JPH03149267A - Photopolymerizable photosensitive coating composition - Google Patents

Abstract

PURPOSE:To obtain the title composition having improve resolution and a low operating voltage by mixing a specified alkali-soluble acrylated resin with a photoinitiator, a reactive diluent monomer, a colorant, a dispersant and conductive ultramicroparticles. CONSTITUTION:An epoxy vinyl ester resin is reacted with a polybasic acid anhydride and an alkylketene dimer to obtain an alkali-soluble acrylated resin represented by the formula [where R1 is a polybasic acid anhydride group; m and n are such positive numbers that n+m=0.9-1.1, and n/(m+n)=0.1-0.4] and having a hydroxyl value <=10mgKOH/g and an acid value of 50-160mgKOH/ g. 100 pts.wt. obtained resin is mixed with 2-10 pts.wt. photoinitiator comprising selfcleaving (S) and hydrogen-cleaving (P) photoinitiators in an S/P ratio of 10/(1-10) by weight, 0.5-10wt.% reactive diluent monomer (e.g. N,N'- methylenebisacryl-amide), 10-200 pts.wt. colorant of a mean particle diameter <=0.4mum, 0.5-10wt.% dispersant (e.g. a nonionic surfactant of an HLB of 11-16) and 4-30wt.% conductive ultramicroparticles of a mean particle diameter <=0.4mum.

Description

[Detailed description of the invention] (Industrial application field) The present invention relates to a photopolymerizable photosensitive coating composition.

More specifically, the present invention relates to a photopolymerizable photosensitive coating composition useful for producing color filters used in various multicolor displays such as color liquid crystal displays and color facsimiles, and optical equipment.

(Prior Art) Conventionally, color filters formed on glass substrates have been widely used in color display devices such as liquid crystal display devices. Color display devices use the GH method, which uses a dichroic dye mixed with the liquid crystal material, the ECB method, which uses the birefringence of the liquid crystal material, and the optical shutter method, which uses color filters for the three primary colors of red, green, and blue. . Among these, the optical shutter method using color filters is practical and preferable.

Such a color filter is produced by a method such as a printing method, an electrodeposition method, or a dyeing method. The printing method allows direct patterning and is advantageous in terms of cost. but,
Due to the bleeding of printing ink, an image with clear boundaries cannot be obtained, and a color image with a fine pattern cannot be obtained. Furthermore, it is difficult to accurately align the three color filter patterns during printing, resulting in drawbacks such as parts of the images overlapping.

In the electrodeposition method, since the shape of the color filter is determined by the shape of the transparent electrode, it is difficult to form a color filter with a complicated shape, for example, a mosaic shape. Furthermore, when the pattern of transparent electrodes becomes finer and more dense, a new problem arises in that short circuits and disconnections between adjacent transparent electrodes rapidly increase.

An improved method of this electrodeposition method was disclosed in Japanese Patent Application Laid-Open No. 61-11703.
It is disclosed in the publication No. In the method disclosed in this publication, first, a transparent electrode formed on the entire surface of a transparent substrate is coated with a resist material. Next, patterning of the resist material is performed, and furthermore, electrodeposition coating is performed.

Such coating with resist material, patterning, and electrodeposition coating are repeated three times to form a color filter. This method has the disadvantage that the process is very complicated. Further, in the electrodeposition method, since the electrodeposition coating film has insulating properties, electrodeposition is preferentially performed on thin portions of the electrodeposition film. Therefore, there is an advantage that a uniform coating film can be obtained.

However, since color filters are made of insulating materials,
When used in a display device, a voltage drop occurs in the color filter layer.

This voltage drop has the drawback that voltage cannot be effectively applied to the liquid crystal layer.

In the dyeing method, a coating film made of a natural polymer such as gelatin or a synthetic polymer such as acrylic resin that has been imparted with photosensitivity is prepared, and only the necessary portions of each coating film are colored with a dye.

Therefore, it is necessary to apply resist dyeing treatment to parts that do not need to be colored, which has the drawback of complicating the process.

(Problems to be Solved by the Invention) Color filters produced by conventional printing methods, electrodeposition methods, and dyeing methods have problems such as low resolution, high operating voltage, or complicated manufacturing process. There are problems. In order to eliminate these drawbacks, photosensitive paints in which colorants are mixed with photosensitive resists have been developed.

If this photosensitive paint is used, the exposed portion of the paint film will directly form a color filter. However, since this photosensitive paint contains an azide compound and a photopolymerizable compound as a photosensitive compound, it cannot be used in the presence of oxygen.
(: The curing reaction does not proceed. Therefore, it is necessary to form an oxygen barrier film before exposure and to peel off the oxygen barrier film before development, which has the disadvantage of complicating the process.

The present invention solves these problems, and an object of the present invention is to provide a photopolymerizable photosensitive coating composition that can form a color filter with high resolution and low operating voltage without using an oxygen barrier film. The goal is to provide the following.

(Means for Solving the Problems) The photopolymerizable photosensitive coating composition of the present invention is an alkali-soluble acrylated resin represented by the following general formula (!H, 1H, where R1 is polybasic acid anhydride. Represents a chemical residue.m and n are n+m=O-9~1,1, and n/n+
m = 0. It is a positive number satisfying 1 to 0.4.

), a photoinitiator, a reactive diluent monomer, a colorant,
It contains a dispersant and conductive ultrafine particles, thereby achieving the above object.

The alkali-soluble acrylated resin used in the composition of the present invention has the structural unit shown in the above formula, and includes (a) an epoxy vinyl ester resin, (b) a polybasic acid anhydride, and (C
) alkyl ketene dimer. The epoxy vinyl ester-fu resin (a) is obtained by reacting a Talesol novolac type epoxy resin with an unsaturated basic acid.

The cresol-tuborafuku type epoxy resin used to obtain the epoxy vinyl ester resin (a) is a resin obtained by reacting a cresol-tuborafuku resin with epichlorohydrin or methylepichlorohydrin. Cresol tubola resin is obtained by reacting cresol and formaldehyde in the presence of an acid catalyst. This cresol tubefuku type epoxy resin has a molecular weight of about 180 to 250
It is preferable to have an epoxy equivalent weight in the range of , and it is preferable that the main component is a novolac deca-nuclear body.

Specific examples of Talesol novolac type epoxy resins include Araldite ECN-1299 (manufactured by Ciba Geigy), Quatex 3710 (manufactured by DuPont),
Examples include Sumiepoxy ECSN-220 (manufactured by Sumitomo Chemical Co., Ltd.), EPO-) YDCN-220H (manufactured by Tobu Kasei Co., Ltd.), and the like. Incidentally, as the cresol novolac type epoxy resin, one in which phenol, bisphenol A, etc. are used in combination with cresol to the extent that properties such as heat resistance are not impaired may be used.

Examples of unsaturated basic acids to be reacted with the cresol-tuborafuku type epoxy resin include acrylic acid, methacrylic acid,
Examples include crotonic acid and cinnamic acid, among which acrylic acid is preferred.

The epoxy vinyl ester resin (a) is obtained by reacting a cresol novolac type epoxy resin and an unsaturated basic acid in the presence of an esterification catalyst. It is preferable to use the unsaturated basic acid in an amount of 0.95 to 1.05 equivalents based on the epoxy equivalent of the cresol novolac type epoxy resin. Among these, those in which all epoxy groups have reacted with an unsaturated basic acid are preferred.

Examples of the polybasic acid anhydride (b) include maleic anhydride, succinic anhydride, itaconic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and endomethylenetetrahydrophthalic anhydride. , dibasic acid anhydrides such as methylendomethylenetetrahydrophthalic anhydride, chlorendic anhydride, methyltetrahydrophthalic anhydride, aromatic polyvalent carboxylic acid anhydrides such as trimellitic anhydride, pyromellitic anhydride, etc. can be exemplified. Among these, hexahydrophthalic anhydride, succinic anhydride and the like are preferred.

The alkyl ketene dimer (C) has the general formula (I) R-CH
=C-CH-R + 1 (I) O-C=O (In formula (1), R is a hydrogen atom or CHH2n+r, and n represents an integer of 1 to 4). Specific examples of i include diketene, methyl ketene dimer, ethyl ketene dimer, propyl ketene dimer, butyl ketene dimer, and the like. Among these, diketene is preferred.

The polybasic acid anhydride (b) is an epoxy vinyl ester resin (
lO- is used to introduce a carboxyl group into a). By introducing a carboxyl group, it is possible to impart alkaline developability to the epoxy vinyl ester resin (a). The alkyl ketene dimer (C) is used to introduce an alkyl ketoester group into the epoxy vinyl ester resin (a). By introducing an alkylketoester group, the adhesion of the epoxy vinyl ester resin <a> can be improved. It is still unclear why the alkylketoester group improves adhesion. In addition, polybasic acid anhydride (b) and alkyl ketene dimer (e) are combined with epoxy vinyl ester resin (
By reacting with the hydroxyl group in a), the resulting alkali-soluble acrylated resin has substantially no hydroxyl group. If the alkali-soluble acrylated resin does not have hydroxyl groups,
The resin may also be moisture resistant.

Polybasic acid anhydride (b) and alkyl ketene dimer (C
) The usage amount and usage ratio cannot be determined in general, but must be determined taking into account the above-mentioned circumstances. Specifically, good results can be obtained within the ranges shown below. That is, for 1 equivalent of hydroxyl group in epoxy vinyl ester 1 [i (a), m equivalents of polybasic acid anhydride (b), alkyl ketene dimer (C)
If we use n equivalents, m+n=o, 9~l
1°, preferably in the range of 0.95 to 1.05, and n
/ (m+n)=O-1~0.4, preferably 0°2~
Good results can be obtained if used within the range of 0.4.

The value of m10m is 0. When it is smaller than 9, the moisture resistance decreases due to residual hydroxyl groups, and voids are generated in the coating film during baking after exposure. On the other hand, if the value of m + n is larger than 1.1, not only will there be no improvement in performance (but the solvent resistance will deteriorate. If the value of n/(m + n) is smaller than 0.1, , sufficient adhesion cannot be obtained.n/(m+n
) is larger than 0.4, there is a tendency for alkali developability to deteriorate.

The alkali-soluble acrylated resin used in the photopolymerizable photosensitive coating composition of the present invention can be obtained under the following reaction conditions. First, the polybasic acid anhydride (b) is added to a system consisting of an epoxy vinyl ester resin (a), a polymerization inhibitor, an esterification catalyst, and a solvent, and a reaction is carried out. As mentioned above, the epoxy vinyl ester resin is obtained by reacting a Talesol novolak type epoxy resin with a basic acid. Examples of the polymerization inhibitor include hydroquinone, methoxylone, acetophenone, and the like. As an esterification catalyst,
Various known ones such as dimethylbenzylamine, triethylamine, triphenyl phosphate, and imidazole can be mentioned. The reaction temperature is 50 to 100°C and the reaction time is 1 to 8 hours. Furthermore, a solvent was added to this reaction mixture, an alkyl ketene dimer (C) was added, and the mixture was heated at 40 to 90°C.
By reacting for 2 to 8 hours, an alkali-soluble acrylated resin is obtained. In addition, the above reaction method is an example for obtaining an alkali-soluble acrylated resin,
It is not limited to this. Any method can be used as long as the desired alkali-soluble acrylated resin can be obtained.

The hydroxyl value of the alkali-soluble acrylated resin obtained as described above is preferably in the range of 1 (IngKOH/g or less), more preferably in the range of 5 mg KOH/g or less. 10mgKO
If it is larger than H/g, moisture resistance tends to be poor. Furthermore, the acid value of the alkali-soluble acrylated resin of the present invention is
It is preferably in the range of 50 to 160 ■KOH/g.

When the acid value is less than 50 mgKOH/g, alkali developability deteriorates, and when it is more than 160, coating film properties such as alkali resistance of the cured film tend to deteriorate.

The photoinitiator used in the photopolymerizable photosensitive coating composition of the present invention is a photopolymerization initiator, and includes a self-cleavage type (S) type and a hydrogen abstraction type (P) type. Self-cleavage type (S)
Examples of photopolymerization initiators include acetophenone, benzoin ether, and ketal initiators. In the present invention, acetophenones are particularly preferred, such as 2-methyl-[4-(methylthio)phenyl]-2-morpholino-1-propanone, 2. 2-dialkoxyacetophenone, 2-hydroxy-2-methylpropiophenone,
Examples include pt-butyltrichloroacetophenone and pt-butyldichloroacetophenone. Examples of the hydrogen abstraction type (P) photopolymerization initiator include thioxanthone type, benzyl type, benzophenone type, and anthraquinone type. In the present invention, thioxanthone series are particularly preferred, such as 2,4-dialkylthioxanthone, 2-
chlorothioxanthone, 2-alkylthioxanthone,
2-alkylanthraquinone, 2,2-dichloro-4-
Examples include phenoxyacetophenone.

The ratio of the self-cleavage type (S) and hydrogen abstraction type CP) photoinitiators is (S)/(P) = 10/1 to 10/1 by weight.
A range of 0 is suitable. In the range where the value of (-S)/(P) exceeds 10/1, that is, in the range where the content ratio of self-cleavable type (S) is large, the absorption wavelength range is on the short wavelength side, so the absorption by colorants, etc. This results in insufficient photocuring. If the value of (S)/(P) is less than lO710, curing will be insufficient, so either add a tertiary amine as a sensitizer and photocure, or form a bar coat film and store in an inert gas. Light curing is required. When a tertiary amine is added and photocured, there is a problem in that the formed film turns yellow. When a bar coat film is formed and photocured in an inert gas, a problem arises in that the number of steps increases.

In the photopolymerizable photosensitive coating composition of the present invention, the photoinitiator is preferably contained in an amount of 2 to 10 parts by weight based on 100 parts by weight of the alkali-soluble acrylated resin. 2
If it is less than 1 part by weight, curing will be insufficient and resolution and solvent resistance will deteriorate. If the amount exceeds 10 parts by weight, the volumetric shrinkage of the coating film during curing will be large, resulting in the formation of minute racks on the coating film surface, which is not preferable.

The reactive diluent monomer used in the composition of the present invention contains at least one polyfunctional monomer selected from the group consisting of water-soluble polyfunctional monomers and water-insoluble polyfunctional monomers. As the water-soluble polyfunctional monomer, N,
N"-methylenebisacrylamide, N,N"-dimethylacrylamide-1 load, N, N\dimethylaminopropylacrylamide, N,N-dimethylaminoethyl acrylate, polyethylene glycol diacrylate, N,
N”-dimethylaminoethyl methacrylate.

etc. Examples of water-insoluble polyfunctional monomers include triethylene glycol diacrylate, ethylene glycol diacrylate, dipropylene glycol diacrylate, polypropylene glycol diacrylate, tripropylene glycol diacrylate, glycerin diglycidyl ether diacrylate, and glycerin diglycidyl ether triacrylate. , pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, and methacrylates corresponding to these.

The reactive diluent monomer is preferably contained in an amount of 0.5 to 10% by weight based on the total weight of the photopolymerizable coating composition. When the amount is less than 0.5% by weight, the resulting photopolymerizable photosensitive coating composition has a high viscosity, and a uniform coating film cannot be formed. Furthermore, the cured film obtained does not have sufficient crosslink density and may have poor solvent resistance and chemical resistance. If the amount exceeds 10% by weight, the resulting cured film has sufficient crosslink density, but tends to become brittle, which is not preferable.

The conductive ultrafine particles used in the composition of the present invention are added in order to impart conductivity to the obtained cured film while maintaining its transparency. Examples of materials for the conductive ultrafine particles include oxide semiconductors such as tin oxide, indium oxide, antimony oxide, zinc oxide, and domium oxide, and chemically stable metals such as gold, silver, and nickel. These ultrafine particles preferably have an average particle diameter of 0.4 μm or less, which is the lower limit of visible light, so as not to impair the transparency of the coating film. It is more preferable that the average particle diameter of the ultrafine particles be 0.2 to 0.3 μm or less, since practical transparency can be maintained. Further, the ultrafine particles blended into the composition of the present invention need to be dispersed in the composition in order to maintain transparency.

The above-mentioned conductive ultrafine particles are contained in a proportion of 4 to 30% by weight, preferably 10 to 25% by weight of the total solid content contained in the photopolymerizable photosensitive coating composition of the present invention. If it is less than 4% by weight, the electrical conductivity of the resulting coating film will decrease. If the amount exceeds 30% by weight, the adhesion of the coating film decreases, which is not preferable.

The dispersant used in the composition of the present invention is added to disperse the conductive ultrafine particles and the colorant. Preferred dispersants are nonionic surfactants with an HLB in the range of 11-16.

The HLB is calculated using the Griffin formula (M, C, Griffin J, Soc, Cosme) based on the weight fraction of the parent xylem.
t, Chemists 5249 (1954>). If a nonionic surfactant with an HLB of less than 11 is used, the conductive ultrafine particles and the colorant will not be dispersed. If a nonionic surfactant with an HLB of more than 16 is used, the resulting photopolymerizable photosensitive coating composition tends to foam, which is not preferred. Specific examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene octyl ether, polyoxyethylene phenol ether,
Examples include polyoxyethylene nonylphenol ether, polyoxyethylene monolaurate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monostearate, and polyoxyethylene styrene ether. In the composition of the present invention, at least one of these nonionic surfactants is used.

The amount of nonionic surfactant added is preferably 0.5 to 10% by weight based on the total solid content of the resulting photopolymerizable coating composition. If the amount added is less than 0.5% by weight, the dispersion effect on the conductive ultrafine particles and the colorant will be reduced, which is not preferable. If the amount added exceeds 10% by weight, a large amount of decomposition gas will be generated due to heat at high temperatures, resulting in a decrease in heat resistance, which is not preferable.

The coloring agent used in the composition of the present invention is used to color a coating film for a color filter.

Pigments or dyes can be used as colorants. Pigments that can be used include organic and inorganic pigments. Examples of organic pigments include azo lake pigments, insoluble azo pigments, phthalocyanine pigments, -quinacridone pigments, dioxazine pigments, isoindolinone pigments, perinone pigments, anthraquinone pigments, perylene pigments, and mixtures thereof. Examples of inorganic pigments include mirolipur, iron oxide, cobalt-based, manganese-based, ultramarine blue, navy blue, cobalt blue, cerulean blue, viridian, emerald green, cobalt green, and mixtures thereof. As a dye,
Oil-soluble dyes or dispersible dyes are suitable.

In order to color the coating film while maintaining its transparency, the colorant is preferably dispersed to a particle size of 0.4 μm or less, which is the lower limit of the wavelength of visible light, and preferably 0.2 to 0. .3μm
It is practically preferable to have the following average particle diameter. The amount of the colorant added is generally preferably in the range of 10 to 200 parts by weight per 100 parts by weight of the alkali-soluble acrylated resin. , if the amount added is less than 10 overlapping parts, desired spectral characteristics cannot be obtained. Addition amounts exceeding 200 parts by weight are not preferable because the adhesion of the coating film decreases.

A solvent may be added to the composition of the present invention if necessary. Examples of solvents that can be blended include methyl ethyl ketone,
Ketones such as cyclohexanone, aromatic hydrocarbons such as toluene and xylene, cellosolves, cellosolves such as butyl cellosolve, carpitol, carpitols such as butyl carpitol, ethyl acetate, butyl acetate, cellosolve acetate, butyl cellosolve acetate, carpitol acetate , acetic esters such as ethoxypyropylacetate, and N-methyl-2-pyrrolidone.

The photopolymerizable photosensitive coating composition of the present invention includes a leveling agent that improves the smoothness of the coating film and an antifoaming agent that suppresses foam generation during stirring, within a range that does not impair the desired properties of the composition. etc,
Any additives may be added.

The photopolymerizable photosensitive coating composition of the present invention can be produced in the following manner. Alkali-soluble acrylic resin, reactive diluent monomer, colorant, conductive ultrafine particles and dispersant,
Stir and mix the solvent as necessary. Next, a photoinitiator is added and stirred and mixed again to obtain a desired photopolymerizable photosensitive coating composition.

An example of a method for producing a color filter using the photopolymerizable photosensitive coating composition of the present invention is shown in FIGS. 1 to 4. first,
On the glass substrate 2 which becomes the medium on which the color filter is formed,
A photopolymerizable photosensitive coating composition 1 containing a coloring agent of any one of red, green, and blue is applied over the entire surface using a spinner or a roll coater (FIG. 1). Preliminary firing may be performed at this stage if necessary. Next, the photomask 3 with a desired pattern formed thereon is fixed at a predetermined position above the substrate 2. Light 4 is irradiated onto the photomask 3 to cure the coating film of the photopolymerizable photosensitive coating composition 1 in the portion not covered with the photomask 3 (FIG. 2). Next, the unexposed portions of the photopolymerizable photosensitive coating composition 1 are washed. The exposed portion of the coating film is fixed on the substrate 2 by baking at a predetermined temperature if necessary. As a result, the first color filter 5 is formed (FIG. 3). Next, using a photopolymerizable photosensitive coating composition containing a colorant of one of the remaining two colors, a second color filter is formed adjacent to the first color filter 5 by the same process as described above. form 6. Furthermore, a third color filter is formed in the same manner using the photopolymerizable photosensitive coating composition containing the remaining one coloring agent,
A color filter consisting of three primary colors is obtained (Figure 4).
.

(Function) In the photopolymerizable photosensitive coating composition of the present invention, the crosslinking reaction proceeds even in the presence of oxygen, so a color filter having high resolution can be produced with a simple process. Since the color filter produced using the photopolymerizable photosensitive coating composition of the present invention has conductivity, when this color filter is used in a display device using liquid crystal or the like, the liquid crystal layer can be driven at a low voltage.

(Example) The invention will now be described with reference to examples.

Raw materials for photopolymerizable photosensitive coating compositions prepared in Examples and Comparative Examples of the present invention are shown below.

(2) Alkali-soluble acrylated resin Alkali-soluble acrylated resins 1 to 6 prepared by the method described below were used.

■Photoinitiator self-cleavage type (S): Acetophenone type, Irgacure 9
07 (manufactured by Nippon Ciba Geigy Co., Ltd.) Hydrogen extraction type (P): Thioxanthone type, Kayacure D
ETX (manufactured by Nippon Kayaku Co., Ltd.) ■Reactive dilution monomer dipentaerythritol hexaacrylate ■Coloring agent HI MICRON BLUE (manufactured by Mikuni Shiki Co., Ltd.) H
I MICRON GREEN (same as above) HI M
ICRON RED (same as above) Note that each average particle diameter is 0.13 μm.

■ Conductive ultrafine particle tin oxide: T-1-A Average particle size 0-4μm (manufactured by Mitsubishi Metals) Tin oxide: T-1-B Average particle size 1, 0μm (manufactured by Mitsubishi Metals) Silver: Ultrafine particle average Particle size 0.4 μm (manufactured by Shinku Yakiniku Co., Ltd.) ■Dispersant Adekanol NK-15HLB=15 (manufactured by Asahi Denka Kogyo Co., Ltd.) Sunofon 40 HLB=17 (manufactured by Kao Atlas Co., Ltd.) Neugen E T Fu 90 HL B = 19
(Manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.) The photopolymerizable photosensitive coating compositions prepared in the Examples and Comparative Examples of the present Examples and the evaluation method of the cured films thereof are shown below.

<a> Volume resistivity A37M Conforms to D257.

(b) Resolution A photopolymerizable photosensitive coating composition was applied and exposed using a stripe and mosaic array of photomasks having the widths shown below. It was evaluated based on the quality of the product. That is, among the stripe widths from which a sharp pattern was obtained, the smallest value was taken as the evaluation value.

Strive width: 128.80.40.20.1 O, 8
, 5 μm (C) Finger tack The photo-cured coating film was touched with a finger at 25°C, and 5 μm was measured according to the criteria shown below.
A graded evaluation was performed.

5... No tackiness at all 4... Slight tackiness, but no finger marks left on the paint film 3... Slight finger marks left on the paint film 2... Paint Clear finger marks left on the film l...The coating composition adheres to the fingers (d) Transmittance Color Micro Analyzer MCPD manufactured by Otsuka Electronics Co., Ltd.
Measured at -1000.

(e) Adhesion Conforms to JIS D-0202. Cross-cut the paint film and make scratches so that the paint film is divided into IOXIO squares. The squares were peeled off with cellophane tape, and evaluated by visually counting the parts of the squares from which the coating film did not peel off.

(f) After mixing and stirring the dispersible photopolymerizable photosensitive coating composition, leave it to stand for 7 days,
The separation status of the pigment and resin was evaluated based on the following criteria.

O: No separation X: Separation (g) Coating film voids The presence or absence of voids in the coating film was evaluated using an optical microscope (100x magnification).

(h) Solvent Resistance After being immersed in methylene chloride at 25° C. for 1 hour, evaluation was performed on a 5-grade scale based on the criteria shown below.

5...No change at all 4...Slightly swollen areas are visible 3...Swelling areas are clearly visible 2...Swelling and peeling is seen partially 2-Fu 1...Full surface Peeling (1) Microcracks in the coating film The presence or absence of microcracks in the coating film was evaluated using an optical microscope (100x magnification).

<Preparation of alkali-soluble acrylated resin solution> Thermometer,
In a 1000+51 three-day flask equipped with a stirrer and a condenser, add hydroxyl M value 225 KOH/g.

Acid value 1.4mgKOH/gs Oxirane oxygen content 0.
996 g of a 251% by weight solution of 13% 0-cresol novolak epoxy acrylate in cellosolve acetate
(1 gram equivalent of hydroxyl value) was added. Furthermore, 0.3 g of hydroquinone monomethyl ether, 4.0 g of dimethylbenzylamine, 74 g of cellosolve acetate, 116 g (0.75 mol) of hexahydrofuric acid were added, and the reaction mixture was reacted at 95° C. for 2 hours. 54 g of selonlubu acetate was added.

The acid value of this reaction mixture was 72.0 mgKOH/g.

The hydroxyl value is 25.6 @ K OH/g, and 0-
It was confirmed that 74% of the hydroxyl value of the cresol novolak epoxy acrylate was esterified.

The temperature of this reaction mixture was maintained at 50°C, and 22 g of diketene was added.
(0.26 mol) was added. After maintaining this temperature for 30 minutes, the humidity was raised to 80°C. After maintaining this temperature for 1.5 hours, the acid value was 70.0 KOH/g and the hydroxyl value was 1.
9 ■ KOH/g alkali-soluble acrylated resin solution l
I got it.

Alkali-soluble acrylated resin solution 6 was prepared under conditions other than those described above. Table 1 shows the preparation conditions and characteristic values of the alkali-soluble acrylated resin solution.

(The following is a blank space) <Examples 1 to 11> The components shown in Table 2 were added to a stirring vessel, and the components were stirred and dispersed to prepare photopolymerizable photosensitive coating compositions of Examples 1 to 11. Next, the compositions of Examples 1 to 11 were uniformly coated to a thickness of about 2 μm on each of the 11 ITO substrates that had been subjected to predetermined patterning using a roll coater. This was preliminarily baked at 80° C. for 10 minutes, and exposed for 60 seconds using an exposure machine using a predetermined mask pattern. After exposure, 1
It was developed with a wt% Na2C0a aqueous solution.

(The following is a blank space) Table 3 shows the evaluation results of the compositions of Examples 1 to 11 and the cured coating films obtained as described above.

As shown in Table 3, in all examples, well-cured coatings were obtained without using an inert gas or force bar coating film, and without using a sensitizer. It was done. The obtained cured film had excellent resolution, adhesion, and solvent resistance, low volume resistivity, and low operating voltage when used in a display device. Furthermore, the coating film had no voids or microcracks, and was highly practical.

(The following is a blank space) S <Comparative Examples 1 to 14> Compositions of Comparative Examples 1 to 14 were prepared with the compositions shown in Table 4. The compositions of Comparative Examples 1 to 14 were combined with the compositions of Examples 1 to 14 described above.
In the same manner as in No. 11, each was applied onto an ITO substrate, and exposed and developed.

Table 5 shows the evaluation results of the compositions of Comparative Examples 1 to 14 and the cured films exposed and developed using the compositions.

In the coating films prepared using the compositions of Comparative Examples 3 to 6, curing failure occurred, and tackiness to the touch and decrease in adhesion were observed.

The coating films prepared using the compositions of Comparative Examples 1.2.9.11 and 14 had poor adhesion. In the coating film prepared using the composition of Comparative Example 7.8, minute cracks occur. The coating film of the composition of Comparative Example 1O has a high volume resistivity value.

In addition, the transmittance of the coating film of Comparative Example 12 was low, and the coating film of Comparative Example 13
The dispersibility of the coating film was extremely poor.

(Leaving space below) 3 Low - Brown II"" - To ♀II = 1 1-11 Town: Akira 3 yen, 111 River 113 bar 0 bar 0 bar 8 yen (Effect of the invention) Photopolymerizable photosensitive paint of the present invention In the composition, the crosslinking reaction proceeds even in the presence of oxygen, so a color filter with high resolution can be produced through a simple process. Further, since the color filter produced using the composition of the present invention has conductivity, when used in a display device using liquid crystal or the like, it can be driven at a low voltage.

Furthermore, the photopolymerizable photosensitive coating composition of the present invention can be applied to color filters for various multicolor displays and optical instruments.

Figures 1 to 4 are process diagrams showing a method for manufacturing a color filter.

DESCRIPTION OF SYMBOLS 1... Photopolymerizable photosensitive coating composition, 2... Glass substrate, 3... Photomask, 4... Light, 5... First color filter, 6... Second color Filter, 7.
-・Third color filter.

that's all

Claims (1)

[Claims] 1. Alkali-soluble acrylic resin represented by the following general formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_1 is a polybasic acid Represents anhydride residues. m and n
is n+m=0.9 to 1.1, and n/(n+
m) is a positive number satisfying 0.1 to 0.4. ), a photoinitiator, a reactive diluent monomer, a colorant, a dispersant, and conductive ultrafine particles. 2. The photoinitiator is a photopolymerization initiator, and is a self-cleavable type (
S) and hydrogen abstraction type (P) photopolymerization initiator, (S)/
(P) is contained in a weight ratio of 10/1 to 10/10, and is contained in a proportion of 2 to 10 parts by weight based on 100 parts by weight of the alkali-soluble acrylated resin. A photopolymerizable photosensitive coating composition. 3. The reactive diluent monomer contains at least one polyfunctional monomer selected from the group consisting of a water-soluble polyfunctional monomer and a water-insoluble polyfunctional monomer, and the photopolymerizable photosensitive coating composition 0.5-1 based on total weight
The photopolymerizable photosensitive coating composition according to claim 1, which accounts for 0% by weight. 4. The conductive ultrafine particles have an average particle diameter of 0.4 μm or less, and account for 4 to 30% by weight of the total solid content of the photopolymerizable photosensitive coating composition. The photopolymerizable photosensitive coating composition described above. 5. The photopolymerizable photosensitive coating composition according to claim 1, wherein the dispersant contains at least one nonionic surfactant having an HLB in the range of about 11 to about 16.