JP2002173624A - Ink jet ink composition for color filter and method for producing color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter having pixels formed by an ink jet method, which is excellent in heat resistance and solvent resistance, especially excellent in heat resistance, and to use the ink composition for a color filter. To provide a method for manufacturing a color filter. SOLUTION: The present invention provides an inkjet ink composition for a color filter, comprising (a) an amino resin having a carboxyl group and / or a phenolic hydroxyl group, and (b) a coloring material, and a method for producing a color filter.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a color filter used in a color liquid crystal display, a color scanner, a solid-state image pickup device, etc., and more particularly, to a durability required after a pattern forming step by an ink jet method. The present invention relates to an inkjet ink composition for a color filter which is suitable for use and has excellent durability, and a method for producing a color filter.

[0002]

2. Description of the Related Art Conventionally, as one of ink jet ink compositions for energy beam polymerizable color filters using a color material such as a pigment or a dye, an ink jet ink composition for a color filter in which a color material is dispersed or dissolved in a binder resin solution. An inkjet ink composition for a photocurable color filter in which a photopolymerizable monomer and a photopolymerization initiator are added to a product, and an inkjet ink composition for a thermosetting color filter in which a coloring material is dispersed or dissolved in a thermosetting resin. A color image forming method is known in which a color pattern is formed by applying this on a substrate using an ink-jet method to form a color pattern, and then irradiating with a light or heat energy ray. Have been. In particular, as one of the fields of application of these ink-jet ink compositions for energy ray polymerizable color filters, there are color filters used for color liquid crystal displays, color scanners, solid-state imaging devices and the like.

[0003] A color filter is provided on a transparent substrate provided with a black matrix, for each of three colors of red, green and blue light.
It is formed by disposing a color material in each pixel portion so as to selectively transmit primary colors or to selectively reflect three primary colors of cyan, magenta, and yellow.

As a method of forming a color filter, a photolithography method, an electrodeposition method, a printing method, an ink-jet method, and the like are known. At present, the photolithography method is mainly used. Apply the inkjet ink composition for the substrate to the substrate, pattern exposure, then dissolve and wash unnecessary parts red,
This is a method with many steps of forming a color filter by repeating three steps for blue, green or cyan, magenta, and yellow. On the other hand, the ink jet method capable of forming pixels red, blue, green or cyan, magenta, and yellow in one step has attracted attention because of a small number of steps and low cost.

A method of forming a color filter by an ink-jet method is disclosed in JP-A-59-75205 and JP-A-61-75205.
As disclosed in JP-A-245106 and JP-A-63-294503, the color filters obtained by these methods are inferior in heat resistance and solvent resistance because the coloring material is dye-based. On the other hand, various methods using a resin and a pigment have been proposed as a method for obtaining a colored layer having higher heat resistance and solvent resistance. For example, JP-A-5-22400
Japanese Patent Application Laid-Open No. H8-1995 discloses a color filter using an inkjet ink comprising a melamine resin and a colorant.
JP-A-171010 discloses a color filter using a heat or photo-curable inkjet ink containing an acrylamide polymer, and JP-A-10-17813 discloses a melamine resin, a polycarboxylic acid derivative and an amine-based stabilizer. A color filter using an ink-jet ink as a component is disclosed in each of JP-A-7-188.
No. 596 discloses a thermosetting ink jet recording ink using a thermosetting resin and a specific amine as a dispersant.

Recently, as the size of LCDs has increased, many of the characteristics required for color filter materials have been attributed to the process of manufacturing color liquid crystal displays.
Heat resistance required in the vapor deposition or sputtering process, baking process, etc. of transparent electrodes such as TO, solvent resistance required in the cleaning process, alignment film coating process, etc. In addition, light transmitted through the color filter during image display is image information Therefore, light resistance is also required.

In the case of using an ink-jet ink containing an acrylic resin, there is a disadvantage that the resin is liable to be decomposed at a temperature exceeding 200 ° C. On the other hand, JP-A-5-224007 discloses an inkjet ink using a thermosetting resin such as a melamine resin for the purpose of improving heat resistance. However, this method uses an organic or inorganic ink in the ink. Acids and their amine salts and ammonium salts are used in combination as a curing accelerator, and these remain in the film as impurities, contaminating the sputtering apparatus when forming the ITO transparent electrode, or forming a one-part ink. It has the disadvantage that the pot life of the ink is shortened.

On the other hand, in the production of a color filter using an ink jet method, a method using a water-based ink has been disclosed due to environmental problems. JP-A-8-319444
Japanese Patent Application Laid-Open Publication No. H11-139,086 discloses a black matrix coating composition containing an aqueous pigment ink. Further, Japanese Patent Application Laid-Open
Japanese Patent Application No. 0-96810 discloses a method in which a polysilane photosensitive layer is exposed to ultraviolet light to form a hydrophilic latent image, and a color filter is formed using hydrophilic ink. However, these methods have a disadvantage that heat resistance cannot be satisfied.

That is, as the temperature of the transparent electrode is increased during vapor deposition, sputtering, or firing, a color filter having higher heat resistance and no color change due to heat has been demanded. Under such circumstances, a color filter having pixels excellent in heat resistance, solvent resistance, and the like is desired.

[0010]

SUMMARY OF THE INVENTION An object of the present invention is to provide a color filter having pixels formed by an ink-jet method, which is excellent in heat resistance and solvent resistance, particularly, heat resistance. An object of the present invention is to provide an inkjet ink composition and a method for producing a color filter using the same.

[0011]

According to the present invention, there is provided an ink jet printer for a color filter comprising (a) an amino resin having a carboxyl group and / or a phenolic hydroxyl group, and (b) a coloring material. An ink composition is provided.

In order to solve the above-mentioned problems, the present invention provides an ink-jet ink composition for a color filter containing (a) an amino resin having a carboxyl group and / or a phenolic hydroxyl group and (b) a coloring material. Provided is a method for manufacturing a color filter in which a pixel portion is formed on a transparent substrate by an inkjet recording method and then the pixel portion is cured.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail. The amino resin having a carboxyl group and / or a phenolic hydroxyl group (hereinafter, referred to as amino resin (a) used in the present invention) used in the ink jet ink composition for a color filter of the present invention is, for example, for example,
(1) A method of condensing an amino compound having a carboxyl group and / or a phenolic hydroxyl group with an aldehyde compound, or (2) A method of condensing an aldehyde compound having a carboxyl group and / or a phenolic hydroxyl group with an amino compound Can be manufactured.

Examples of the amino compound having a carboxyl group include 2-, 3- or 4- (4,6-diamino-1,3,5-triazin-2-yl) benzoic acid,
Methyl-2- (4,6-diamino-1,3,5-triazin-2-yl) benzoic acid, 4-methoxy-2- (4
6-diamino-1,3,5-triazin-2-yl) benzoic acid, 2-methyl-4- (4,6-diamino-1,
3,5-triazin-2-yl) benzoic acid, 2-chloro-4- (4,6-diamino-1,3,5-triazine-
2-yl) benzoic acid, and the like.

Examples of the amino compound having a phenolic hydroxyl group include 2-, 3- or 4- (4,6-diamino-1,3,5-triazin-2-yl) phenol and 4-methyl-2- (4,6-diamino-1,3,5
-Triazin-2-yl) phenol, 2-methoxy-
4- (4,6-diamino-1,3,5-triazine-2
-Yl) phenol, 3-chloro-4- (4,6-diamino-1,3,5-triazin-2-yl) phenol, and the like.

Examples of the aldehyde compound having a carboxyl group include glyoxylic acid and its hydrate,
And succin semialdehyde.

Examples of the aldehyde compound having a phenolic hydroxyl group include 2-, 3- or 4-hydroxybenzaldehyde, 3,4-, 3,5-, 2,5- or 2,4-dihydroxybenzaldehyde, 4,6-
Trihydroxybenzaldehyde, and the like.

Examples of the aldehyde compound include, in addition to the above-mentioned aldehyde compounds having a carboxyl group and / or a phenolic hydroxyl group, for example, formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, glyoxal, and trioxane and paraformaldehyde. Formaldehyde condensates; aqueous solutions such as aqueous formaldehyde; methylhemiformal, n-butylhemiformal or isobutylhemiformal.

Examples of the amino compound include, in addition to the above-mentioned amino compounds having a carboxyl group and / or a phenolic hydroxyl group, for example, urea, melamine, benzoguanamine, acetoguanamine, cyclohexanecarboguanamine, phthaloguanamine, steloguanamine, spiroguanamine and the like. Is mentioned.

The amino resin (a) used in the present invention
Can be used by the above method (1) or (2), a plurality of types of amino compounds and / or a plurality of types of aldehyde compounds can be used. For example, benzoguanamine and 4
-(4,6-diamino-1,3,5-triazine-2-
(Ill) Benzoic acid may be used in a desired ratio, and formaldehyde and glyoxylic acid may be used in a desired ratio. As described above, by using a plurality of amino compounds and / or aldehyde compounds as raw materials, it is possible to adjust the acid value of the obtained amino resin and control the solubility of the curable color filter inkjet ink composition in a solvent. it can.

The condensation product having a phenolic hydroxyl group obtained by the above method can be stabilized by etherifying the phenolic hydroxyl group with an alcohol.

The amino resin (a) used in the present invention is described in, for example, JP-A-9-143169 and JP-A-8-17.
No. 6,249, JP-A-9-208821, JP-A-10-140015, and the like.
８8 mol and 3-20 mol of the alcohol for etherification can be produced, if necessary, by a reaction method in the presence of a known and commonly used solvent.

[0023] When used in combination the amino compound and / or aldehyde compounds of two or more, there is no particular limitation on the ratio, the acid value of the resulting amino resin (a) is too low, solubility in water-soluble solvent In addition, the curing action due to the carboxyl group or phenolic hydroxyl group at the time of heat curing tends to decrease. On the other hand, if the acid value of the obtained amino resin (a) is too high, the water resistance after curing tends to deteriorate. is there. Therefore, amino acid (a) has an acid value of 20 to 250 mg KO.
It is preferable to adjust the composition so as to be in the range of H / g.

The amino resin (a) having a phenolic hydroxyl group etherified can be produced by a known and commonly used method. That is, for example, (1) an amino compound is added to a solution obtained by adding an aldehyde compound to an alcohol for etherification, and 50-
At a temperature of 140 ° C., react for 20 minutes to 7 hours,
A method of simultaneously performing a condensation reaction and an etherification reaction,

(2) The solution in which the aldehyde compound and the amino compound are added is subjected to methylolation within a pH range of 8 to 10, and then, in the presence of an alcohol for etherification, alkylation within a pH range of 2 to 6. How to carry out etherification,

(3) At least one selected from the group consisting of urea, melamine, benzoguanamine, acetoguanamine, cyclohexanecarboguanamine, phthaloguanamine, steroganamin and spiroguanamine in a solution obtained by adding an aldehyde compound to an alcohol for etherification. And during the condensation reaction and the etherification reaction, (4,6-diamino-1,3,5-triazin-2-yl) benzoic acid and / or (4,6-diamino-
Adding 1,3,5-triazin-2-yl) -phenol;

(4) The alcohol for etherification is selected from the group consisting of formaldehyde, paraformaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, glyoxal, glyoxylic acid, succin semialdehyde and 2-, 3- or 4-hydroxybenzaldehyde. , At least one aldehyde compound, then urea, melamine, benzoguanamine,
Acetoguanamine, cyclohexanecarboguanamine,
Phthaloganamin, steroganamin, spiroguanamine, (4,6-diamino-1,3,5-triazine-2
-Yl) benzoic acid and (4,6-diamino-1,3,3)
A method of adding at least one amino compound selected from the group consisting of 5-triazin-2-yl) -phenol and performing a condensation reaction and an etherification reaction.

The carboxyl groups and / or phenolic hydroxyl groups introduced into the amino resin (a) are completely or partially neutralized with various volatile bases such as ammonia or organic amines, It is also possible to dissolve or disperse in water or a mixture of water and a water-soluble solvent.

The organic amine used for neutralizing the carboxyl group and / or the phenolic hydroxyl group introduced into the amino resin (a) is not particularly limited.
Alkylamines such as monomethylamine, dimethylamine, monoethylamine, diethylamine or triethylamine; N-methylaminoethanol, N, N-dimethylaminoethanol, N, N-diethylaminoethanol, 2-amino-2-methylpropanol, diethanolamine Or hydroxylamines such as triethanolamine; and polyvalent amines such as ethylenediamine or diethylenetriamine. These can be used alone or in combination of two or more.

As the coloring material used in the present invention, dyes and pigments usually used for color filters can be used without any particular trouble. However, pigments are preferably used from the viewpoint of heat resistance and light resistance.

The average particle size of the pigment is preferably in the range of 0.005 to 3 μm. More preferably 0.01-1μ
m. If the average particle size is less than this, thixotropy is likely to occur and good coating properties cannot be obtained, and if it is larger than this, the coating film lacks transparency. To achieve such a particle size, a ball mill, sand mill, peas mill, three rolls, paint shaker, attritor,
A dispersion treatment such as a dispersion stirrer or ultrasonic waves is effective.

The ink-jet ink composition for a color filter of the present invention comprises the above-mentioned coloring material and an amino resin (a).
And using a solvent. As the solvent used at that time, for example, aromatic solvents such as toluene, xylene, and methoxybenzene; acetate solvents such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate; ethoxy; Propionate solvents such as ethyl propionate; alcohol solvents such as methanol, ethanol, propanol and ethylene glycol; ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether and diethylene glycol dimethyl ether;

Ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; aliphatic hydrocarbon solvents such as hexane; N, N-dimethylformamide, γ-butyrolactam, N-methyl-2-pyrrolidone, aniline and pyridine Nitrogen compound solvent; γ
Lactone solvents such as butyrolactone; carbamates such as a 48:52 mixture of methyl carbamate and ethyl carbamate; water; Among these solvents, those having a boiling point in the range of 80 ° C. to 200 ° C. are preferable, and these solvents can be used alone or in combination of two or more.

Since the amino resin (a) used in the present invention is also hydrophilic, the solvent used in the ink jet ink composition for a color filter may be water or a solvent containing water as a main component.

When preparing an ink-jet ink composition for a color filter in which a coloring material is dispersed, a dispersant may be used in combination. Such a dispersant is not particularly limited, and a known and commonly used dispersant can be used. Examples of such dispersants include surfactants, pigment intermediates, dye intermediates, polyester-based compounds, resin-based dispersants such as polyamide-based compounds and polyurethane-based compounds.

Commercially available resin-type dispersants include, for example, “Dispervic 130” manufactured by BYK Chemie,
"Dispervic 161", "Dispervic 16"
2, "Dispervic 163", "Dispervic 170", "Fuka 4" manufactured by Fcar Chemicals.
6 "," Efka 47 ", and" SOLSPARSE 3 "manufactured by Zeneca
2550 "," SOLSPARSE 24000 "," Ajispar PB811 "," Ajispar PB81 "manufactured by Ajinomoto Co.
4 "and the like. In addition, resin-type dispersants such as acryl-based and polyethylene-based resins can also be used.

The ratio of the coloring material is 1 to the nonvolatile content in the ink jet ink composition for a color filter of the present invention.
The range of 0 to 70% by mass is preferable. When a dispersant is used in combination, the proportion of the dispersant is preferably in the range of 5 to 50% by mass based on the colorant.

A color filter can be produced by forming a pixel portion on a transparent substrate by an ink jet recording method using the ink jet ink composition for a color filter of the present invention, and then thermally curing the pixel portion. At that time, the amino resin (a) itself is thermoset. Since the amino resin (a) used in the present invention has a carboxyl group or a phenolic hydroxyl group, there is no need to use a curing accelerator in combination, and the amino resin (a) has an advantage that it does not contain impurities caused by the curing accelerator remaining after curing. .

The ink-jet ink composition for a color filter of the present invention can contain a compound having a photopolymerizable functional group. In this case, a color filter can also be manufactured by a method in which a pixel portion is formed on a transparent substrate by an inkjet recording method, the pixel portion is photopolymerized, and then thermally cured. In that case, it is desirable to use a photopolymerization initiator in the ink jet ink composition for a color filter. The energy ray at the time of photopolymerization is preferably a ray having a wavelength of 200 to 500 nm.

The compound having a photopolymerizable functional group used in the present invention is a compound having a functional group capable of undergoing a polymerization or cross-linking reaction by irradiation with ultraviolet light or visible light. Compounds and cationic polymerization compounds. Specifically, a (meth) acrylic compound, a maleimide compound, and the like can be given.

Examples of the (meth) acrylic compound used as the compound having a photopolymerizable functional group include, for example, trimethylolethanetri (meth) acrylate, trimethylolpropanetri (meth) acrylate, and trimethylolpropanedi (meth) acrylate. , Neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, hexanediol di (meth) acrylate Acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) isocyanurate, tri (acryloyloxyethyl) Cyanurate, glycerin tri (meth) acrylate;

Phenol novolak type epoxy resin,
Reaction products of epoxy resin such as cresol / novolak type epoxy resin, bisphenol A type epoxy resin and (meth) acrylic acid; ethylene glycol, polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethoxydiol of bisphenol A, polyester polyol , Polybutadiene polyols, polyols such as polycarbonate polyols, and organic polyisocyanates (eg, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc.)
And a hydroxyl group-containing (meth) acrylate (for example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,4-butanediol mono (meth) acrylate, etc.).

As the maleimide compound used as the compound having a photopolymerizable functional group, a compound in which a maleimide group is bonded by an aliphatic group is preferable. Specifically, N-hexylmaleimide or N, N'-4 Alkyl or alkyl ether maleimides such as, 9-dioxa-1,12-bismaleimidododecane, ethylene glycol bis (maleimido acetate), poly (tetramethylene glycol) bis (maleimido acetate), tetra (ethylene glycol modified) pentaerythritol tetra Maleimide carboxylic acid (poly) alkylene glycol esters such as (maleimide acetate), bis (2-
Carbonate maleimides such as (maleimidoethyl) carbonate; and urethane maleimides such as isophoronebisurethanebis (N-ethylmaleimide).

Among these, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, N, N'-4,9 -Dioxa-1,12-bismaleimide dodecane, ethylene glycol bis (maleimide acetate), poly (tetramethylene glycol) bis (maleimide acetate), (ethylene glycol-modified) pentaerythritol tetra (maleimide acetate), bis (2-maleimidoethyl) ) Carbonate, isophorone bis urethane bis (N-
Polyfunctional (meth) acrylates such as ethylmaleimide) and polyfunctional maleimides are particularly preferred in terms of curing when irradiated with ultraviolet light, visible light, or the like.

The compound having a photopolymerizable functional group may be used singly or in combination of two or more. The proportion of the compound used is not particularly limited. 2 to the total amount of the binder resin containing the amino resin (a) used in the product.
A range of 5 to 150% by mass is preferred. If it exceeds 150% by mass, the heat resistance aimed at by the present invention is reduced, while
If the amount is less than 5% by mass, a cured coating film having desired coating film physical properties tends to be difficult to obtain, which is not preferable.

The ink-jet ink composition for a color filter of the present invention may optionally contain a photopolymerization initiator. As the photopolymerization initiator, a photopolymerization initiator that dissociates by light to generate a radical can be used,
Known and commonly used photopolymerization initiators are used.

Further, a known and commonly used photosensitizer can be used in combination with the above photopolymerization initiator. Examples of the photosensitizer include amines, ureas, sulfur-containing compounds, phosphorus-containing compounds, chlorine-containing compounds, nitriles, and other nitrogen-containing compounds. These can be used alone or in combination of two or more. The use ratio is not particularly limited, but is preferably in the range of 0.1 to 30% by mass relative to the compound having a photopolymerizable functional group in the color filter inkjet ink composition used in the present invention, Especially, the range of 1 to 20% by mass is particularly preferable. If it is less than 0.1% by mass, the sensitivity tends to decrease,
If the content exceeds 30% by mass, precipitation of crystals and deterioration of physical properties of the coating film tend to be caused, which is not preferable.

The viscosity of the ink-jet ink composition for a color filter of the present invention is preferably adjusted to 50 mPa · s or less, particularly preferably 10 mPa · s or less, from the viewpoint of dischargeability from an ink-jet head. For this reason, the amount of the solvent is preferably in the range of 1 to 19 parts by mass per 1 part by mass of the total solid content.

The ink-jet ink composition for a color filter of the present invention thus obtained is of a one-pack type, has excellent storage stability, and uses an amino resin having a carboxyl group and / or a phenolic hydroxyl group. For this purpose, the composition can be constituted by using an aqueous or non-aqueous solvent. Further, according to the production method of the present invention, in the baking step after pixel formation, a crosslinked structure is generated by a thermal crosslinking reaction of the amino resin, so that the obtained color filter has excellent heat resistance and solvent resistance.

The ink-jet ink composition for a color filter of the present invention may further comprise, if necessary, a range which does not deviate from the object of the present invention, especially a range which can maintain storage stability, heat resistance, solvent resistance and the like. Other components can be included. As such other components, known and commonly used coupling agents, antioxidants, stabilizers, fillers, silicon-based, fluorine-based, acrylic-based leveling agents, polycarboxylic acids and their anhydrides, epoxy And the like. Thus, it can be suitably used as an inkjet ink for a color filter.

The coupling agent is a compound that chemically links the inorganic material and the organic material or improves the affinity with a chemical reaction to enhance the function of the composite material. Typical coupling agents include silane compounds, titanium compounds, and aluminum compounds.

Among them, γ-glycidoxypropyltrimethoxysilane, β- (3,4) are particularly preferred in that they provide particularly excellent smoothness, adhesion, water resistance and solvent resistance to various transparent substrates. -A silane coupling agent having an epoxy group such as (epoxycyclohexyl) ethyltrimethoxysilane is preferred. These coupling agents may be used alone or in combination of two or more.

The amount of the coupling agent used is in the range of 0.1 to 30 parts by mass, preferably 0.5 to 20 parts by mass, per 100 parts by mass of the amino resin (a). When the amount of the coupling agent is less than 0.1 part by mass, the smoothness of the formed coating film, the adhesion to the transparent substrate, the water resistance and the solvent resistance are insufficient, and the amount exceeds 30 parts by mass. In addition, it is not preferable because no improvement in adhesiveness can be expected, and furthermore, the energy ray curability of the formed coating film decreases.

The polycarboxylic acid and its anhydride are used for the purpose of adjusting the solubility in an aqueous solvent, and the epoxy compound is used for the purpose of eliminating the carboxyl group remaining after photocuring by a thermal reaction.

Examples of the epoxy compound include phenol novolak epoxy resin, cresol novolak epoxy resin, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol A novolak epoxy resin, alicyclic epoxy resin, and the like. Examples include various glycols, alkylene oxide-modified epoxy resins, glycidyl group-containing acrylic resins, alicyclic epoxy group-containing acrylic resins, and the like. These can be used alone or in combination of two or more.

The ink jet ink composition for a color filter of the present invention prepared as described above is formed on a transparent substrate by an ink jet method after forming a color filter pattern and then heat curing, or after photopolymerization, heat By curing, a color filter can be manufactured.

The transparent substrate used in the present invention can be used as long as it is a transparent substrate used for a color filter and has heat resistance that can withstand heat curing. Examples of such a transparent substrate include a glass substrate and the like. Is mentioned.

The ink jet system used in the present invention includes a bubble jet (registered trademark) system using an electrothermal converter as an energy generating element, and a piezo jet system using a piezoelectric element.

In order to form a colored pattern, first, the inkjet ink composition for a color filter of the present invention may be ejected from an ejection head into a prescribed colored pattern on a transparent substrate provided with a black matrix by an inkjet method. Black matrix is a known formation method,
That is, a method of forming a metal thin film pattern by sputtering or vapor deposition, a method of patterning by a photolithography process using a black resin composition,
It can be provided on a transparent substrate by an inkjet method or the like. At this time, depending on the properties of the ink-jet ink composition, the black matrix may be subjected to a hydrophilic treatment, a hydrophobic treatment or an oil repellency treatment. Further, if necessary, applying a surface treatment to the substrate using an adhesion aid such as the above-described coupling agent is effective as a means for improving the adhesive force between the substrate and the pixel pattern. Further, the substrate may be provided with an inkjet ink receiving layer.

The color filter can be formed, for example, by the following method. That is, after the ink jet method for color filters of the present invention is discharged from a discharge head to form a pixel portion on a transparent substrate provided with a black matrix by an ink jet method, the pixel portion is thermally cured, or After the polymerization, heat curing is performed. Next, a method of forming a protective film on the pixel portion, if necessary, and after-baking, if necessary, forming a transparent conductive electrode of ITO or the like may be used.

Examples of the heat source used for thermosetting include well-known conventional heat sources such as a hot plate, an electric oven, and an infrared heating furnace. Heating temperature is 150
The range of -300 ° C is preferred. If the temperature is lower than 150 ° C, thermal curing is insufficient, so that the film strength, solvent resistance and alkali resistance tend to be inferior. If the temperature exceeds 300 ° C, excessive volume shrinkage occurs in the pixel portion, and the adhesion to the substrate and the precision This is not preferred because problems are likely to occur.

The light source used for photocuring the composition is preferably a light source having a wavelength in the ultraviolet region to the visible light region.
Light sources with a wavelength between 00 and 500 nm are preferred. For these light sources, use of ultraviolet light is particularly preferable for economic reasons. Sources of ultraviolet light or visible light include, for example, low-pressure mercury lamp, high-pressure mercury lamp, ultra-high-pressure mercury lamp, metal halide lamp, chemical lamp, black light lamp, mercury-xenon lamp, excimer lamp, short arc lamp, helium. THG using cadmium laser, argon laser and Nd-YAG laser
And an FHG optical laser. The photocuring conditions are affected by the type of light source used and the type and amount of the photopolymerization initiator, and cannot be unconditionally determined.
The range of 0 to 3000 J / m ² is preferred. When photopolymerization and thermosetting are used in combination, the above thermosetting conditions are applied.

According to the production method of the present invention,
Three types of ink jets for color filters each containing a color material that selectively transmits three primary colors of red, green and blue light, or a color material that selectively reflects three primary colors of cyan, magenta and yellow. After preparing an ink composition and forming, on a transparent substrate provided with a black matrix, pixel portions of three primary colors composed of three types of ink jet ink compositions for a color filter using a known ink jet method, as described above. Then, by curing the pixel portion, a color filter can be manufactured. Further, according to the manufacturing method of the present invention, a black matrix portion can be formed in addition to the above-described three color pixel portions.

[0064]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the following, “parts” and “%” are all based on mass unless otherwise specified. The performance test for the prepared coating film was performed by the following method.

<Performance Test and Evaluation Criteria><< Storage Stability >> The viscosity of the ink composition for color filters when stored at 40 ° C. for 24 hours was measured. ,
Those with 10% or more were evaluated as x. The viscosity was measured using an E-type viscometer manufactured by Tokimec.

<< Curing Conditions >> Photopolymerization conditions: A pattern was formed by an ink-jet method, followed by drying at 110 ° C. for 10 minutes, followed by exposure to 1000 J / m ² with a high pressure mercury lamp to cure. Thermal curing conditions: A pattern was formed by an inkjet method, then dried at 110 ° C. for 10 minutes, and then cured in an oven at 200 ° C. for 30 minutes. After bake: In light or heat curing,
After baking was performed at 230 ° C. for 15 minutes.

<< Evaluation of Physical Properties of Coating Film >> Heat resistance-1: A coating film applied and cured on a glass plate by an ink-jet method was heated at 280 ° C. for 30 minutes, and the transparency (Y value) in the color tone before and after heating was measured. The change was evaluated. At this time, the difference ΔY in the change rate was less than 0.5, and the result was 0.5 or more. The chromaticity measurement was performed using an Olympus microspectrophotometer OSP-SP200.

[0068] heat resistance -2: The coating film was on a glass plate was coated by an inkjet method curing, heating for 30 minutes at 280 ° C., was evaluated by the change in maximum light transmittance before and after heating. If the rate of change at this time is less than 5%, it is ○.
And

Solvent resistance -1: After immersing in N-methyl-2-pyrrolidone at 23 ° C. for 30 minutes using a coating film applied and cured on a glass plate by an ink jet method, the boundary of the liquid immersion portion The surface was observed, and the case where the boundary was visually confirmed was evaluated as x, and the case where the boundary was not visually observed was evaluated as ○.

Solvent resistance-2: 100 g of a coating film coated and cured on a glass plate by an inkjet method using a rubbing tester [Taira Rika Kogyo Co., Ltd.] at 25 ° C.
Rubbing was performed with acetone under a load, and the number of rubbings until reaching the glass substrate as the base was evaluated. At this time, the rubbing frequency of less than 25 times was evaluated as x, 25 or more and less than 100 times as ○, and 100 or more times as ◎.

Production Example 1 [Preparation of amino resin having carboxyl group] In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 2- (4,6- Diamino-
1,3,5-triazin-2-yl) benzoic acid
7 parts, 202.8 parts of 37% aqueous formaldehyde solution, n
-222.3 parts of butanol were charged and immersed in an oil bath heated to 115 ° C with stirring. After 15 minutes, a homogeneous solution was obtained and reflux was started. After continuing the reaction for 2 hours, water and excess formaldehyde were distilled off under reduced pressure of 5.33 × 10 ⁴ Pa for 3 hours.

Then, after distilling off water and n-butanol, propylene glycol monomethyl ether acetate (hereinafter abbreviated as PGMAc) was added and cooled.
Further, PGMAc was added, and the nonvolatile matter (107.5 ° C., 1
(Resin mass% after drying for 4 hours) was adjusted to 40.0%.
An amino resin having a carboxyl group of 94.6 mgKOH / g having an acid value of the resin solids of 94.6 mgKOH / g (the number of milligrams of potassium hydroxide required to neutralize the acid content present in 1 g of the sample based on a prescribed method) a-1) was obtained. Number average molecular weight in terms of polystyrene; Mn = 2150, degree of dispersion: Mw / M
n was 5.12.

Production Example 2 [Preparation of amino resin having carboxyl group] In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 37.4 parts of benzoguanamine, 118.4 parts of a 50% aqueous glyoxylic acid solution, 88.8 parts of n-butanol was charged, and immersed in an oil bath heated to 115 ° C. with stirring. After 15 minutes, a homogeneous solution was obtained and reflux was started. After continuing the reaction for 1 hour, 5.33 × 10 ⁴ Pa
The water and excess formaldehyde were distilled off under reduced pressure for 4 hours. Next, after distilling off water and n-butanol, PGMAc was added and cooled, and PGMAc was further added to adjust the nonvolatile content to 40.0%. An amino resin (A-2) having a carboxyl group and an acid value of the resin solid content of 136 mgKOH / g was obtained. Number average molecular weight in terms of polystyrene; Mn is 1,624, dispersity: Mw / Mn is 1.2.
It was 8.

Production Example 3 [Preparation of Amino Resin Having Phenolic Hydroxyl Group] In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 18.7 parts of benzoguanamine, 48.8 parts of p-hydroxybenzaldehyde, 88.8 parts of n-butanol was charged and immersed in an oil bath heated to 125 ° C. with stirring. After 20 minutes, a homogeneous solution was obtained. The reaction was continued at the same temperature for 24 hours. 5.33x after the reaction
After n-butanol was distilled off under a reduced pressure of 10 ⁴ Pa, the obtained solid was washed with a mixed solution of n-hexane / ethyl acetate (2/1) to remove excess p-hydroxybenzaldehyde. PGMAc is added and cooled.
MAc was added to adjust the nonvolatile content to 40.0%. An amino resin (A-3) having a phenolic hydroxyl group having an acid value of 85.2 mgKOH / g of a resin solid content was obtained. Number average molecular weight in terms of polystyrene; Mn is 4000, dispersity: M
w / Mn was 3.26.

Production Example-4 [Preparation of Acrylic Resin Having Carboxyl Group] In a four-necked flask equipped with a thermometer, a reflux condenser, a stirrer, and a nitrogen gas inlet, 425.0 parts of PGMAc was charged and stirred. After the temperature was raised to 90 ° C., 42.8 parts of methacrylic acid (hereinafter abbreviated as MAA) and benzyl methacrylate (hereinafter abbreviated as BzMA) 28 were used.
A mixed solution of 6.1 parts, 96.0 parts of PGMAc and 16.5 parts of t-butylperoxy-2-ethylhexanate (hereinafter abbreviated as “PO”) was added dropwise over 1 hour. . After holding at 90 ° C. for 2 hours after dropping,
1.7 parts of “PO” were added, and the mixture was further reacted at the same temperature for 7 hours to obtain a solution of an acrylic resin (A-4) having a carboxyl group having an acid value of 84.0 mgKOH / g in the resin solid content. . The nonvolatile content of the obtained resin solution is 39.7%, the Mn in terms of polystyrene is 9500, and the degree of dispersion Mw / Mn is 2.
07.

Example 1 A carboxyl group-containing amino resin solution (A-1) prepared in Production Example 1 using a high-speed disperser “TSG-6H” (manufactured by Igarashi Kikai) loaded with zirconia beads of 0.5 mmφ. 25.0 parts, C.I. I. Pigment Red 25
8.0 as a dispersant, "AJISPER PB814"
(Resin type dispersant manufactured by Ajinomoto Co.) 2.5 parts and PGMAc
A dispersion of 64.5 parts was dispersed at a rotation speed of 2000 m ^-1 for 8 hours to obtain a red pigment dispersion. Next, based on 100 parts of the above red pigment dispersion, 7.0 parts of dipentaerythritol hexaacrylate (hereinafter abbreviated as DPHA) and "Irgacure # 369" (manufactured by Ciba Specialty Chemical Co., Ltd.) as a photopolymerization initiator. ) 0.
After adding 3 parts and mixing, the mixture was filtered through a filter having a pore size of 1.0 μm to obtain a photopolymerizable inkjet ink composition (R-1) for a color filter.

The thus-obtained ink-jet ink composition for photopolymerizable color filter (R-1) 2
5 g was transferred into a glass container, sealed, stored at 40 ° C. for 24 hours, and the storage stability was evaluated according to the performance test method. As a result, the storage stability was good.

Next, a pixel pattern was formed from the photopolymerizable ink-jet ink composition for color filter (R-1) using a piezo jet type head.
Pre-dried at 0 ° C. for 10 minutes to form a red patterned coating. The obtained coating film pattern was exposed to 1000 J / m ² using a high-pressure mercury lamp according to photopolymerization conditions. The obtained coating film pattern was thermally cured at 230 ° C. for 15 minutes,
A red pixel pattern for a color filter was obtained.

The red pixel pattern for a color filter thus obtained was evaluated according to the performance test items. The pixel pattern was excellent in heat resistance and solvent resistance. Further, when the absorption spectrum and the thin film X-ray diffraction of the pixel pattern after the heat resistance test were measured, no change in the crystal type of the red pigment and no increase in the particle diameter were observed. These evaluation results are summarized in Table 1.

Example 2 Example 1 was repeated except that the amino resin (A-2) obtained in Production Example 2 was used instead of the amino resin (A-1).
In the same manner as in Example 1, a photopolymerizable inkjet ink composition (R-2) for a color filter was obtained.

25 g of the obtained photopolymerizable ink-jet ink composition for a color filter (R-2) was transferred into a glass container, sealed, stored at 40 ° C. for 24 hours, and the storage stability was evaluated. As a result, the storage stability was good.

Next, using the obtained photopolymerizable ink-jet ink composition for color filter (R-2),
A pixel pattern was formed on a glass substrate in the same manner as in Example 1. Exposure and heat curing were performed in the same manner as in Example 1 to obtain a red pixel pattern for a color filter.

The red pixel pattern for a color filter thus obtained was evaluated in accordance with the performance test items. The pixel pattern was found to be excellent in heat resistance and solvent resistance. Further, when the absorption spectrum and the thin film X-ray diffraction of the pixel pattern after the heat resistance test were measured, no change in the crystal type of the red pigment and no increase in the particle diameter were observed. These evaluation results are summarized in Table 1. Evaluation was made according to the performance test items.

Example 3 The procedure of Example 1 was repeated, except that the amino resin (A-3) obtained in Production Example 3 was used instead of the amino resin (A-1). A photopolymerizable inkjet ink composition for a color filter (R-3) was obtained.

25 g of the obtained photopolymerizable ink-jet ink composition for color filter (R-3) was transferred into a glass container, sealed, and stored at 40 ° C. for 24 hours to evaluate the storage stability. As a result, the storage stability was good.

Next, using the obtained photopolymerizable ink-jet ink composition for color filter (R-3),
A pixel pattern was formed on a glass substrate in the same manner as in Example 1. Exposure and heat curing were performed in the same manner as in Example 1 to obtain a red pixel pattern for a color filter.

The red pixel pattern for a color filter thus obtained was evaluated according to the performance test items. The pixel pattern was found to be excellent in heat resistance and solvent resistance. Further, when the absorption spectrum and the thin film X-ray diffraction of the pixel pattern after the heat resistance test were measured, no change in the crystal type of the red pigment and no increase in the particle diameter were observed. These evaluation results are summarized in Table 1. Evaluation was made according to the performance test items.

Example 4 In Example 1, the amino resin (A-1) 12.5 obtained in Production Example 1 was replaced with 25 parts of the amino resin (A-1).
Part and acrylic resin (A-4) obtained in Production Example 4
Except for using 5 parts of the mixture, the same as in Example 1
A photopolymerizable inkjet ink composition for a color filter (R-4) was obtained.

25 g of the obtained photopolymerizable ink-jet ink composition for color filter (R-4) was transferred into a glass container, sealed, and stored at 40 ° C. for 24 hours to evaluate the storage stability. As a result, the storage stability was good.

Next, using the obtained photopolymerizable ink-jet ink composition for color filter (R-4),
A pixel pattern was formed on a glass substrate in the same manner as in Example 1. Exposure and heat curing were performed in the same manner as in Example 1 to obtain a red pixel pattern for a color filter.

The red pixel pattern for a color filter thus obtained was evaluated according to the performance test items. The pixel pattern was found to be excellent in heat resistance and solvent resistance. The measured absorption spectrum and thin-film X-ray diffraction of the pixel pattern after the heat resistance test, the increase in crystal form change and the particle size of the red pigment were not observed. These evaluation results are summarized in Table 1. Evaluation was made according to the performance test items.

Example 5 In Example 1, compound DP having a photopolymerizable functional group was used.
In the same manner as in Example 1 except that pentaerythritol triacrylate (hereinafter abbreviated as “PETA”) was used instead of HA, a photopolymerizable ink jet ink composition for color filter (R-5) was prepared. Obtained. Example 1
In the same manner as above, evaluate the storage stability and various physical properties of the coating film,
Table 1 shows the evaluation results.

25 g of the obtained photopolymerizable ink-jet ink composition for color filter (R-5) was transferred into a glass container, sealed, and stored at 40 ° C. for 24 hours to evaluate the storage stability. As a result, the storage stability was good.

Next, using the obtained photopolymerizable ink-jet ink composition for color filter (R-5),
A pixel pattern was formed on a glass substrate in the same manner as in Example 1. Exposure and heat curing were performed in the same manner as in Example 1 to obtain a red pixel pattern for a color filter.

When the red pixel pattern for a color filter thus obtained was evaluated according to the performance test items, the pixel pattern was excellent in heat resistance and solvent resistance. Further, when the absorption spectrum and the thin film X-ray diffraction of the pixel pattern after the heat resistance test were measured, no change in the crystal type of the red pigment and no increase in the particle diameter were observed. These evaluation results are summarized in Table 1. Evaluation was made according to the performance test items.

Example 6 In Example 1, compound DP having a photopolymerizable functional group was used.
Instead of HA, poly (tetramethylene glycol) bis (maleimide acetate) [average molecular weight of poly (tetramethylene glycol) 250] (hereinafter referred to as “MIA25
0 ”. ) Was used in the same manner as in Example 1 to obtain a photopolymerizable ink-jet ink composition for a color filter (R-6).

25 g of the obtained photopolymerizable ink-jet ink composition for color filter (R-6) was transferred into a glass container, sealed, and stored at 40 ° C. for 24 hours to evaluate the storage stability. As a result, the storage stability was good.

Next, using the obtained photo-polymerizable ink-jet ink composition for color filter (R-6),
A pixel pattern was formed on a glass substrate in the same manner as in Example 1. Exposure and heat curing were performed in the same manner as in Example 1 to obtain a red pixel pattern for a color filter.

The red pixel pattern for a color filter thus obtained was evaluated according to the performance test items. The pixel pattern was found to be excellent in heat resistance and solvent resistance. Further, when the absorption spectrum and the thin film X-ray diffraction of the pixel pattern after the heat resistance test were measured, no change in the crystal type of the red pigment and no increase in the particle diameter were observed. These evaluation results are summarized in Table 1. Evaluation was made according to the performance test items.

Comparative Example 1 The procedure of Example 1 was repeated, except that the amino resin (A-1) was replaced by the acrylic resin (A-4) obtained in Production Example 4. A comparative photopolymerizable inkjet ink composition for a color filter (R-7) was obtained. The storage stability and various physical properties of the coating film were evaluated in the same manner as in Example 1, and the evaluation results are shown in Table 1.

25 g of the obtained photopolymerizable ink-jet ink composition for color filter (R-7) was transferred into a glass container, sealed, and stored at 40 ° C. for 24 hours to evaluate the storage stability. As a result, the storage stability was good.

Next, using the obtained photopolymerizable ink-jet ink composition for color filter (R-7),
A pixel pattern was formed on a glass substrate in the same manner as in Example 1. Exposure and heat curing were performed in the same manner as in Example 1 to obtain a red pixel pattern for a color filter.

The thus obtained red pixel pattern for a color filter was evaluated according to the performance test items. The pixel pattern was inferior in heat resistance and solvent resistance. Further, when the absorption spectrum and the thin film X-ray diffraction of the pixel pattern after the heat resistance test were measured, it was confirmed that the particle diameter of the red pigment was increased.

The red pixel pattern for a color filter of Comparative Example 1 in which only an acrylic resin was used as a binder resin was compared with the red pixel pattern for a color filter obtained in Examples 1 to 6 in heat resistance and resistance. It is clear that the solvent properties are poor.

[0105]

[Table 1]

[0106] * The CF composition, representative of the color filter for the inkjet ink compositions of the present invention. All numbers in the table represent parts by mass. DPHA: dipentaerythritol hexaacrylate PETA: pentaerythritol triacrylate MIA250: poly (tetramethylene glycol) bis (maleimidoacetate) [average molecular weight of poly (tetramethylene glycol) 250] Irg # 369: Irgacure # 369

Example 7 Using a high-speed disperser “TSG-6H” (manufactured by Igarashi Kikai Co., Ltd.) charged with 0.5 mmφ zirconia beads, a carboxyl group-containing amino resin solution (A-1) prepared in Production Example 1 25.0 parts, C.I. I. Pigment Blue 1
8.0 of 5: 6, "Dispersic 1" as a dispersant
63 "and a dispersion composed of 64.5 parts of PGMAc are dispersed at a rotation speed of 2000 m- ¹ for 8 hours, and then filtered through a filter having a pore size of 1.0 [mu] m to obtain a thermosetting inkjet ink for a color filter. Composition (B-
1) was obtained.

25 g of the obtained thermosetting ink-jet ink composition for color filter (B-1) was transferred into a glass container, sealed, stored at 40 ° C. for 24 hours, and the storage stability was evaluated. As a result, the storage stability was good.

Next, the obtained thermosetting ink-jet ink composition for color filter (B-1) was applied on a glass substrate by using a piezo jet type head, and then preliminarily dried at 110 ° C. for 10 minutes. To form a blue pattern coating film. The obtained coating film pattern was cured in an oven at 200 ° C. for 30 minutes according to the thermal curing conditions. The obtained coating film pattern was subjected to after-baking at 230 ° C. for 15 minutes to obtain a blue pixel pattern for a color filter.

The thus obtained blue pixel pattern for a color filter was evaluated according to the performance test items.

As a result, the heat resistance-1 was ○, the heat resistance-2 was ○, the coating appearance after the heat test was good, and the solvent resistance -1 was −１,
The solvent resistance-2 was ○, and this pixel pattern was excellent in heat resistance and solvent resistance. Further, when the absorption spectrum and the thin film X-ray diffraction of the pixel pattern after the heat resistance test were measured, no change in the crystal type of the blue pigment and no increase in the particle diameter were observed.

Comparative Example 2 In Example 7, the amino resin solution (A-1) 25.0 was used.
Part, melamine resin [Super Beckamine J-820-60 manufactured by Dainippon Ink and Chemicals, Inc.]
(N-butanol / xylene solution)] In the same manner as in Example 7 except that 25.0 parts were used, a comparative inkjet ink composition for a thermosetting color filter (B-
2) was obtained.

In Comparative Example 2, the dispersibility of the blue pigment was poor, and when the piezo jet type head was discharged onto a glass substrate, the discharge performance was poor and the head was clogged. Therefore, the evaluation according to the performance test items was not performed.

From the above results, the thermosetting color filter of Comparative Example 2 using a melamine resin was compared with the ink-jet ink composition for a thermosetting color filter using the amino resin solution having a carboxyl group of Example 7. It is clear that the performance of the inkjet ink composition for filters is inferior.

Example 8 In Production Example 1, water and n-butanol were distilled off.
Followed by propylene glycol monomethyl ether acetate
2-butanone is added in place of
(Resin mass% after drying at 7.5 ° C. for 1 hour) is 40.0%
% Amino resin 2-butanone solution (A-1-1)
Was. 2-butanone solution of this amino resin (A-1-1)
And neutralized by adding aqueous ammonia,
Tanone was distilled off. Then add ion-exchanged water
Adjust so that the departure amount becomes 30.0%, and neutralize amino resin water
Solution (A-1-2) was obtained. 0.5mmφ zirconia
High-speed disperser “TSG-6H” loaded with beads (Igarashi
Using the above neutralized amino resin aqueous solution (A-
1-2) 33.0 parts, C.I. I. Pigment Blue 15:
8.0 of dispersant 16 as a dispersant
3 "2.5 parts, diethylene glycol 20.0 parts and b
2000 m of a dispersion composed of 40.0 parts of on-exchange water ^-1
The mixture was stirred at a rotational speed of 8 hours for 8 hours.
Filter with a filter
An ink jet ink composition (B-3) was obtained.

25 g of the obtained thermosetting ink-jet ink composition for color filter (B-3) was transferred into a glass container, sealed, stored at 40 ° C. for 24 hours, and the storage stability was evaluated. As a result, the storage stability was good.

Next, the thermosetting ink-jet ink composition for a color filter (B-3) was applied on a glass substrate having a hydrophobic black matrix and a hydrophilic ink-jet receiving layer formed thereon using a piezo jet type head. After forming the pixel pattern, it was pre-dried at 110 ° C. for 10 minutes to form a blue pattern. The resulting pattern was cured in an oven at 200 ° C. for 30 minutes. The obtained pattern was further after-baked at 230 ° C. for 15 minutes, and then subjected to a heat resistance test 1, a heat resistance test 2, a solvent resistance test 1, and a solvent resistance test 2.

As a result, the heat resistance test-1 was ○, the heat resistance test-2 was ○, the appearance of the coating film after the heat test was good, the solvent resistance test-1 was ○, and the solvent resistance test-2 was ○. A blue pattern for a color filter having excellent heat resistance and solvent resistance was obtained. Further, when the absorption spectrum and the thin film X-ray diffraction of the coating film after the heat resistance test were measured, no change in the crystal type of the blue pigment and no increase in the particle diameter were observed.

Comparative Example 3 In Example 8, a neutralized amino resin aqueous solution (A-1-
2) Neutralization of a nonvolatile content of 30.0% obtained by neutralizing in the same manner as in Example 8 using the acrylic resin (A-4) obtained in Production Example 4 instead of 33.0 parts Acrylic resin aqueous solution 3
A comparative thermosetting inkjet ink composition for color filters (B-4) was obtained in the same manner as in Example 8, except that 3.0 parts were used.

Next, in Example 8, a thermosetting ink-jet ink composition for a color filter (B-3)
Instead of using a thermosetting inkjet ink composition for a color filter (B-4) in the same manner as in Example 8, except that a hydrophobic black matrix and a hydrophilic inkjet receiving layer were formed on a glass substrate. After a cured pixel pattern was formed, a heat resistance test 1, a heat resistance test 2, a solvent resistance test 1 and a solvent resistance test 2 were performed.

As a result, the heat resistance test-1 was ×, the heat resistance test-2 was ×, the appearance of the coating film after the heat resistance test was fine corrugation, the solvent resistance test-1 was ○, and the solvent resistance test-2 was Poor, and a blue pattern for a color filter having poor heat resistance and solvent resistance was obtained. Further, when the absorption spectrum and the thin film X-ray diffraction of the pixel pattern after the heat resistance test were measured, it was recognized that the crystal type change of the blue pigment and the particle size of the blue pigment were increased.

The blue pixel pattern for a color filter of Comparative Example 3 using only an acrylic resin as a binder resin was compared with the blue pixel pattern for a color filter obtained in Example 8 in heat resistance and solvent resistance. It is clear that it is inferior.

[0123]

According to the present invention, heat resistance and solvent resistance,
In particular, a color filter having pixels with excellent heat resistance can be provided. In addition, by including a compound having a photopolymerizable functional group in the inkjet ink composition for a color filter of the present invention, a color filter having excellent photopolymerizability and high practicability can be provided.

────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] October 24, 2001 (2001.10.
24)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0021

[Correction method] Change

[Correction contents]

Amino resin obtained by the above method
(A) is obtained by etherification using an alcohol.
Ri, it can be stabilized.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0024

[Correction method] Change

[Correction contents]

Further, the etherified amino resin (a)
It may be prepared by methods conventionally known. That is, for example, (1) an amino compound is added to a solution obtained by adding an aldehyde compound to an alcohol for etherification, and if necessary, at a temperature of 50 to 140 ° C. for 20 minutes to 7 hours in the presence of an acidic catalyst. Reacting, simultaneously performing a condensation reaction and an etherification reaction,

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0073

[Correction method] Change

[Correction contents]

Production Example 2 [Preparation of amino resin having carboxyl group] In a four-necked flask equipped with a thermometer, a reflux condenser and a stirrer, 37.4 parts of benzoguanamine, 118.4 parts of a 50% aqueous glyoxylic acid solution, 88.8 parts of n-butanol was charged, and immersed in an oil bath heated to 115 ° C. with stirring. After 15 minutes, a homogeneous solution was obtained and reflux was started. After continuing the reaction for 1 hour, 5.33 × 10 ⁴ Pa
Water was distilled off under reduced pressure for 4 hours . Next, after distilling off water and n-butanol, PGMAc was added and cooled, and PGMAc was further added to adjust the nonvolatile content to 40.0%. An amino resin (A-2) having a carboxyl group and an acid value of the resin solid content of 136 mgKOH / g was obtained.
The number average molecular weight in terms of polystyrene; Mn was 1,624, and the degree of dispersion: Mw / Mn was 1.28.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) G02F 1/1335 505 B41J 3/04 101Y 101Z

Claims (8)

[Claims] 1. An ink jet ink composition for a color filter, comprising: (a) an amino resin having a carboxyl group and / or a phenolic hydroxyl group; and (b) a coloring material. (2) The amino resin having a carboxyl group and / or a phenolic hydroxyl group is (a-1) (4,
Condensation of 6-diamino-1,3,5-triazin-2-yl) benzoic acid with (a-2) at least one aldehyde compound selected from the group consisting of formaldehyde, glyoxylic acid, succin semialdehyde, and hydroxybenzaldehyde The ink-jet ink composition for a color filter according to claim 1, which is an amino resin obtained by the above method. 3. The method according to claim 1, wherein (a) the amino resin having a carboxyl group and / or a phenolic hydroxyl group is (a-3) melamine, benzoguanamine, or (4,6-diamino-1,3,3).
At least one triazine compound selected from the group consisting of (5-triazin-2-yl) benzoic acid;
4) The inkjet ink composition for a color filter according to claim 1, which is an amino resin obtained by condensing at least one aldehyde compound selected from the group consisting of glyoxylic acid, succin semialdehyde, and hydroxybenzaldehyde. 4. The ink jet ink composition for a color filter according to claim 1, further comprising (c) a compound having a photopolymerizable functional group. 5. A pixel portion is formed on a transparent substrate by an ink-jet recording method using (a) an amino resin having a carboxyl group and / or a phenolic hydroxyl group and (b) an ink-jet ink composition for a color filter containing a coloring material. A method for manufacturing a color filter, comprising curing the pixel portion after the formation. 6. The method for producing a color filter according to claim 5, wherein the pixel portion is thermally cured. 7. The method for producing a color filter according to claim 5, wherein the ink-jet ink composition for a color filter is a composition containing (c) a compound having a photopolymerizable functional group. 8. The method for producing a color filter according to claim 7, wherein the photocuring is performed after the pixel portion is photopolymerized.