone (PY138), quinacdrine, dioxazine (PV -23), isoindolinone (PY-139), berylone, anthraquinone (PR-177), pyrrolopyrrole (PR-254), perylene, etc., one or two of these More than one species can be used in combination. Examples of inorganic pigments include miloli blue, iron oxide, cobalt-based, manganese-based, ultramarine blue, bitumen, cobalt blue, cerulean blue, pyridian, emerald green, cobalt green, and the like. It can also be used together. These pigments are preferably dispersed to an average particle diameter of 0.4 μm or less, which is the lower limit of the wavelength of visible light, in order to color while maintaining the transparency of the coating film (pixel) of the obtained color filter. It is more preferable that the average particle diameter range is 0.01 to 0.25 μm practically.

  And it disperse | distributes by a predetermined method using a dispersing agent, a solvent, and a pigment (D), and obtains a pigment dispersion liquid (dispersion). Among these, the ink composition for inkjet color filters of the present invention is prepared by setting the ratio of the amount of dispersant to the amount of pigment (dispersant / pigment) in the range of 35 to 120 wt%. When the amount of the dispersant and the pigment (D) in the pigment dispersion deviates from the ratio within this range, good ink characteristics cannot be exhibited. That is, when the amount is lower than 35 wt%, the viscosity increases during storage at room temperature, and refrigeration is required. If it further decreases and falls below 25 wt%, the viscosity cannot be kept stable even in refrigerated storage. Especially when it is prepared into an ink, it is stable when the ratio of the dispersant to the pigment is 35 wt% or more when the composition changes as necessary, such as viscosity adjustment, color characteristic adjustment, and drying characteristic adjustment. . On the other hand, when the dispersant ratio exceeds 120 wt%, the ratio of resin and monomers necessary for film formation and function addition such as curing is relatively reduced when preparing an ink, and sufficient reliability in film properties is obtained. It is not possible to exhibit it, and it is 120% wt or less that can realize a composition capable of exhibiting sufficient reliability in a wide range. Therefore, the ratio of the pigment (D) and the dispersant in the pigment dispersion to be used is 35 to 120 wt%, more preferably 40 to 100 wt%.

  In addition, the ink composition in the present invention has a ratio (pigment / resin amount) of the pigment amount in the solid component excluding the solvent and the resin amount (the solid component amount excluding the solvent from the ink composition and not including the pigment component). ) Is in the range of 20-60 wt%, preferably 40-60 wt%. If the ratio of the pigment to the resin amount is less than 20 wt%, desired color characteristics cannot be obtained. Conversely, if the ratio exceeds 60 wt%, the pigment tends to aggregate, causing the head to be blocked during ink ejection.

  Moreover, the ink composition in this invention contains the unsaturated compound (A) represented by General formula (1) mentioned above as a structural component of resin. This component (A) is a polybasic acid dicarboxylic acid obtained by reacting (meth) acrylic acid with an epoxy compound having two glycidyl ether groups derived from bisphenols. Alternatively, it reacts with one or more of each of an acid anhydride thereof (hereinafter also referred to as “dicarboxylic acids”) and tetracarboxylic acid or an acid dianhydride thereof (hereinafter also referred to as “tetracarboxylic acids”). It is an epoxy (meth) acrylate acid adduct obtained. In the present specification, (meth) acrylic acid means acrylic acid, methacrylic acid or both.

The component (A) is preferably derived from an epoxy compound represented by the following general formula (2). This epoxy compound is derived from bisphenols, and when bisphenols are converted to glycidyl ether, oligomer units will be mixed. However, if the average value of l in the general formula (2) is in the range of 0-10. There is no problem in the performance as an ink composition.

In the general formula (2), R ₁ , R ₂ , R ₃ , R ₄ and A represent the same meaning as in the general formula (1), but are preferably R ₁ , R ₂ , R ₃ and R ₄ . Is a hydrogen atom, and A is preferably a 9,9-fluorenyl group. l is an integer of 0 to 10, preferably 0 or an integer of 0 to 2. Here, the 9,9-fluorenyl group refers to a group represented by the following general formula (3).

  In the present invention, the reaction between the epoxy compound and (meth) acrylic acid in obtaining the component (A) is performed using about 2 moles of (meth) acrylic acid with respect to 1 mole of the epoxy compound. Good. The reaction product obtained by this reaction is an epoxy (meth) acrylate compound represented by the following general formula (5). Then, the hydroxy group in the epoxy (meth) acrylate compound molecule is reacted with a) dicarboxylic acid and b) tetracarboxylic acid to obtain an acid adduct of epoxy (meth) acrylate.

  Examples of the a) dicarboxylic acids include chain hydrocarbon dicarboxylic acids or acid anhydrides thereof, alicyclic dicarboxylic acids or acid anhydrides thereof, aromatic dicarboxylic acids or acid anhydrides thereof, and the like. Among these, as the chain hydrocarbon dicarboxylic acid or its acid anhydride, for example, succinic acid, acetyl succinic acid, maleic acid, adipic acid, itaconic acid, azelaic acid, citralmalic acid, malonic acid, glutaric acid, citric acid, tartaric acid, Examples thereof include compounds such as oxoglutaric acid, pimelic acid, sebacic acid, suberic acid, and diglycolic acid, and further dicarboxylic acids into which an arbitrary substituent is introduced or acid anhydrides thereof. Examples of the alicyclic dicarboxylic acid or its acid anhydride include compounds such as hexahydrophthalic acid, cyclobutane dicarboxylic acid, cyclopentane dicarboxylic acid, norbornane dicarboxylic acid, and further, an arbitrary substituent is introduced. Dicarboxylic acids or acid anhydrides thereof may also be used. Furthermore, examples of the aromatic dicarboxylic acid or acid anhydride thereof include compounds such as phthalic acid and isophthalic acid, and further dicarboxylic acids into which an arbitrary substituent is introduced or acid anhydrides thereof may be used. .

  In addition, as b) tetracarboxylic acids, chain hydrocarbon tetracarboxylic acid or its acid dianhydride, alicyclic tetracarboxylic acid or its acid dianhydride, aromatic polycarboxylic acid or its acid dianhydride, etc. Can be used. Among these, examples of the chain hydrocarbon tetracarboxylic acid or its acid anhydride include butanetetracarboxylic acid, pentanetetracarboxylic acid, hexanetetracarboxylic acid, and the like, and tetracarboxylic acids into which a substituent is further introduced. Or its acid anhydride may be sufficient. Examples of the alicyclic tetracarboxylic acid or its acid anhydride include cyclobutanetetracarboxylic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, cycloheptanetetracarboxylic acid norbornanetetracarboxylic acid, and the like. May be a tetracarboxylic acid having a substituent introduced therein or an acid anhydride thereof. Furthermore, examples of the aromatic polyvalent carboxylic acid or acid anhydride thereof include pyromellitic acid, benzophenone tetracarboxylic acid, biphenyl tetracarboxylic acid, biphenyl ether tetracarboxylic acid or acid anhydride thereof, and further substitution. It may be a tetracarboxylic acid having an introduced group or an acid anhydride thereof.

  As for the above a) dicarboxylic acids and b) tetracarboxylic acids, one or more can be used, respectively, and the use ratio of a) dicarboxylic acids and b) tetracarboxylic acids is 0.1 by a molar ratio of a / b. 10 to 10 and preferably 0.2 to 1.0. As for this use ratio, an appropriate ratio can be selected in consideration of the optimum molecular weight, curability, light transmittance, heat resistance, solvent resistance and the like of the component (B).

  Moreover, in order to make the said epoxy (meth) acrylate compound at the time of obtaining (A) component react with a) dicarboxylic acid and b) tetracarboxylic acid, a well-known method can be employ | adopted, However, Preferably epoxy (meta) is used. ) It is preferable to carry out the reaction quantitatively so that the acid component is 3/4 mol per 1 mol of hydroxy group in the acrylate compound molecule. The reaction temperature is 90 to 130 ° C, preferably 95 to 125 ° C.

An example of a method for producing the component (A) is as follows when 9,9-bis (4-hydroxyphenyl) fluorene is used as a starting material.
First, 9,9-bis (4-hydroxyphenyl) fluorene and epichlorohydrin are reacted to synthesize a bisphenolfluorene type epoxy compound represented by the following general formula (4). A bisphenolfluorene type epoxy acrylate resin represented by the following general formula (5) is synthesized by reacting with (meth) acrylic acid represented by CH ₂ = CR ₅ -COOH, and then bisphenolfluorene in a propylene glycol monomethyl solvent. A fluorene type alkali-soluble resin represented by the above formula (1), which is the component (A), can be obtained by reacting the epoxy acrylate resin with the acid component under heating.
Here, R ₁ , R ₂ , R ₃ , R ₄ , and R ₅ in general formulas (4) and (5) are the same as in general formula (1), and A represents a 9,9-fluorenyl group. .

  On the other hand, as the polyfunctional acrylate compound of component (B), for example, methylolpropane such as ditrimethylolpropane tetra (meth) acrylate, tetrafunctional or higher acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) ) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, skeletons such as pentaerythritol and dipentaerythritol, tetra- or higher functional acrylate, acrylic esters such as pentaacrylate ester, etc. Can be mentioned. These may be used alone or in combination of two or more. Furthermore, these acrylates may be monomers or oligomers. In addition, regarding the acrylate structure described above, the trifunctional or lower functional group is excluded even in the same structure, and at the same time, the functional group may be tetrafunctional or higher other than the above structure, and is not affected by the main skeleton of the acrylate.

  In the present invention, the weight ratio (A) / (B) of the component (A) to the component (B) is 10/90 to 90/10, preferably 70/30 to 40/60. When (A) / (B) is out of the range of 10/90 to 90/10, the ink composition is not sufficiently cured, or the light transmittance of the obtained cured film is lowered, and the liquid crystal is colored. The liquid crystal voltage holding ratio may be reduced. Here, the weight average molecular weight (Mw) of the component (A) is preferably in the range of 2000 to 20000.

  In this invention, you may make it contain 20 weight% or less of polyfunctional epoxy compounds (C) more than bifunctional with respect to the sum of (A) component and (B) component. Here, the polyfunctional epoxy compound (C) is composed of an epoxy compound having two or more epoxy groups in one molecule. Typical examples include novolak type epoxy resins such as phenol novolac type epoxy and cresol novolak type epoxy, bis type epoxy resins such as bisphenol A type epoxy and bisphenol F type epoxy, biphenyl type epoxy resins, and alicyclic epoxy resins. It can be illustrated. That is, the polyfunctional epoxy compound (C) in the present invention may have a maximum of 20% by weight and a minimum of 0% by weight.

  The ink composition for a color filter of the present invention is obtained by dissolving or dispersing the component (C) added as necessary in addition to the components (A), (B) and (D) in the solvent (H). . Solvents include ketones such as methyl ethyl ketone, cyclohexanone, methylcyclohexanone, cellosolves such as methyl cellosolve, ethyl cellosolve, cellosolve acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol n-propyl ether, propylene glycol n- Propylene glycol monoalkyl ethers such as butyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol n-propyl ether acetate, propylene glycol monoalkyl ether acetates such as propylene glycol n-butyl ether acetate, diethylene glycol dimethyl ether, Diethylene In addition to diethylene glycol dialkyl ethers such as recall diethyl ether and diethylene glycol dibutyl ether, lactates such as methyl lactate and ethyl lactate, acetates such as n-butyl acetate, γ-butyrolactone, N-methylpyrrolidone, dimethyl sulfoxide, etc. An organic solvent can be illustrated.

  In the present invention, a mixed solvent using two or more of these organic solvents is preferable. In this case, it is more preferable that the solvent used has a boiling point in the range of 120 to 350 ° C.

  In addition, when the component (B) is used, the photopolymerization initiator (F) includes acetophenones such as acetophenone and p-tert-butylacetophenone, benzophenone, 2-chlorobenzophenone, p, p'-bis (dimethyl). Benzophenones such as amino) benzophenone, benzoin ethers such as benzoin methyl ether, benzoin isopropyl ether and benzoin butyl ether, 2-methyl-1 [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- Α-Aminoalkylphenones such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, bis such as bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine-oxide Acylphosphine oxides, glycines such as N-phenylglycine, 2,4-trichloromethyl- (piperonyl) -6-triazine, 2,4- Rikuroromechiru - (4'-methoxy styryl) it is preferable to add a 6-triazine triazines such like. These may be used alone or in combination of two or more. The photopolymerization initiator (F) can also be used in combination with known photopolymerization accelerators (sensitizers) such as p-dimethylaminobenzoic acid isoamyl ester and p-dimethylaminobenzoic acid ethyl ester. About the usage-amount of (F) component, it is preferable that it is 0.1-20 weight part with respect to 100 weight part of total amounts of (B) component and (A) component.

  Furthermore, in this invention, if it is a range which does not inhibit the other performance of the ink composition for color filters, a viscosity modifier (G) can also be added from the objective of adjusting an inkjet suitability. The viscosity modifier (G) includes those that lower the viscosity and those that increase the viscosity. In general, a solvent for reducing the viscosity includes a solvent, but in the present invention, a normal solvent is regarded as a solvent, not a viscosity modifier, and a reactive diluent having a low molecular functional group. Is a viscosity modifier (G). On the other hand, those that increase the viscosity include silica airgel in which silica particles are dispersed, amide wax, and bentonite thickener. Viscosity adjustment is performed by adding these as needed.

  Furthermore, the color filter ink composition of the present invention may contain other components as long as the effects of the present invention are not impaired. For example, a surfactant may be used to improve wettability, and a coupling agent is preferably used to improve adhesion. In this case, the surfactant is preferably contained in the range of 0.01 to 0.2 wt%.

  About the ink composition in this invention, after apply | coating to the predetermined | prescribed area | regions, such as a glass substrate, by the inkjet method, for example, the drying process is performed for 1 to 10 minutes at 50-130 degreeC, and then 0.5-200 at 200-260 degreeC. A predetermined image can be formed by performing thermosetting for 2 hours. As the ink jet method at this time, generally used means may be employed. For example, the ink composition may be discharged, applied, dried and cured in a recess having a predetermined black matrix pattern shape.

  The ink-jet ink composition of the present invention is an ink composition used for an ink-jet method that is suitable for forming a pixel pattern on a glass substrate that is increasing in size, and that can be reduced in cost and mass-produced. The ink composition of the present invention is an ink material for an ink jet color filter that can maintain reliability such as voltage holding ratio while maintaining a stable viscosity at room temperature while maintaining ink jet characteristics as described above.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in more detail, this invention is not limited to this. In the examples, unless otherwise specified, parts represent parts by weight and% represents% by weight.

[Blue dispersion A (pigment dispersion) formulation example]
Pigment PB; 15.6 (100 g) was collected in a 2 L stainless steel container, and 61 g of PB824 (dispersant manufactured by Ajinomoto Co., Inc.), which had been made into a 50% butyl carbitol acetate solution in advance, was added. This is kneaded with three rolls coated with ceramic coating until fluidity comes out. To this kneaded product, 130 g of butyl carbitol acetate was further added and mixed, and then dispersed with a horizontal sand mill until the average particle size of the pigment was 100 nm or less. After the dispersion was completed, the dispersion was diluted with butyl carbitol acetate (400 g) to a solid content of 19%, and a test dispersion was obtained.

[Blue dispersion B (pigment dispersion) formulation example]
Pigment PB; 15.6 (100 g) was collected in a 2 L stainless steel container, and 107 g of PB824 (dispersant made by Ajinomoto Co., Inc.), which was previously made into a 50% solution of butyl carbitol acetate, was added, and butyl carbitol acetate added later was changed to 168 g. Was processed in the same manner as the Blue Dispersion A formulation. After the dispersion was completed, the dispersion was diluted with butyl carbitol acetate (400 g) to a solid content of 20%, and a test dispersion was obtained.

[Red dispersion A (pigment dispersion) formulation example]
100 g of a mixture of pigments PR254 and PY150 in 80/20 was collected in a 2 L stainless steel container, and 75.5 g of Disperbyk-2000 (a dispersing agent manufactured by BYK Chemie) was added. This was kneaded with a three roll coated with ceramic coating until fluidity appeared. Further, 200 g of butyl carbitol acetate was added and mixed, and then the kneaded product was dispersed with a horizontal sand mill until the average particle size of the pigment was 100 nm or less. After the dispersion was completed, the dispersion was diluted with butyl carbitol acetate (400 g) to a solid content of 17%, and a test dispersion was obtained.

[Prescription Example of Red Dispersion B (Pigment Dispersion)]
100g of pigment PR254 and PY150 mixed in 80/20 was collected in a 2L stainless steel container, Disperbyk-2000 (dispersant manufactured by BYK Chemie) was added, and butyl carbitol acetate added later was changed to 105g. Treated as for Red Dispersion A formulation. After completion of dispersion, the dispersion was diluted with butyl carbitol acetate (400 g) to a solid content of 23%, and a test dispersion was obtained.

[Green dispersion A (pigment dispersion) formulation example]
100g of pigment PG36 and PY150 mixed in 60/40 was collected in a 2L stainless steel container and PB827 (dispersed by Ajinomoto Co., Inc.) previously made into a 50% solution of diethylene glycol butyl ether acetate (also known as butyl carbitol acetate (hereinafter BCA)). 60 g) was added. This was kneaded with a three roll coated with ceramic coating until fluidity appeared. Further, BCA (107 g) was added and mixed, and then the kneaded product was dispersed with a horizontal sand mill until the average particle size of the pigment was 100 nm or less. After the dispersion was completed, the dispersion was diluted with BCA (400 g) to give a solid content of 20% to obtain a test dispersion.

[Green dispersion B (pigment dispersion) formulation example]
100g of pigment PG36 and PY150 mixed in 60/40 was collected into a 2L stainless steel container, 91g of PB827 (dispersant made by Ajinomoto Co., Inc.) previously made into 50% BCA solution was added, and BCA added later was 141g. Treated as for Green Dispersion A formulation. After the dispersion was completed, the dispersion was diluted with BCA (300 g) to a solid content of 23%, and a test dispersion was obtained.

[Green dispersion C (pigment dispersion) formulation example]
100g of pigment PG36 and PY150 mixed in 60/40 was collected in a 2L stainless steel container, 200g of PB827 (dispersant made by Ajinomoto Co., Inc.) previously made into 50% BCA solution was added, and BCA added later was 350g. Treated as for Green Dispersion A formulation. After the dispersion was completed, the dispersion was diluted with BCA (350 g) to give a solid content of 30% to obtain a test dispersion.

[Green dispersion D (pigment dispersion) formulation example]
100g of pigment PG36 and PY150 mixed in 60/40 was collected into a 2L stainless steel container, 266g of PB827 (dispersant made by Ajinomoto Co., Inc.) previously made into BCA 50% solution was added, and BCA added later was 204g. Treated as for Green Dispersion A formulation. After the dispersion was completed, the dispersion was diluted with BCA (400 g) to give a solid content of 24% to obtain a test dispersion.

  For all the dispersions, about 1 g was collected after preparation, dried at 160 ° C. for 2 hours, and the composition ratio calculated based on the solid content calculated from the difference from the initial weight is shown in Table 1.

  The rotor was placed in a beaker (1000 ml) and placed on a magnetic stirrer. 210.5 g of BCA was weighed as a solvent, and 4.0 g of YX4000HK (manufactured by Japan Epoxy Resin Co., Ltd.) was added as component (C) while stirring. After confirming their dissolution, PGMEA (propylene glycol monomethyl ether acetate) solution of (A) component fluorene type epoxy acrylate / acid anhydride polymerization adduct (V259ME resin component made by Nippon Steel Chemical Co., Ltd.) 56.5% 42.5 g and (B) component dipentaerythritol hexaacrylate DPHA (manufactured by Nippon Kayaku Co., Ltd.) 16.0 g were added and stirred. Next, 227.0 g of Green dispersion B composed of component (D), a dispersant and a solvent, which were previously dispersed and prepared, was added and further stirred. Finally, 2.5 g and 0.3 g of the additive silane coupling agent and surfactant were added, and the mixture was further stirred for 30 minutes to obtain a test ink composition. Table 2 shows the composition and evaluation results described below.

  The rotor was placed in a beaker (1000 ml) and placed on a magnetic stirrer. 133.7 g of BCA was weighed as a solvent, and 2.4 g of YX4000HK (manufactured by Japan Epoxy Resin Co., Ltd.) was added as component (C) while stirring. After confirming these dissolutions, 24.7 g of PGMEA solution (5259% V259ME resin component, etc., manufactured by Nippon Steel Chemical Co., Ltd.) of (A) component fluorene type epoxy acrylate / anhydride polymer adduct ) Component dipentaerythritol hexaacrylate DPHA (manufactured by Nippon Kayaku Co., Ltd.) 9.3 g was added and stirred. Next, 330.0 g of Green dispersion B composed of component (D), a dispersant and a solvent, which had been dispersed and prepared in advance, was added and further stirred. Finally, 2.5 g and 0.3 g of the additive silane coupling agent and surfactant were added, and the mixture was further stirred for 30 minutes to obtain a test ink composition. The composition and evaluation results are shown in Table 2.

  The rotor was placed in a beaker (1000 ml) and placed on a magnetic stirrer. Weigh 139.65g of BCA as a solvent and stir, while stirring, add PGMEA solution of component (A) fluorene type epoxy acrylate / acid anhydride polymerization adduct (V259ME resin component etc. made by Nippon Steel Chemical Co., Ltd. 56.5%) 38.0 g and 14.5 g of (B) component dipentaerythritol hexaacrylate DPHA (manufactured by Nippon Kayaku Co., Ltd.) were added and stirred. Next, 307.9 g of Blue Dispersion B composed of component (D), a dispersant and a solvent previously dispersed and prepared was added and further stirred. Finally, 2.5 g and 0.3 g of the additive silane coupling agent and surfactant were added, and the mixture was further stirred for 30 minutes to obtain a test ink composition. The composition and evaluation results are shown in Table 2.

  The rotor was placed in a beaker (1000 ml) and placed on a magnetic stirrer. BCA 368.0 g was weighed as a solvent, and 2.5 g of YX4000HK (manufactured by Japan Epoxy Resin Co., Ltd.) was added as component (C) while stirring. After confirming their dissolution, 26.0 g of PGMEA solution (5259% V259ME resin component, etc., manufactured by Nippon Steel Chemical Co., Ltd.) of (A) component fluorene type epoxy acrylate / acid anhydride polymerization adduct (B) ) Component dipentaerythritol hexaacrylate DPHA (manufactured by Nippon Kayaku Co., Ltd.) 10.0 g was added and stirred. Next, 284.0 g of Red dispersion B composed of component (D), a dispersant and a solvent, which were previously dispersed and prepared, was added and further stirred. Finally, 2.5 g and 0.3 g of the additive silane coupling agent and surfactant were added, and the mixture was further stirred for 30 minutes to obtain a test ink composition. The composition and evaluation results are shown in Table 2.

  The rotor was placed in a beaker (1000 ml) and placed on a magnetic stirrer. 222.7 g of BCA was weighed as a solvent, and 1.3 g of YX4000HK (manufactured by Japan Epoxy Resin Co., Ltd.) was added as component (C) while stirring. After confirming their dissolution, 12.7 g of PGMEA solution (5259% V259ME resin component, etc. manufactured by Nippon Steel Chemical Co., Ltd.) of (A) component fluorene type epoxy acrylate / anhydride polymer adduct ) Component dipentaerythritol hexaacrylate DPHA (manufactured by Nippon Kayaku Co., Ltd.) 4.8 g was added and stirred. Next, 351.5 g of Green dispersion C composed of component (D), a dispersant, and a solvent, which were previously dispersed and prepared, was added and further stirred. Finally, 3.0 g and 0.3 g of the additive silane coupling agent and surfactant were added, and the mixture was further stirred for 30 minutes to obtain a test ink composition. The composition and evaluation results are shown in Table 2.

[Comparative Example 1]
The rotor was placed in a beaker (1000 ml) and placed on a magnetic stirrer. 118.5 g of BCA was weighed as a solvent, and 1.2 g of YX4000HK (manufactured by Japan Epoxy Resin Co., Ltd.) was added as component (C) while stirring. After confirming their dissolution, 12.2 g of PGMEA solution of component (A), fluorene type epoxy acrylate / acid anhydride polymerization adduct (V259ME resin component 56.5%, manufactured by Nippon Steel Chemical Co., Ltd.) ) Component dipentaerythritol hexaacrylate DPHA (manufactured by Nippon Kayaku Co., Ltd.) (4.6 g) was added and stirred. Next, 363.5 g of Green dispersion D composed of component (D), a dispersant and a solvent, which had been dispersed and prepared in advance, was added and further stirred. Finally, 2.5 g and 0.3 g of the additive silane coupling agent and surfactant were added, and the mixture was further stirred for 30 minutes to obtain a test ink composition. The composition and evaluation results are shown in Table 2.

[Comparative Example 2]
The rotor was placed in a beaker (1000 ml) and placed on a magnetic stirrer. 96.5 g of BCA was weighed as a solvent, and 3.5 g of YX4000HK (manufactured by Japan Epoxy Resin Co., Ltd.) was added as component (C) while stirring. After confirming these dissolutions, 35.0 g of PGMEA solution (5259% V259ME resin component, etc., manufactured by Nippon Steel Chemical Co., Ltd.) of (A) component fluorene type epoxy acrylate / anhydride polymer adduct 13.5 g of dipentaerythritol hexaacrylate DPHA (manufactured by Nippon Kayaku Co., Ltd.) was added and stirred. Next, 351.5 g of Green dispersion A composed of component (D), a dispersant and a solvent, which had been dispersed and prepared in advance, was added and further stirred. Finally, 2.5 g and 0.3 g of the additive silane coupling agent and surfactant were added, and the mixture was further stirred for 30 minutes to obtain a test ink composition. The composition and evaluation results are shown in Table 2.

[Comparative Example 3]
The rotor was placed in a beaker (1000 ml) and placed on a magnetic stirrer. 206.2 g of BCA was weighed as a solvent, and 3.1 g of YX4000HK (manufactured by Japan Epoxy Resin Co., Ltd.) was added as component (C) while stirring. After confirming the dissolution, 32.2 g of PGMEA solution (5259% V259ME resin component, etc., manufactured by Nippon Steel Chemical Co., Ltd.) of (A) component fluorene type epoxy acrylate / acid anhydride polymerization adduct was obtained (B ) Component dipentaerythritol hexaacrylate DPHA (manufactured by Nippon Kayaku Co., Ltd.) 12.4 g was added and stirred. Next, 246.1 g of Red dispersion A composed of component (D), a dispersant and a solvent previously dispersed and added was added and further stirred. Finally, 2.5 g and 0.3 g of the additive silane coupling agent and surfactant were added, and the mixture was further stirred for 30 minutes to obtain a test ink composition. The composition and evaluation results are shown in Table 2.

[Comparative Example 4]
The rotor was placed in a beaker (1000 ml) and placed on a magnetic stirrer. Weigh 146.0 g of BCA as a solvent, and stir 48.5 g of PGMEA solution of component (A) fluorene type epoxy acrylate / acid anhydride polymerization adduct (V259ME resin component 56.5% made by Nippon Steel Chemical Co., Ltd.) g and 18.5 g of component (B) dipentaerythritol hexaacrylate DPHA (manufactured by Nippon Kayaku Co., Ltd.) were added and stirred. Next, 287.0 g of Blue dispersion A composed of component (D), a dispersing agent and a solvent previously dispersed and prepared was added and further stirred. Finally, 2.5 g and 0.3 g of the additive silane coupling agent and surfactant were added, and the mixture was further stirred for 30 minutes to obtain a test ink composition. The composition and evaluation results are shown in Table 2.

  The test ink composition obtained above was evaluated by the following procedure, and the results are shown in Table 2.

<Viscosity stability test>
The prepared ink composition was previously measured for its viscosity at 50 rpm and 23 ° C. with an E-type viscometer. Thereafter, 100 g was transferred to a container that could be sealed, and after accelerated aging at 40 ° C. for one week, the viscosity was measured under the same conditions, and an increase in viscosity from the initial viscosity was 1 mPa · sec or less was accepted.

<Discharge test>
Connected to Toshiba Tec head (CA-3), purged and washed, checked ink composition ejection status with strobe camera, no droplets ejected, flight trajectory not clearly vertical, etc. If there was no defect, it was rated as “Good”. The state of the pass level in this test is shown in FIG.

<NMP immersion test>
A glass substrate coated and cured with an ink composition is cut into 5 cm squares, immersed in NMP (N-methylpyrrolidone) for 24 hours at room temperature, then discolored (passed with ΔE <3) and film peeling The presence or absence of cracks was confirmed.

<Heat resistance test>
A glass substrate coated and cured with an ink composition is cut into 5 cm squares and placed in an oven set at 250 ° C. for 1 hour, and then the coating color changes (passes ΔE <3) and film peeling or cracking occurs. The presence or absence was confirmed.

<Liquid crystal contamination test (VHR)>
20 mg of a cured film is collected from a glass substrate coated and cured with the ink composition, mixed in a screw tube in which 1.0 g of liquid crystal ZLI4792 is weighed in a draft, and sealed. After this was aged at 100 ° C./72 h, liquid crystal was injected into the glass cell for measurement. This cell was set in a voltage holding ratio measurement system (VHR-1A) manufactured by Toyo Technica and measured. As a result, a retention rate of 95% or more was considered acceptable.

<Comprehensive evaluation>
The results of the above evaluation tests were listed, and when all passed, it was determined as acceptable.

FIG. 1 is an example of a stroboscopic photograph when it is determined that the discharge test is good.

Claims (8)

  In a color filter ink composition used for producing a color filter by an inkjet method, the ratio of pigment amount to resin amount (pigment / resin amount) in the solid component excluding the solvent in the ink composition is 20 to 20 An ink composition for an ink jet color filter, characterized in that the ratio (dispersant / pigment) of the pigment amount and the amount of the dispersant that disperses the pigment is in the range of 35 to 120 wt%. . An unsaturated compound (A) represented by the following general formula (1), a polyfunctional acrylate compound (B) having 4 or more functional groups, a pigment (D), and a solvent (H), and the component (A) 2. The ink composition for an inkjet color filter according to claim 1, wherein the weight ratio (A) / (B) of the component (B) is in the range of 10/90 to 90/10.
[Wherein, R ₁ , R ₂ , R ₃ and R ₄ independently represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom or a phenyl group, and R ₅ represents a hydrogen atom or a methyl group. . A is -CO-, -SO _2- , -C (CF ₃ ) _2- , -Si (CH ₃ ) _2- , -CH _2- , -C (CH ₃ ) _2- , -O-, 9 , 9-fluorenyl group or a direct bond, X represents a tetravalent carboxylic acid residue, Y ₁ and Y ₂ independently represent a hydrogen atom or -OC-Z- (COOH) _m Represents an acid residue, m represents a number of 1 to 3, and n represents a number of 1 to 200. ]   The polyfunctional epoxy compound (C) having two or more functions is added to the ink composition for a color filter according to claim 1 or 2 with respect to the sum of the components (A) and (B) [(A) + (B)]. Ink composition for ink-jet color filters added with 0 to 20% by weight.   The ink composition for inkjet color filters which added the viscosity modifier (E) and surfactant and / or coupling agent (F) to the ink composition for color filters in any one of Claims 1-3. object.   The ink composition for an inkjet color filter according to any one of claims 1 to 4, wherein the solvent (H) is composed of two or more kinds of mixed solvents, and the boiling point of any solvent is in the range of 120 to 350 ° C.   The ink composition for an inkjet color filter according to any one of claims 1 to 5, wherein the solvent is used in an amount of 50 to 1000 parts by weight based on 100 parts by weight of the total of components (A) to (F).   A color filter cured film obtained by drying and curing a pixel formed by an ink jet method using the ink composition for an ink jet color filter according to claim 1. A color filter comprising the cured color filter film according to claim 7.