JP2002318309A - Coloring resin composition for color filter substrate, method for manufacturing color filter substrate and color filter substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a coloring resin composition for manufacturing a color filter substrate with improved water and moisture resistance and excellent color characteristics. SOLUTION: A water soluble vinyl type resin is a copolymer composed of at least a vinyl type monomer (A) expressed by the general formula (I), a vinyl type monomer with a carboxyl group (B) and a vinyl type monomer with a hydroxyl group (C). Ink for the color filter substrate is characterized by having a weight ratio of the monomer A to the monomer B to be A:B=1:0.8-8, a weight ratio of the monomer A to the monomer C to be A:C=1:0.8-10 and the total sum of three components, i.e., the monomers A, B, C, is equal to or more than 80 wt.% in the water soluble vinyl type resin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored resin composition for a color filter substrate for producing a color filter substrate by an ink jet recording technique, and more particularly, to a color filter substrate having a colored pixel having water resistance by heat treatment. The present invention relates to a colored resin composition. In addition, the present invention relates to a color filter substrate of a color liquid crystal display used in a color television, a personal computer, a pachinko game board, and the like, and in particular, using an ink jet recording technique, a plurality of colored pixels are formed by using such a composition. The present invention relates to a formed color filter substrate. Further, the present invention relates to a liquid crystal display device having a color filter substrate manufactured by using an inkjet recording technique.

[0002]

2. Description of the Related Art Conventionally, as a color filter substrate,
A mordant layer made of a hydrophilic polymer such as gelatin, casein, glue or polyvinyl alcohol is provided on a substrate,
A dyeing method color filter substrate in which the mordant layer forms a colored pixel with a dye, a dispersion color filter substrate in which a colored pixel is formed by a photolithography method using a colored resin in which a colored pigment is dispersed in a transparent resin, and the like. It has been known. Such a dyeing method has a complicated process of performing an anti-dyeing treatment for each color, has drawbacks in terms of productivity, product yield, and the like, and is disadvantageous in terms of cost. In addition, the dispersion method is disadvantageous in terms of cost due to low utilization efficiency when applying an expensive colored resin for each color onto a substrate by spin coating.

[0003]

On the other hand, conventionally, an ink jet system has been used in order to meet the demand for a color filter substrate which can be manufactured at a low cost from the device side by increasing the efficiency of using a coloring material in a simple process. The color filter substrate was disclosed in JP-A-59-75205,
JP-A-63-235901 or JP-A-Hei1-2
17320 and the like.

[0004] However, a colored resin composition for drawing using an ink jet recording technique is generally composed of a water-soluble material. As a result, the colored resin composition has high solubility in water, and a color filter substrate having a colored pixel formed by such a colored resin composition has not obtained a color filter substrate having sufficiently satisfactory water resistance and moisture resistance. . An object of the present invention is to solve the above-mentioned problems of the conventional example, to improve a color filter substrate by an ink-jet method that can be formed in a simple process, to improve water resistance and moisture resistance, and to improve color characteristics of a color filter substrate. It is to provide a colored resin composition which can be used for producing a colored resin composition. Another object of the present invention is to provide an inexpensive color filter substrate from which a color device having excellent characteristics can be obtained.

[0005]

The above object is achieved by the present invention described below. That is, the present invention relates to a colored resin composition for a color filter substrate (hereinafter, also simply referred to as “ink”) produced by an inkjet method comprising at least a water-soluble vinyl resin, a coloring material, and water. Are at least a vinyl monomer represented by the following general formula (I) (hereinafter also simply referred to as "monomer A") and a vinyl monomer having a carboxyl group (hereinafter simply referred to as "monomer B") ) And a vinyl monomer having a hydroxyl group (hereinafter also simply referred to as “monomer C”), wherein the weight ratio of the monomer A to the monomer B is A: B
= 1: 0.8-8, the weight ratio of monomer A and monomer C is A: C = 1: 0.8-10, and monomers A and B
And C, wherein the total of the three components is 80% by weight or more in the water-soluble vinyl resin. [Wherein, R represents H or CH ₃ , X represents a single bond or a structure represented by the following formula (II) or (III),
Represents a single bond or a structure represented by the following formulas (IV) to (VI), and Ar represents an aromatic group. ]

Further, the present invention provides the above-mentioned ink, wherein the proportion of the monomer A in the water-soluble vinyl resin is 5% by weight to 30% by weight: The ratio of the vinyl monomer (B) is 20
The above-mentioned ink which is 50% by weight to 50% by weight; the above-mentioned ink wherein the carboxyl group contained in the above-mentioned water-soluble vinyl resin is neutralized with ammonia; the monomer occupying in the above-mentioned water-soluble vinyl resin The above-mentioned ink in which the ratio of C is 20% by weight to 60% by weight; the weight-average molecular weight of the water-soluble vinyl resin is 1,000 to 300 in terms of polystyrene.
The above ink having a viscosity of 30 mPa · s or less; and having a surface tension of 20 mN / m or more.
An ink as above is provided which is 55 mN / m.

Further, the present invention provides a step of applying the ink to a concave portion of a color pixel forming surface of a color filter substrate having a concave portion in a light transmitting portion by an ink-jet method, and a step of curing the applied ink by heat treatment. A method of manufacturing a color filter substrate, comprising: a color filter substrate manufactured by the method; and a liquid crystal display device having the color filter substrate.

[0008]

Next, the present invention will be described in more detail with reference to preferred embodiments. In the present invention, the ink contains at least a water-soluble vinyl resin, a coloring material and water, and the water-soluble vinyl resin is a copolymer comprising at least a monomer A, a monomer B, and a monomer C. is there.

At least monomer A, monomer B and monomer C
Examples of the water-soluble vinyl resin which is a copolymer of the following include copolymer resins such as a water-soluble vinyl resin, an acrylic resin, a methacryl resin, and derivatives thereof. Such a resin can be obtained by copolymerizing at least the monomer A, the monomer B, and the monomer C.

The monomers A include, for example, styrene, α-methylstyrene, divinylbenzene, 2-phenoxyethyl (meth) acrylate, benzyl (meth) acrylate, triethoxyphenol (meth) acrylate,
-Hydroxy-3-phenoxypropyl (meth) acrylate, N-benzyl (meth) acrylamide and the like. These monomers A are contained in a water-soluble vinyl resin
It is desirable that the content be contained in an amount of 30 to 30% by weight. If the content is less than this, the water resistance of the colored pixels obtained by heating and curing the ink cannot be sufficiently ensured. If the content exceeds this, the solubility of the water-soluble vinyl resin in water is significantly reduced.

The monomer B includes acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and anhydrides thereof. Further, the monomer C is 2-
Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like can be mentioned. Since these monomers B and C have a water-soluble residue and cause a cross-linking reaction upon heating, they can be suitably used for converting a water-soluble vinyl resin into a thermosetting resin.

The proportion of the monomer B in the water-soluble vinyl resin is preferably 20% by weight to 50% by weight. If it is less than this, the ink is not sufficiently crosslinked by heating,
Water resistance of the formed colored pixels is not sufficiently ensured. On the other hand, if it exceeds this, the water-soluble vinyl resin is easily hydrolyzed by the alkali solution, and the alkali resistance of the colored pixel becomes insufficient.

In order to increase the solubility of the water-soluble vinyl resin in water, all or a part of the carboxyl groups contained in the resin may be neutralized with a compound showing alkalinity in the solution. Examples of the compound exhibiting alkalinity in a solution include hydroxides and ammonia of alkali metals such as sodium hydroxide and potassium hydroxide, and quaternary ammonium compounds such as tetramethylammonium hydroxide. And amine compounds such as 2-methyl-1-propanol and 2-dimethylaminoethanol. In particular, when ammonia is used, the water resistance of the colored pixels formed by heating the ink can be further improved.

The proportion of the monomer C in the water-soluble vinyl resin is preferably from 20% by weight to 60% by weight. If it is less than this, the solubility of the water-soluble vinyl resin in water decreases and the viscosity of the ink increases. If it exceeds this, the water resistance of the colored pixels obtained by heating and curing the ink cannot be sufficiently secured.

The weight ratio of monomer A to monomer B in the water-soluble vinyl resin is preferably A: B = 1: 0.8 to 8
It is. If the ratio of the monomer B to the monomer A is less than this, the water resistance of the colored pixel obtained by heat-curing the ink decreases. The solution is not sufficiently resistant.

The weight ratio of monomer A to monomer C in the water-soluble vinyl resin is preferably A: C = 1: 0.8.
10 to 10. If the ratio of the monomer C to the monomer A is less than this, the solubility of the water-soluble vinyl resin in water decreases, and if it exceeds this, the water resistance of the ink after heat curing is not sufficiently ensured. The total of the three components of the monomers A, B and C is preferably 8% of the copolymer resin obtained.
0% by weight or more. If it is less than this, the water resistance of the formed colored pixel is not sufficiently ensured.

The monomers A, B, and C may be copolymerized with a vinyl monomer other than these to form a water-soluble vinyl resin. Other vinyl monomers that can be used here may be any as long as they have a vinyl group, for example, acrylonitrile, allylamine, vinylamine,
Vinyl monomers such as vinyl acetate and vinyl propionate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, glycidyl (meth) acrylate, lauryl ( Monofunctional (meth) such as meth) acrylate, stearyl (meth) acrylate, cyclohexyl (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate
Acrylate, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate,
Water-soluble (meth) acrylic esters such as methoxypolyethylene glycol (meth) acrylate and morpholine (meth) acrylate, (meth) acrylamide, N
-(Meth) acrylamide compounds such as methylol (meth) acrylamide, N- (3- (dimethylamino) propyl) (meth) acrylamide, diacetone (meth) acrylamide, ethylene glycol di (meth) acrylate, 1,4- Butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipenta Erythritol hydroxypenta (meta)
Examples include polyfunctional (meth) acrylates such as acrylates, and oligomers such as (meth) acrylate oligomers and urethane acrylate oligomers.

The water-soluble vinyl resin is prepared as follows. The monomers A, B and C and, if necessary, other vinyl compounds are dissolved in a solvent such as 2-propanol, methyl ethyl ketone, dimethylformamide or the like, and α, α′-azobisisobutyronitrile or the like is dissolved. And the polymerization is carried out by heating while stirring.
A solvent having low solubility of the water-soluble vinyl resin produced by polymerization, such as hexane or toluene, is added to the solution after the polymerization to precipitate the water-soluble vinyl resin, and the precipitate is dried by vacuum drying or the like to remove excess water. By removing the solvent, a desired resin can be obtained.

The molecular weight of the copolymer resin produced at this time is as follows:
1000 to 30 in weight average molecular weight in terms of polystyrene
About 000 is good. If it is less than this, the ink cannot form a film by heating, and if it exceeds this, the ink cannot be ejected by the ink jet method.

As the coloring material used in the present invention, both dyes and pigments are used. As the dye, C.I. I. Acid red 118, C.I. I. Acid Red 254, C.I. I. Acid Green 25, C.I.
I. Acid blue 113, C.I. I. Acid Blue 1
85, C.I. I. Pigments such as Acid Blue 7
C. I. Pigment Red 177, C.I. I. Pigment Red 5, C.I. I. Pigment Red 12, C.I. I. Pigment Green 36, C.I. I. Pigment Blue 20
9, C.I. I. Pigment Blue 16 and the like,
Of course, it is not limited to these. These dyes and pigments are preferably used at a ratio of about 0.1 to 30% by weight in the ink.

The ink is prepared by dissolving or dispersing the water-soluble vinyl resin and the coloring material in water by a known method. As the water, it is preferable to use ion-exchanged water (deionized water) instead of general water containing various ions. In addition, a water-soluble solvent can be used if necessary. The water-soluble solvent may be any as long as it can be dissolved in water. Amides such as dimethylformamide and dimethylacetamide; ketones or ketoalcohols such as acetone and diacetone alcohol; ethers such as tetrahydrofuran and dioxane; polyalkylene glycols such as polyethylene glycol and polypropylene glycol. Ethylene glycol, propylene glycol, butylene glycol, triethylene glycol,
1,2,6-hexanetriol, thiodiglycol,
Alkylene glycols having an alkylene group containing 2 to 6 carbon atoms, such as hexylene glycol and diethylene glycol; glycerin; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Lower alkyl ethers of polyhydric alcohols such as monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, and triethylene glycol monobutyl ether; N-methyl-2-pyrrolidone;
2-pyrrolidone, 1,3-dimethyl-2-imidazoline and the like. Among these many water-soluble organic solvents, polyhydric alcohols such as diethylene glycol and lower alkyl ethers such as triethylene glycol monomethyl ether are preferred.

Further, in order to obtain the stability of the ink ejection from the ejection head of the ink jet recording apparatus, a lower alkyl ether such as ethanol, isopropyl alcohol, or polyhydric alcohol is added to the ink. This is presumably because in the case of the jet (registered trademark) type, the ink can be discharged more stably by foaming the ink on the thin film resistor in the ink jet discharge head.

Further, in addition to the above components, a surfactant, an antifoaming agent, a preservative, and the like may be added to the ink according to the present invention, if necessary, to obtain a solution having desired physical properties. it can. For example, any surfactant can be used as long as it does not adversely affect the storage stability of the ink, such as fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, and alkyl. There are anionic surfactants such as allyl sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, polyoxyethylene sorbitan alkyl esters, acetylene alcohol, and nonionic surfactants such as acetylene glycol. One or more of these can be appropriately selected and used.

Next, a color filter substrate produced using such an ink will be described. FIG. 1 is a cross-sectional view of a color filter substrate showing one example of the present embodiment. A black matrix 2 provided in a grid on a translucent substrate 1 such as a glass substrate, a plastic substrate, and a film.
There is a colored pixel 3 formed by heating and curing the ink in the opening of the black matrix. In addition, a protective layer 4 is provided on the upper part as necessary, and a transparent electrode layer 5 is formed on the upper part. Such a color filter substrate can be manufactured as follows.

(A) Black Matrix Forming Step First, a black matrix 2 is formed on a translucent substrate 1. As a result, the pixel recess 6 for applying the above-described ink is formed in the opening of the black matrix 2. The black matrix forming material can be formed by a general photolithography method using a black pigment resist. At this time, the thickness of the black pigment resist is 0.1.
It is desirable that the thickness be 5 μm or more. If it is less than 0.5 μm, the optical density as a black matrix will be low and the black matrix will not function sufficiently. In addition, when the above-described ink is applied, the ink may overflow from the pixel recesses 6 and mix adjacent compositions of different colors.

(B) Colored Pixel Forming Step Next, R, G, and B inks 7 are ejected from the ink jet nozzles 9 of the ink jet recording apparatus 8 toward the substrate so as to fill the pixel recesses 6, and each color pixel pattern is formed. To form Further, it is preferable that the ink is applied on the black matrix 2 in a range where the respective color inks are not mixed. In addition, as the ink jet system used in the present invention,
As the energy generating element, a bubble jet type using an electrothermal converter or a piezo jet type using a piezoelectric element can be used, and the discharge area and the discharge pattern can be set arbitrarily.

The ejected ink 7 is cured by heat treatment to form a colored pixel 3. In the present invention, in order to sufficiently develop heat resistance and solvent resistance, heat treatment in a post-process, and a color filter substrate that can withstand the solvent,
It is desirable to heat-treat at a temperature of 150 ° C. or higher.

(C) Protective Film Forming Step A protective film 4 is formed on the colored pixels 3 as required. As the protective film 4, a resin material curable by light irradiation or heat treatment, or both of them, or an inorganic film formed by vapor deposition or sputtering can be used. However, any material can be used as long as it can withstand the subsequent transparent electrode forming process, alignment film forming process, and the like.

As the resin material of the protective film, for example,
Acrylic resin, epoxy resin, polyimide resin and the like are preferably used, but not limited thereto. In addition, as a method of applying these resin materials, methods such as spin coating, roll coating, bar coating, spray coating, and dip coating can be preferably used, but are not limited thereto.

(D) Transparent electrode layer forming step Subsequently, the transparent electrode layer 5 is formed. As a material for forming the transparent electrode layer 5, a metal oxide such as indium tin oxide, zinc oxide, or titanium oxide when a color filter substrate is used can be suitably used. In addition, as a forming method, a known film forming method such as a sputtering method or an evaporation method can be used. A color filter substrate can be manufactured as described above.

[0031]

The present invention will be described more specifically below with reference to examples and comparative examples. (Example 1) A water-soluble vinyl resin having the following composition was prepared. At this time, the weight ratio between the vinyl monomers is as follows. Weight ratio between vinyl monomers : styrene: methacrylic acid = 1: 2.66 styrene: 2-hydroxyethyl acrylate = 1: 3

According to the above composition, each vinyl monomer was dissolved in dimethylformamide, and 3 g of α, α'-azobisisobutyronitrile was added to prepare a reaction solution. The reaction was heated under reflux at 60 ° C. for 1 hour. After heating, hexane was added to the reaction solution to obtain a white precipitate. The precipitate was dried under vacuum to remove the solvent and obtain a powdery resin. When the infrared spectrum of this powdery resin was measured, it was confirmed that the resin was a styrene, methacrylic acid and 2-hydroxyethyl acrylate copolymer. When the molecular weight of this resin was measured by gel filtration chromatography (GPC), the weight average molecular weight of this resin was 3,500 in terms of polystyrene.

The ink was obtained by dissolving the copolymer and the coloring material in water. The composition of the ink is as follows. Composition of ink 10 g of copolymer 10 g of dye R, G, B) 80 g of 1% by weight aqueous ammonia

The R (red) dye is CIDirect Red 2
40, CIAcidGreen 12 was used for G (green) dye, and CIDirect Blue 273 was used for B (blue) dye. The viscosity and surface tension of these inks are as shown in Table 1 below. here,
The viscosity was measured with an R115 type viscometer (manufactured by Toki Sangyo Co., Ltd.), and the surface tension was measured at 25 ° C. with an automatic surface tensiometer CBVP-Z (manufactured by Kyowa Interface Chemical Co., Ltd.).

[0035]

These inks were ejected onto a glass substrate for 10 minutes using an ink jet printer, but no clogging occurred in 36 nozzles for each color, and the ejection property was extremely good. Further, the glass substrate from which the ink was discharged was heated at 230 ° C. for 30 minutes to form a colored layer.

This substrate was immersed in pure water and a 5% by weight aqueous sodium hydroxide solution for 30 minutes to evaluate water resistance and alkali resistance. For the evaluation of water resistance and alkali resistance, the spectral transmittance of the colored layer was measured before and after immersion, and the color difference ΔE ^* ab of the color system L ^* a ^* b ^* specified by the CIE was evaluated. At this time, the smaller the ΔE ^* ab value, the smaller the change in transmittance before and after immersion, indicating higher water resistance and alkali resistance. The results are as shown in Table 2 below.

[0038] From the above, it was found that the color difference after the water resistance and alkali resistance test was extremely small, and a colored layer having extremely excellent water resistance and alkali resistance was formed.

(Examples 2 to 11) In the following examples, evaluations were made for each of the vinyl monomers used and the case where their composition ratios were different. The vinyl monomers constituting the resin used in each example and the composition ratio thereof are as shown in Table 3 below.

[0040]

In the table, BZMA indicates benzyl methacrylate and TEMPMA indicates triethoxyphenyl methacrylate. MMA indicates methyl methacrylate. 2-
HEA converts 2-hydroxyethyl acrylate to 2-
HEMA converts 2-hydroxyethyl methacrylate to
2-HPMA indicates 2-hydroxypropyl methacrylate.

Table 4 below shows the molecular weight of the water-soluble vinyl resin, the viscosity of the ink, and the surface tension in each example.

Table 5 below shows the discharge properties of the inks in each example by an ink jet printer and the results of water resistance and alkali resistance tests of the colored layers prepared by heat-treating the ink discharged on a glass substrate at 230 ° C. for 30 minutes. Is shown. The experimental method followed Example 1.

[0044]

In the column of dischargeability, ◎ indicates extremely good (0 to 2 nozzle clogging in 36 nozzles), and 、 indicates good (3 to 7 nozzle clogging in 36 nozzles). As described above,
It was found that the inks used in these examples had excellent ejection properties, and that the colored layer formed by the heat treatment had excellent water resistance and alkali resistance.

(Embodiment 12) In this embodiment, the case where the water-soluble vinyl resin of Example 1 is used and a pigment is used as a coloring material will be described. At this time, R pigment is Pigment Red 177, G
Pigment Green 36 was used for the pigment, Pigment Blue 15: 6 was used for the B pigment, and the composition of the ink was the same as in Example 1. Table 6 below
The viscosity and surface tension of the ink, the dischargeability of the ink jet printer and the ink discharged on the glass substrate
The results of the water resistance and alkali resistance tests of the colored layers produced by heat treatment at 0 ° C. for 30 minutes are shown.

[0047] In addition, the evaluation of the ejection property was performed in the same manner as in Examples 2 to 11. As described above, even when a pigment was used as a coloring material, it was found that the ink was excellent in ejection properties, and the colored layer formed by the heat treatment was extremely excellent in water resistance and alkali resistance.

(Example 13) In this example, the case where the carboxyl group contained in the water-soluble vinyl resin is neutralized with sodium hydroxide will be described. Example 1 was repeated except that the alkali compound used for neutralization was changed from ammonia to sodium hydroxide. However, in order to make the degree of neutralization with respect to the water-soluble vinyl resin equal, the concentration of the aqueous sodium hydroxide solution was 2.3% by weight.

Table 7 below shows the viscosity and surface tension of the ink, the dischargeability of the ink jet printer, and the water resistance and alkali resistance test of the colored layer prepared by heat-treating the ink discharged on a glass substrate at 230 ° C. for 30 minutes. The result is shown.

[0050] The evaluation of the ejection property was performed in the same manner as in Examples 2 to 11. As described above, even if the alkali compound used for neutralization is changed to other than ammonia, the ink has excellent ejection properties,
It was found that the water resistance and alkali resistance of the colored layer formed by the heat treatment were good.

(Embodiments 14 to 19) In the following embodiments,
When the viscosity and surface tension of the ink are changed by changing the molecular weight or changing the resin content of the ink using a water-soluble vinyl resin having the same composition ratio as in Example 1. Is described. Table 8 below shows the differences between Example 1 and Example 1 and the viscosity and surface tension of the ink. In the case where the resin content is changed, the dye content is also changed in order to keep the weight ratio between the dye and the resin in the ink constant.

[0052]

Table 9 below shows the discharge properties of the ink in each example by an ink jet printer and the results of the water resistance and alkali resistance tests of the colored layer prepared by heat-treating the ink discharged on a glass substrate at 230 ° C. for 30 minutes. Show.

The evaluation of the dischargeability was performed in the same manner as in Examples 2 to 11. As described above, even when the molecular weight is changed in the range of the present embodiment or the resin content of the ink is changed to change the viscosity and surface tension of the ink, the ink has good ejection properties and is formed by heat treatment. The water resistance and alkali resistance of the colored layer to be obtained were found to be good.

(Embodiment 20) In this embodiment, a case where a color filter substrate is manufactured using the ink described in Embodiment 1 will be described. The color filter substrate was manufactured as follows. A black resist (trade name: CK-S171X, manufactured by Fuji Film Ohlin) was applied on a glass substrate (1737, manufactured by Corning) by spin coating, and a black matrix 2 was formed by a photolithography method. This black matrix has an opening of 70 μm ×
The thickness was 220 μm and the film thickness was 2 μm.

Each color of the ink described in Example 1 was applied to the opening using an ink jet recording apparatus. FIG. 3 shows the colored pixel pattern at this time. Pixels adjacent to the opening of the black matrix 2 in the short side direction have colors of R, G,
Each ink was applied such that the same color was lined up in the order of B and adjacent colored pixels in the long side direction of the opening.
After the ink is ejected, 100 minutes at 100 ° C and 1 minute at 200 ° C
The solid content in the ink was cured by performing heat treatment for a long time to form a colored pixel 3.

Subsequently, a protective film was formed on the colored pixels. The protective film is a two-component type thermosetting resin (SS-6500)
(JSR Co., Ltd.) by spin coating, and then
It was formed by performing heat treatment for a long time and curing. The film thickness after the heat treatment was 1 μm. A transparent electrode was formed on the protective film. The transparent electrode was formed by sputtering a mixture of indium oxide and tin oxide on the protective film. The thickness of the transparent electrode layer was 100 nm.

The color filter substrate thus produced had extremely excellent color characteristics. The results of the water resistance and alkali resistance tests for each color of the color filter substrate are as shown in the table below.

[0059] As described above, a color filter substrate having extremely excellent water resistance and alkali resistance was produced.

(Comparative Examples 1 to 8) Comparative examples with respect to the above embodiment will be described below. Table 11 below shows the composition ratio of each vinyl monomer of the water-soluble vinyl resin used in the comparative example.

[0061] Table 12 below shows the viscosity and surface tension of inks prepared by using the water-soluble vinyl resin of each comparative example and the same dye as in Example 1 and changing only the resin and using other components at the same composition ratio.

[0062]

Table 13 below shows the discharge properties of the inks in the ink jet printers in Comparative Examples and the results of the water resistance and alkali resistance tests of the colored layers prepared by heat-treating the ink discharged on the glass substrate at 230 ° C. for 30 minutes. Show.

[0064]

The discharge performance was evaluated in the same manner as in Examples 2 to 11.
Bad), × is bad (nozzle clogging out of 36 nozzles 19 or more)
Represents As described above, the ink of this comparative example has either a large number of nozzles that cause nozzle clogging of the ink jet printer in the ejection property test or a large ΔE ^* ab value in the water resistance and alkali resistance test of the colored layer formed by the heat treatment. Was. From this, it was found that the ink of this comparative example had at least either poor ejection property or poor water resistance and alkali resistance of the colored layer formed by the heat treatment.

[0066]

According to the ink of the present invention, a colored pixel formed by heat treatment while using a water-soluble resin is excellent in water resistance and alkali resistance. In addition, a color filter substrate having excellent alkali resistance can be obtained.

When a color filter substrate is prepared using the ink of the present invention, a color filter substrate having excellent water resistance and alkali resistance can be formed by an ink-jet method.
It becomes possible to manufacture with high productivity.

[Brief description of the drawings]

FIG. 1 is a schematic cross-sectional view showing one embodiment of a color filter substrate of the present invention.

FIG. 2 is a schematic cross-sectional view showing steps of one embodiment of a method for manufacturing a color filter substrate of the present invention.

FIG. 3 is a schematic view showing one embodiment of a color pixel pattern of the color filter substrate of the present invention.

[Explanation of symbols]

 1: Translucent substrate 2: Black matrix 3: Colored pixel 4: Protective film 5: Transparent electrode layer 6: Depressed portion for pixel 7: Ink 8: Ink jet recording device 9: Ink jet nozzle

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 101/14 C08L 101/14 C09D 11/00 C09D 11/00 F term (Reference) 2H048 BA57 BA64 BB02 BB44 4J002 BC071 BC091 BG011 BG041 BG051 BG071 BG121 BH001 DE027 FD096 FD207 GP00 HA04 4J039 AD02 AD03 AD09 AD10 AD12 AD13 AD14 GA24 4J100 AB02R AB03R AB16R AJ02Q AJ08Q AJ09Q AK02QBA31 BA03 BA08 BA08 AL08A JA32

Claims (11)

[Claims] 1. A colored resin composition for a color filter substrate produced by an ink-jet method comprising at least a water-soluble vinyl resin, a coloring material and water, wherein the water-soluble vinyl resin has at least the following general formula (I): And a vinyl monomer (B) having a carboxyl group and a vinyl monomer (C) having a hydroxyl group. A weight ratio of the vinyl monomer (A) to the vinyl monomer having a carboxyl group (B) is A: B = 1: 0.8 to 8, and the vinyl monomer (A) and the hydroxyl When the weight ratio with the vinyl monomer (C) having a group is A: C = 1: 0.
8 to 10, wherein the total of the three components A, B and C is at least 80% by weight in the water-soluble vinyl-based resin. [Wherein, R represents H or CH ₃ , X represents a single bond or a structure represented by the following formula (II) or (III),
Represents a single bond or a structure represented by the following formulas (IV) to (VI), and Ar represents an aromatic group. ] 2. The proportion of the vinyl monomer represented by the general formula (I) in the water-soluble vinyl resin is from 5% by weight to 5% by weight.
The colored resin composition for a color filter substrate according to claim 1, which is 30% by weight. 3. The coloring for a color filter substrate according to claim 1, wherein the proportion of the vinyl monomer having a carboxyl group (B) in the water-soluble vinyl resin is 20% by weight to 50% by weight. Resin composition. 4. The colored resin composition for a color filter substrate according to claim 3, wherein a carboxyl group contained in the water-soluble vinyl resin is neutralized with ammonia. 5. The water-soluble vinyl resin according to claim 1, wherein the proportion of the vinyl monomer (C) having a hydroxyl group in the water-soluble vinyl resin is 20% by weight to 60% by weight. A colored resin composition for a color filter substrate. 6. The colored resin composition for a color filter substrate according to claim 1, wherein the water-soluble vinyl resin has a weight average molecular weight of 1,000 to 30,000 in terms of polystyrene. 7. The colored resin composition for a color filter substrate according to claim 1, which has a viscosity of 30 mPa · s or less. 8. The surface tension is from 20 mN / m to 55 mN / m
The colored resin composition for a color filter substrate according to any one of claims 1 to 7, wherein m is m. 9. A step of applying the colored resin composition according to any one of claims 1 to 8 to a concave portion on a color pixel forming surface of a color filter substrate having a concave portion in a light transmitting portion by an inkjet method. Curing the applied colored resin composition by heat treatment. 10. A color filter substrate manufactured by the method according to claim 9. 11. A liquid crystal display device comprising the color filter substrate according to claim 10.