JPH08201611A - Color-filter resist - Google Patents

Abstract

PURPOSE: To improve the transparency, solvent resistance and adhesion to a substrate of the color-filter resist consisting of a coloring material, photopolymerization composition containing photopolymerization initiator and ethylenic compd. CONSTITUTION: An ethylenic unsaturated compd. having 2 double bonds obtained by the addition reaction between an aromatic polyglycidyl ether compd. and an unsaturated monocarboxylic acid or the addition reaction between an aromatic polyhydroxy compd. and an epoxy-monocarboxylic ester is used as the ethylenic compd. This ethylenic compd. is effective in improving the adhesion in development and effectively prevents the missing of a picture. A high-quality color filter is easily formed at a low cost in this way.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color filter resist used for manufacturing optical color filters used in color televisions, liquid crystal display devices, cameras and the like.

[0002]

2. Description of the Related Art A color filter is usually a 10 to 50 .mu.m wide stripe pattern or a mosaic pattern on the surface of a transparent substrate such as glass or plastic sheet provided with a black matrix, which has three different hues of red, green and blue. It is manufactured by forming color patterns such as shapes with an accuracy of several μm.

Typical color filter manufacturing methods include a dyeing method, a printing method, a pigment dispersion method and an electrodeposition method.
However, these methods have poor heat resistance, poor pattern positioning accuracy, high production cost, poor productivity, etc.
Both have advantages and disadvantages, and each method is used properly according to the application. Among these production methods, a photopolymerizable composition containing a color material is applied onto a transparent substrate provided with a black matrix, and a pigment that forms a color filter image by repeating image exposure, development and heat curing treatment. The dispersion method has been widely used in the past because it has high accuracy in the position of the color filter pixel, film thickness, etc., has a long life, and has few defects such as pinholes.

However, in this method, since a pigment having a lower coloring power than that of a dye is used, it is necessary to add a large amount of pigment. However, addition of a large amount of pigment is liable to cause deterioration of development of the photopolymerizable composition. On the other hand, when the addition amount is small, it is necessary to increase the film thickness, and it is difficult to increase the transparency of the color material pixel.

There is also a problem that the cost of forming a black matrix such as chromium provided on the transparent substrate is high. As a solution to this problem, there has been proposed a method of forming a black matrix on a transparent substrate by using a photopolymerizable composition containing a black material (Japanese Patent Laid-Open No. HEI-1).
-293306, JP-A-2-902, etc.).

[0006]

However, in the black matrix using the photopolymerizable composition containing such a black material, the light-shielding property is not sufficient and the film thickness is 1.5 μm or more. When a red, blue, and green color material image is formed, the peripheral portion of the color material image is raised by 1 μm or more, which is a drawback that a smooth color filter cannot be manufactured.

The present invention has been made in view of the above conventional circumstances, and its first purpose is suitable for producing a color filter having excellent transparency, solvent resistance, and adhesion to a substrate. To provide a color filter resist.

A second object of the present invention is to provide a color filter resist for a black matrix which has a low manufacturing cost, is excellent in light-shielding property, is excellent in solvent resistance and is excellent in adhesiveness to a substrate.

[0009]

A color filter resist according to claim 1, wherein the color filter resist comprises a photopolymerizable composition containing a color material, a photopolymerization initiation system and an ethylenic compound, the aromatic compound is an ethylenic compound. A compound having two or more ethylenically unsaturated double bonds obtained by an addition reaction of an aromatic polyhydroxy compound with an epoxy monocarboxylic acid ester, or an addition reaction of an aromatic polyhydroxy compound with an unsaturated monocarboxylic acid It is characterized by including.

The color filter resist according to claim 2 is
The color filter resist according to claim 1,
The aromatic polyglycidyl ether compound is a co-condensate of bisphenol A and epichlorohydrin.

The color filter resist of claim 3 is
The color filter resist according to claim 1 or 2, further comprising, as an ethylenic compound, two or more ethylenically unsaturated double bonds obtained by an addition reaction of an aliphatic polyhydroxy compound and an unsaturated monocarboxylic acid. It is characterized by containing a compound.

The color filter resist according to claim 4 is
The color filter resist according to any one of claims 1 to 3, wherein the photopolymerizable composition excluding the color material is applied to a transparent substrate so as to have a dry film thickness of 2 µm, dried, and exposed to an appropriate exposure amount. When the whole surface is exposed and immersed in propylene glycol monomethyl ether acetate at 25 ° C. for 5 minutes, the elution rate is 50% by weight or less.

The color filter resist according to claim 5 is
The color filter resist according to any one of claims 1 to 4, wherein the photopolymerizable composition contains a copolymer to which 2 to 50 mol% of epoxy (meth) acrylate is added.

The color filter resist according to claim 6 is
The color filter resist according to claim 5,
The copolymer is characterized by using a monomer containing 10 to 80 mol% of phenyl groups.

A color filter resist for producing a black matrix according to claim 7 is the color filter resist according to any one of claims 1 to 6, wherein the photopolymerizable composition contains a black material and the dry film thickness is 1 μm. The coating film formed below has a minimum absorbance of 2.0 or more in the range of 400 to 700 nm.

The color filter resist for producing a red, green or blue color material pixel according to claim 8 is the color filter resist according to any one of claims 1 to 6, wherein
The photopolymerizable composition contains a red, green or blue material, and the maximum absorbance in the range of 400 to 700 nm of the coating film formed to have a dry film thickness of 1 μm or less is 1.1 or more.

That is, the inventors of the present invention have conducted extensive studies in order to achieve the above object, and as a result, the use of a photopolymerizable composition containing a specific ethylenic compound results in sensitivity, developability and solvent resistance. The inventors have found that the adhesiveness is improved and arrived at the present invention.

The present invention will be described in detail below.

The color filter resist of the present invention comprises a color material, a photopolymerization initiation system that absorbs light to generate radicals, and an addition-polymerizable ethylenically unsaturated double bond in which polymerization is induced by the radicals. A compound having at least two or more (hereinafter, referred to as “ethylenic compound”), and more preferably as a binder for improving compatibility, film-forming property, developability, adhesiveness and the like. A photopolymerizable composition containing an organic polymer substance.

Among these components, as the photopolymerization initiation system, those having the sensitivity in the ultraviolet to visible region as described below can be appropriately selected according to the exposure light source used.

That is, in the present invention, the photopolymerization initiation system for absorbing the ultraviolet light having a wavelength of less than 400 nm to generate radicals is, for example, Fine Chemical, 1991.
, March 1, Vol. 20, No. 4, P. 16-P. 26
Dialkyl acetophenone type, benzyl dialkyl ketal type, benzoin, benzoin alkyl ether type, thioxanthone derivative, acylphosphine oxide type, etc.
Hexaarylbiimidazole type, s-trihalomethyltriazine type, described in JP-B-45-37377.
The titanocene compounds described in JP-A-59-152396 can be used.

On the other hand, examples of the photopolymerization initiation system sensitive to visible light having a wavelength of 400 nm or more and 500 nm or less include, for example, a system of hexaarylbiimidazole, a radical generator and a dye (Japanese Examined Patent Publication No. 45-37377), and hexaarylbiimidazole. System of imidazole and (p-dialkylaminobenzylidene) ketone (JP-A-47-2528 and JP-A-54)
No. 155292), a system of a cyclic cis-α-dicarbonyl compound and a dye (JP-A-48-84183), a system of substituted triazine and a merocyanine dye (JP-A-54-151024), and ketocoumarin. Activator system (JP-A-52-112681, JP-A-58-155)
03, JP-A-60-88005), a system of substituted triazine and a sensitizer (JP-A-58-29803, JP-A-58-40302), biimidazole, a styrene derivative, and a thiol. System (JP-A-59-56403), a sensitizer containing a dialkylaminophenyl group and biimidazole (JP-A-2-69, JP-A-57-1).
68088, JP-A-5-107761, and JP-A-5-10761.
No. 210240, JP-A-4-288818),
System of organic peroxide and dye (JP-A-59-140203)
No. 59, JP-A-59-189340), and titanocene (JP-A-59-152396, JP-A-61-151).
197, JP-A-63-10602, JP-A-63-4
1484, JP-A-2-291, JP-A3-1240
3, JP-A-3-20293, JP-A-3-27393.
JP-A-3-52050), a system in which a titanocene and a xanthene dye and an addition-polymerizable ethylenic saturated double bond-containing compound having an amino group or a urethane group are combined (JP-A-4-221958, JP Kaihei 4-219
No. 756).

Suitable examples of the photopolymerization initiation system sensitive to light having a wavelength of 400 nm or more and 500 nm or less include wavelengths of 400 to 400 nm.
A sensitizing dye having absorption at 500 nm, 2,2′-bis (o-chlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole (hereinafter referred to as “compound R-1”), 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetra (p-carboethoxyphenyl) biimidazole (hereinafter referred to as "compound R-2"), 2,2'-bis (o-chlorophenyl) -4,
4 ', 5,5'-tetra (p-bromophenyl) biimidazole, 2,2'-bis (o-chlorophenyl)-
Hexaarylbiimidazoles such as 4,4 ′, 5,5′-tetra (o, p-dichlorophenyl) biimidazole, and organic thiols such as 2-mercaptobenzthiazole, 2-mercaptobenzoxazole and 2-mercaptobenzimidazole A compound photopolymerization initiator composed of a compound, or a sensitizing dye having absorption at a wavelength of 400 to 500 nm and dicyclopentadienyl-Ti-bis-2,
6-difluoro-3- (pyrrol-1-yl) -phenyl-1-yl, dicyclopentadienyl-Ti-bis-
2,3,5,6-tetrafluorophenyl-1-yl (hereinafter referred to as "compound S-1"), di-cyclopentadienyl-Ti-bis-2,3,4,5,6- Examples thereof include a titanocene compound such as pentafluorophenyl-1-yl, and a composite photopolymerization initiator including a dialkylaminophenyl compound such as ethyl p-diethylaminobenzoate and Michler's ketone.

Examples of the above-mentioned dyes that sensitize hexabiimidazole include, for example, JP-A-2-69, JP-A-57-168088, and JP-A-5-107761.
Japanese Patent Application Laid-Open No. 5-210240, Japanese Patent Application No. 4-2
The sensitizing dyes described in No. 88818 can be mentioned.

Examples of dyes that sensitize titanocene include Japanese Patent Application Nos. 5-83588 and 5-848.
17, JP-A-5-83587, Japanese Patent Application No. 6-12
949, Japanese Patent Application No. 6-74743, Japanese Patent Application No. 6-141
The sensitizing dyes described in No. 588 can be mentioned.

Of these photopolymerization initiation systems sensitive to the visible light region, they have absorption in the ultraviolet as well as visible light,
Those exhibiting high sensitivity may be used as a photopolymerization initiation system for a light source in the ultraviolet region.

Examples of compounds having high sensitivity in both the visible light region and the ultraviolet light region include a photopolymerization initiation system containing hexaarylbiimidazole or titanocene.

Among the above-mentioned photopolymerization initiation systems, a photopolymerization initiation system containing hexaarylbiimidazole and titanocene is preferable because it exhibits high sensitivity. Compared with the photopolymerization initiation system containing arylbiimidazole, it shows high sensitivity even in a small amount and is stable even under high drying conditions, and is therefore more preferable for a color filter resist having a high color material concentration as in the present invention. .

The ethylenic compound used in the present invention is
An addition reaction between an aromatic polyglycidyl ether compound and an unsaturated monocarboxylic acid, or an addition reaction between an aromatic polyhydroxy compound and an epoxy monocarboxylic acid ester,
The ethylenic compound (A) having two or more ethylenically unsaturated double bonds obtained in 1. is an addition reaction of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid together with the ethylenic compound (A) (ester It is preferable to use the ethylenic compound (B) containing two or more ethylenically unsaturated double bonds obtained in the reaction) together.

The ethylenic compound (A) is for improving the adhesiveness to a transparent substrate, especially the adhesiveness at the time of development (developed image adhesiveness), and physical irritation with a brush, spray or sponge. On the other hand, it fulfills the function of preventing image loss.

Specific examples of the ethylenic compound (A) include polyhydroxybenzenes such as hydroquinone, resorcin, and pyrogallol, and bisphenol A derivatives such as bisphenol A, polybisphenol A, brominated bisphenol A, and polybrominated bisphenol A. , An aromatic polyhydroxy compound such as novolac and an aromatic polyglycidyl ether compound obtained by addition reaction of epichlorohydrin under alkaline conditions, and an unsaturated monocarboxylic acid such as (meth) acrylic acid using a quaternary ammonium salt as a catalyst. Or an ethylenic compound obtained by the addition reaction of polyhydroxybenzene such as hydroquinone, resorcinol, pyrogallol, bisphenol A, polybisphenol A, brominated bisphenol A, polybrominated vinyl A bisphenol A derivative such as phenol A, an aromatic polyhydroxy compound such as novolac and glycidyl (meth) acrylate, and an epoxy (meth) acrylate having a structure such as the following [T-1] or [T-2] are added to "SYNTHETIC COMMUNICATION, 24 (21) "3099-3019
(1994) and the like, there may be mentioned ethylenic compounds obtained by addition reaction using an acid or alkali catalyst, and more specifically, for example, the following [M-1], [M
-2], [M-3], [M-4], and the like.

[0032]

Embedded image

[0033]

Embedded image

Particularly, it is preferable to use an ethylenic compound (A) of a copolycondensation type of bisphenol A and epichlorohydrin because it has excellent developed image adhesiveness as compared with other ethylenic compounds.

Particularly preferred ethylenic compound (A)
As for the viscosity at 25 ° C is 100 cps or more, further 25
The viscosity at 1000C is 1000 cps or more. If this viscosity is significantly lower than 100 cps, the developed image adhesion will deteriorate.

On the other hand, the ethylenic compound (B) has the function of enhancing the solubility of the non-image area during development and forming a high quality image. Specific examples of the ethylenic compound (B) include ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate , (Meth) acrylic acid esters such as dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, glycerol (meth) acrylate, etc., and itaconic acid esters obtained by replacing the (meth) acrylate of these exemplified compounds with itaconate. , Crotonic acid ester in place of crotonate or maleic acid ester in place of maleate. Among these, especially four functional
Hexafunctional dipentaerythritol polyacrylate is preferable from the viewpoint of excellent image forming property.

In the production of the ethylenic compound (A) and the ethylenic compound (B), when an aromatic polyglycidyl ether compound or an aliphatic polyhydroxy compound is reacted with an unsaturated monocarboxylic acid, It is also possible to add a saturated monocarboxylic acid together with an unsaturated monocarboxylic acid to control the physical properties such as viscosity of the ethylenic compound.

In the present invention, the ethylenic compound (A)
And the ethylenic compound (B) are used in a weight ratio,
Ethylenic compound (A): Ethylenic compound (B) = 1
00: 00-10: 90, preferably 90: 10-20:
80, more preferably 80:20 to 30:70.

Other examples of the ethylenic compound that can be used in the present invention include acrylamides such as ethylenebisacrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinylphthalate, and unsaturated divalent carboxylic acids. A polyester obtained by a polycondensation reaction of a dihydroxy compound with a polyamide, a polyamide obtained by a polycondensation reaction of an unsaturated divalent carboxylic acid and a diamine, a divalent carboxylic acid having an unsaturated bond in a side chain, for example, itaconic acid, propylidene Succinic acid, condensation polymer of ethylidene malonic acid and the like and dihydroxy or diamine compound,
A polymer having a functional group having a reactive activity such as a hydroxy group or a methyl halide group in its side chain, for example, polyvinyl alcohol, poly (2-hydroxyethyl methacrylate), polyepichlorohydrin, etc. and acrylic acid, methacrylic acid, crotonic acid, etc. Polymers obtained by the polymer reaction with the unsaturated carboxylic acid of are mentioned.

In the present invention, as the organic polymer substance used as the binder of the photopolymerizable composition, methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, butyl (meth) can be used. ) Acrylic acid, 2-
Alkyl ester of (meth) acrylic acid such as ethylhexyl (meth) acrylic acid, hydroxyethyl (meth) acrylic acid, hydroxypropyl (meth) acrylic acid, benzyl (meth) acrylic acid; hydroxyphenyl (meth) acrylic acid, methoxyphenyl Phenyl ester which may have a substituent of (meth) acrylic acid such as (meth) acrylic acid; acrylonitrile; vinyl acetate, vinyl versatate, vinyl propionate, vinyl cinnamate, vinyl pivalate, etc .; Copolymers of styrene, α-methyl-styrene, etc., polyether of epichlorohydrin and bisphenol A, soluble nylon, polyvinyl alkyl ether, polyamide, polyurethane, polyethylene terephthalate isophthalate, acetyl cellulose and poly Niruhorumaru, polyvinyl butyral. In the present specification,
"(Meth) acrylic" means "acrylic or methacrylic"
Indicates. The same applies to "(meth) acrylate".

In the present invention, for the purpose of enhancing the film strength, coating solvent resistance, and substrate adhesion of the resulting coating film, among the above organic polymer substances, those having a carboxylic acid group but a part of the carboxylic acid group Alternatively, all of them may be reacted with glycidyl (meth) acrylate and the epoxy (meth) acrylate having the structure of [T-1] or [T-2] to obtain a photopolymerizable organic polymer substance.

In the present invention, particularly preferable organic polymer substances include styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylic acid, methoxyphenyl (for the purpose of enhancing the adhesion to the substrate. 10 to 80 mol%, preferably 20 to 70 mol% of a phenyl group-containing copolymerization monomer such as (meth) acrylic acid, hydroxyphenyl (meth) acrylamide, and hydroxyphenyl (meth) acrylsulfoamide.
It is more preferably contained in a proportion of 30 to 60 mol%, and other (meth) acrylic acid is contained in a proportion of 2 to 50 wt%, preferably 5
To 40% by weight, more preferably 5 to 30% by weight, or 2 to 50% by mole, preferably 5 to 40% by mole, more preferably 10 to 100% by weight based on the total amount of the copolymerized monomers. A reactant with 30 mol% epoxy (meth) acrylate added is desirable.

The weight average molecular weight (Mw) of the organic polymer material is 1,000 to 1,000,
000, preferably 2,000 to 500,000, more preferably 3,000 to 200,000.
If the Mw of the organic polymer substance is significantly lower than this range, film-verification of the image area occurs at the time of development, and conversely, if the Mw of the organic polymer material is extremely high, defective removal of the non-image area tends to occur at the time of development. .

In the present invention, the content of the photopolymerization initiation system is based on the total solid content of the photopolymerizable composition excluding the color material.
0.1-40% by weight, preferably 0.2-30% by weight,
The content of the ethylenic compound is more preferably 0.2 to 20% by weight, and the content of the ethylenic compound is 20 to 99% by weight, preferably 50 to 100% by weight based on the total solid content of the photopolymerizable composition excluding the color material.
95% by weight, more preferably 60 to 90% by weight,
The content of the organic polymer substance is 0 to 80% by weight, preferably 10 to 70% by weight, more preferably 20 to 60% by weight, based on the total solid content of the photopolymerizable composition excluding the color material. .

As the color material used in the present invention, a black color material is used for the black matrix color filter resist, and corresponding color materials are used for the red, green and blue color filter resists.

As a black color material, carbon black, JP-A-5-311109, and JP-A-6-116 can be used.
Graphite described in Japanese Patent Publication No. 13, etc., Japanese Patent Application Laid-Open No. 4-322219,
Inorganic black pigments described in JP-A-3-274503 and the like, organic black pigments such as azo black dyes described in JP-A-2-216102, etc., and red, green, blue,
Examples thereof include a black pigment mixed with an organic color material such as yellow, cyan and magenta.

Specific examples of color materials corresponding to red, green, and blue include Victoria Pure Blue (42595), Auramine O (41000), Catillon brilliant flavin (Basic 13), and Rhodamine 6GCP (451).
60), Rhodamine B (45170), Safranine OK
70: 100 (50240), Erioglaucine X (4
2080), No. 120 / Rionol Yellow (21
090), Lionol Yellow GRO (21090),
Shimla Fast Yellow 8GF (21105), Benzidine Yellow 4T-564D (21095), Shimla Fast Red 4015 (12355), Lionol Red 7B4401 (15850), Fastgen Blue TGR-L (74160), Lionol Blue SM (26150). , Rionol Blue ES (Pigment Blue 15: 6, Pigment Blue 1536), Rionogen Red GD (Pigment Red 168, Pigment Red 108), Rionol Green 2YS (Pigment Green 36) and the like (in the above (). Means the color index (C.I.)).

Regarding other pigments (C.I.)
For example, C.I. I. Yellow pigment 20, 24, 8
6, 93, 109, 110, 117, 125, 137,
138, 147, 148, 153, 154, 166,
C. I. Orange pigment 36, 43, 51, 55, 59,
61, C.I. I. Red pigment 9,97,122,123,1
49,168,177,180,192,215,21
6,217,220,223,224,226,22
7,228,240, C.I. I. Violet pigment 19,
23, 29, 30, 37, 40, 50, C.I. I. Blue pigment 15, 15: 1, 15: 4, 22, 60, 64, C.I.
I. Green pigment 7, C.I. I. Brown pigment 23,25,2
6 etc. can be mentioned.

The contents of these color materials in the photopolymerizable composition are as follows.

That is, the black matrix formed of the black colorant photopolymerizable composition is 1.0 μm or less, preferably 0.3 to 0.7 μm, and more preferably 0.3 to 0.6.
The photopolymerizable composition for forming a black matrix having a minimum absorbance (ODmin.) in the range of 400 to 700 nm of 2.0 or more, preferably 2.2 or more in the coating film formed to a film thickness of μm. The content of the black color material contained therein is 40 to 90% by weight, preferably 50 to 80% by weight, more preferably 6 based on the total solid content.
It is in the range of 0 to 70% by weight.

On the other hand, the color material pixels formed of the red, green, and blue color material photopolymerizable composition are 1.0 μm or less, preferably 0.3 to 0.7 μm, and more preferably 0.3 to 0. .6μ
In order to form a color material pixel having a maximum absorbance (OD peak.) in the range of 400 to 700 nm of 1.1 or more, preferably 1.3 or more, the photopolymerizable composition The amount of the red, green, and blue color materials contained in the product is 40 to 90% by weight, preferably 50 to 80% by weight, more preferably 60 to 70% by weight based on the total solid content.
It is in the range of% by weight.

The photopolymerizable composition according to the present invention is formed by forming a high-quality black matrix image or a color material pixel in such a state that the content of the color material is high, and coating it on each pixel. The coloring material photopolymerizable layer or the protective layer of polyamide, polyimide or the like has a function of providing solvent resistance to a coating solvent and high adhesiveness to a transparent substrate.

Such a photopolymerizable composition is applied as a coating solution prepared by using a suitable solvent.

In the present invention, the solvent used for coating the photopolymerizable composition is methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate (hereinafter abbreviated as "PGMAc"), methyl ethyl ketone. , Methyl isobutyl ketone, cyclohexanone, toluene, chloroform, dichloromethine, ethyl acetate, methyl lactate, ethyl lactate, methanol, ethanol, propanol, butanol, tetrahydrofuran and the like.

The coating solution used in the present invention is prepared using these solvents so that the concentration of the photopolymerizable composition is in the range of 5 to 50% by weight, preferably 10 to 30% by weight.

By the way, the photopolymerizable composition of the present invention comprises a protective layer of polyamide, polyimide, etc.
Alternatively, it has a function of imparting sufficient coating solvent resistance to the color material photocurable image with respect to the coating solvent used when laminating the color material photopolymerizable layer, but in order to sufficiently develop this function. The photopolymerizable composition of the present invention is obtained by applying a photopolymerizable composition excluding color materials on a transparent substrate so as to have a dry film thickness of 2 μm, and then performing total exposure at an appropriate exposure amount. Two
The dissolution rate of the photopolymerizable layer when immersed in a PGMAc solvent at 5 ° C. for 5 minutes (hereinafter referred to as “PGMAc dissolution rate”) is preferably 50% by weight or less. This elution rate is 5
When it exceeds 0% by weight, the above-mentioned coloring material photocured image is easily swollen or dissolved by the coating solvent. The elution rate is preferably 15% by weight or less.

In the present specification, the proper exposure amount (the proper exposure amount on the coating surface side) means that the Ugla test chart is placed on the color material photopolymerizable layer, and the exposure amount is passed through the test chart. The amount of exposure when the line width of the thinnest fine line of the negative and positive fine line images in the test chart image is the same as the color material image of the test chart obtained by irradiating with light while changing the Say

In the production of the color filter, a polyvinyl alcohol layer is provided on the color material photopolymerizable layer for the purpose of preventing the sensitivity of the photopolymerizable layer from being lowered by oxygen during the exposure of the photopolymerizable layer. There is a case where an oxygen-barrier layer such as is coated, but in the present invention, it is possible to form an image by exposing and developing the photopolymerizable layer without coating such an oxygen-barrier layer. It is preferable from the viewpoint of a significant decrease in When the oxygen blocking layer is not provided, hydroxyphenyl (meth) acrylic acid, hydroxyphenyl (meth) acrylamide, hydroxyphenyl (meth) are added to the photopolymerizable composition for coloring material.
An organic polymer substance having a monomer having an aromatic hydroxyl group such as a hydroxyphenyl group such as acrylsulfoamide in a proportion of 5 to 50 mol%, preferably 10 to 30 mol% as a comonomer component is used, or 4-21
1 to 20% by weight, preferably 2 to 10% by weight of the diazo compound described in JP-A No. 8048 and JP-A No. 5-19453.
It may be included by weight%. As a result, the decrease in sensitivity due to oxygen can be suppressed to a low level, and the oxygen barrier layer can be eliminated.

Next, a method of manufacturing a color filter using the color filter resist of the present invention will be described.

Examples of the transparent substrate of the color filter used in the present invention include polyester sheets such as polyethylene terephthalate, plastic sheets such as polypropylene and polyolefin such as polyethylene, and various glass plates.

On such a transparent substrate, corona discharge treatment, ozone treatment, thin film formation of various polymers such as silane coupling agent and urethane polymer, etc., as necessary, in order to improve physical properties such as surface adhesiveness. Processing etc. can be performed.

The plate thickness of the transparent substrate is 0.05 to 10
mm, particularly preferably in the range of 0.1 to 7 mm. When a thin film forming treatment of various polymers is performed, the film thickness is 0.01 to 10 μm, particularly 0.05 to 5 μm.
It is preferably in the range of μm.

This transparent substrate is usually provided with a metal thin film or a black matrix using the above-mentioned photopolymerizable composition for the black matrix before forming the red, green and blue pixel images. Examples of the former include a single layer of chromium or a double layer of chromium and chromium oxide. After forming a thin film of these by vapor deposition or sputtering, a photosensitive film is formed thereon to form stripes, One in which a black matrix is formed on a transparent substrate by exposing and developing using a photomask having a repeating pattern such as mosaic or triangle to form a resist image, and then etching the thin film is mentioned.

On the transparent substrate thus provided with the black matrix, a photopolymerizable composition containing a color material of one of red, green and blue is applied by a spinner, a wire bar, a flow coater, a die coater. Tar, roll coater,
50-200 after coating with a coating device such as a spray
15 seconds to 10 ° C., preferably 100 to 150 ° C.
The coloring material photopolymerizable layer is formed by drying for 30 minutes to 5 minutes. Here, the film thickness of the photopolymerizable layer obtained by applying a coating solution of the photopolymerizable composition and drying is:
Preferably 0.2-2 μm, more preferably 0.5-1
μm.

Here, the higher the drying temperature is, the more the adhesion to the transparent substrate is improved. On the other hand, if the drying temperature is too high, the photopolymerization initiation system is decomposed and thermal polymerization is apt to be induced to cause defective development.

Next, a negative photomask for color material pixels is placed on the color material photopolymerizable layer, and the negative photomask for the color material pixels is placed through the photomask.
Image exposure is performed using a light source such as ultraviolet light or visible light. On this occasion,
If necessary, in order to prevent the sensitivity of the photopolymerizable layer from lowering due to oxygen, exposure may be performed after coating an oxygen blocking layer such as a polyvinyl alcohol layer on the photopolymerizable layer.

Subsequently, development processing is performed with an alkali developing solution or a water-containing organic solvent developing solution to form a first color material pixel image on the transparent substrate. Prior to the development treatment, if necessary, the exposed sample is exposed to 70 to 200 ° C. for 15 seconds to 20 minutes, preferably 80 to 150 ° C. for the purpose of increasing the sensitivity or γ value (gradation) of the photopolymerizable layer. The heat treatment can be performed for 30 seconds to 10 minutes.

Examples of the alkaline developer used for development include inorganic alkali agents such as sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide and potassium hydroxide, or diethanolamine, triethanolamine and water. Contains an organic alkali agent such as tetraalkylammonium oxide salt, and if necessary, a surfactant for the purpose of improving image quality and shortening development time,
An aqueous solution containing a water-soluble organic solvent, a low molecular weight compound having a hydroxyl group or a carboxylic acid group, and the like can be used.

As the surfactant of the developing solution, an anionic surfactant having a sodium naphthalenesulfonate group, a sodium benzenesulfonate group, a nonionic surfactant having a polyalkyleneoxy group, a cation having a tetraalkylammonium group. Examples of the water-soluble organic solvent include ethanol, propion alcohol, butanol, methyl cellosolve, butyl cellosolve, phenyl cellosolve, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene. Examples thereof include glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol and propylene glycol monomethyl ether.

Examples of the low molecular weight compound having a hydroxyl group or a carboxy group include 1-naphthol, 2-naphthol, pyrogallol, benzoic acid, succinic acid and glutaric acid.

On the other hand, the organic solvent used in the water-containing organic solvent developer can be appropriately selected and used from the water-soluble organic solvents used in the alkali developer.

The above-mentioned development processing is usually carried out in the range of 20-4.
It is carried out at a developing temperature of 0 ° C., preferably 25 to 35 ° C., by a method such as immersion development, spray development, brush development, ultrasonic development and the like.

The sample after development is, if necessary, a coloring material photopolymerizable layer or polyamide, which is applied on the sample.
For the purpose of improving the durability of the protective layer such as polyimide against the coating solvent or the adhesiveness with a transparent substrate such as a glass substrate, the sample is subjected to a heat curing treatment at 100 to 250 ° C. for 5 to 60 minutes, or It is possible to perform the photo-curing treatment with an exposure amount of not less than the proper exposure amount, preferably an exposure amount of 1 to 10 times the proper exposure amount.

Subsequently, the photopolymerizable composition of the other two colors of red, green and blue was applied and dried on the sample in the same manner as described above, and then the sample was used for a color material pixel. Using the negative photomask of No. 3, exposure, development and heat or photo-curing treatment are repeated as described above to form pixels of three colors between the black matrix to produce a color filter.

In the color filter thus manufactured, the ITO (transparent electrode) is formed on the color filter as it is and used as a part of the component of the color display. Alternatively, a top coat layer of polyamide, polyimide or the like may be provided for the purpose of improving durability.

As the light source used for image exposure in the present invention, a lamp light source such as a xenon lamp, a halogen lamp, a tungsten lamp, a high pressure mercury lamp, a metal halide lamp, a medium pressure mercury lamp, a low pressure mercury lamp, an argon ion laser, a YAG laser, A laser light source such as an excimer laser or a nitrogen laser can be used. An optical filter may be appropriately used for these light sources depending on the required wavelength range of irradiation light.

When the black matrix is formed by using the photopolymerizable composition according to the present invention containing a black color material, a method for forming red, green and blue pixel images on a transparent substrate is used. A black matrix is formed by adopting the same method. At this time, by repeating the operation of forming the black matrix two or more times, it is possible to stack the black matrix images and complete the black matrix image of the desired transmission density.

Although the method of forming the red, green and blue pixel images on the transparent substrate on which the black matrix is formed has been described above, the method of forming the black matrix after forming the red, green and blue pixel images is also adopted. It is possible.

Further, using the color filter resist of the present invention, a black stripe or a transparent stripe is formed on a transparent substrate.
When forming a red, green and blue color material pixel image, a color material is formed on the transparent substrate for the purpose of enhancing the adhesiveness of the developed image and / or the adhesiveness of the thermosetting image between the color filter resist and the transparent substrate. It is possible to provide a photocurable adhesive layer obtained by photocuring a photopolymerizable composition containing no.

The photopolymerization initiation system contained in the photopolymerizable composition used for the photocurable adhesive layer, the ethylenic compound, and the organic polymer substance used as necessary are the color filter resist of the present invention. The photopolymerizable composition of the present invention can be appropriately selected and used. Such a photocurable adhesive layer can be obtained by using the photopolymerizable composition in a dry film thickness of 0. 01 to 2 μm, preferably 0.0
After being coated on a transparent substrate so as to be in the range of 2 to 1 μm, 1 to 1 of the appropriate exposure amount of the coated photopolymerizable composition layer is applied.
It can be formed by exposing with a 10 times exposure amount and photocuring.

Furthermore, a black stripe formed on a transparent substrate using the color filter resist of the present invention, or a resist image such as red, green, and blue color material pixels is peeled from the transparent substrate over time. For the purpose of preventing the occurrence of defects such as scratches, a photocurable layer can be provided on the transparent substrate on which the resist image is formed by the same method as in the case of the photocurable adhesive layer.

[0082]

The ethylenic compound (A) used in claim 1
Is effective in improving the adhesiveness during development, and effectively prevents image loss.

With the ethylenic compound according to the second aspect, the developed image adhesion is further enhanced.

By using the ethylenic compound (B) according to the third aspect together, the solubility of the non-image area at the time of development can be enhanced and a high quality image can be formed.

With the color filter resist according to the fourth aspect, since the coating solvent resistance is excellent, it is possible to form a pixel image having sufficient durability against the coating of the photopolymerizable composition.

According to the fifth aspect, particularly the sixth aspect, the adhesion of the pixel image to the substrate is further enhanced.

According to claim 7, a good color filter resist for forming a black matrix is provided.

According to the eighth aspect, a good color filter resist for forming a color material pixel image is provided.

The photopolymerizable composition according to the present invention forms a high-quality black matrix image or a color material pixel with a high content of a color material and a color formed by coating each pixel. The material has a function of providing solvent resistance to a coating solvent such as a photopolymerizable layer or a protective layer of polyamide, polyimide or the like, and high adhesiveness to a transparent substrate.

[0090]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples below, but the present invention is not limited to the following Examples unless it exceeds the gist.

Examples 1 to 24, Comparative Examples 1 to 11 The following types and formulations of I to VIII are adopted as the photopolymerization initiation system, the following are used as the organic polymer substance, and the following a to the ethylenic compound are used. Using p, a coating liquid of a photopolymerizable composition for forming a black matrix containing a black coloring material was prepared with the following composition.

[0092]

Embedded image

[0093]

[Chemical 4]

[0094]

Embedded image

[0095]

[Chemical 6]

[0096]

[Chemical 7]

[Ethylene Compound] a: Cocondensation monomer of bisphenol A and epichlorohydrin (“VR-60” manufactured by Showa High Polymer Co., Ltd., solid, melting point: 70-80 ° C.) b: Bisphenol A and epichlorohydrin Co-condensation polymer type monomer (Showa Polymer Co., Ltd. "SP-1509"
Viscosity: 10000 cps / 25 ° C) c: Copolycondensate monomer of bisphenol A and epichlorohydrin (Showa Polymer Co., Ltd. "SP-5003")
Viscosity: 1700-2000cps / 25 ° C) d: Copolycondensate monomer of bisphenol A and epichlorohydrin ("SP-2600" manufactured by Showa High Polymer Co., Ltd.)
Viscosity: 200-250 cps / 25 ° C) e: Novolac-based monomer (Showa Polymer Co., Ltd. "SP-4"
010 "Viscosity: 170-200 cps / 25 ° C) f: Bisphenol A-based monomer (" A "manufactured by Shin-Nakamura Chemical Co., Ltd.
-BPE-4 "Viscosity: 1100 cps / 25 ° C) g: Dipentaerythritol hexaacrylate (Kyoeisha Chemical Co., Ltd." DPE-6A ") h: Trimethylolpropane triacrylate (Shin Nakamura Chemical Co., Ltd." TMPT ") i: Tetra Methylol methane triacrylate ("A-TMM-3" manufactured by Shin Nakamura Chemical Co., Ltd.) j: Tetramethylol methane tetraacrylate ("A-TMM-T" manufactured by Shin Nakamura Chemical Co., Ltd.) k: Polyethylene glycol diacrylate (Shin Nakamura Chemical Co., Ltd.) Manufactured by "9AG") 1: dipentaerythritol-based monomer ("DPCA-30" manufactured by Nippon Kayaku Co., Ltd.) m: trimethylol-based monomer ("TM" manufactured by Kyoeisha Chemical Co., Ltd.)
P-6EO-3A "): Polyester monomer (" M-61 "manufactured by Toyo Gosei Co., Ltd.
00 ”) o: Polyester monomer (“ M-80 ”manufactured by Toyo Gosei Co., Ltd.
60 ") p: Urethane-based monomer (" U-4H "manufactured by Shin-Nakamura Chemical Co., Ltd.)
A ") [Black colorant photopolymerizable coating liquid composition] Photopolymerization initiation system: described in Tables 1 to 5 organic polymer substance: described in Tables 1 to 5 ethylenic compound: described in Tables 1 to 5 coating solvent ( PGMAc): 140 parts by weight Black pigment (carbon black (“MA-7” manufactured by Mitsubishi Chemical Co., Ltd.)): Addition rates are shown in Tables 1-5. (Corning No. 705
9) is applied by a wire bar coater to the dry film thickness shown in Tables 1 to 5, and dried for 2 minutes at the drying temperature shown in Tables 1 to 5, and further the polyvinyl alcohol aqueous solution is dried to a film thickness of 2 μm. Was applied and dried by the same method. Next, using a negative photomask for a black matrix which is repeated at a pitch of 330 μm in width and 330 μm in width with a width of 30 μm, a 2 Kw high-pressure mercury lamp was used to expose with an appropriate exposure amount shown in Tables 1 to 5, and then 0.5 wt% of diethanolamine was used. , 0.05 wt% phenoxyethanol, 0.
Immersion in an aqueous solution containing 5% by weight of anionic surfactant (“Perex NBL” manufactured by Kao Corporation) at 25 ° C., development treatment by rubbing 5 times with a sponge to form a black matrix, and then 200 ° C., 7 It was heat-cured by heat treatment for 1 minute. The sample was evaluated by the following evaluation methods, and the results are shown in Tables 1-5.

[Absorbance (OD)] The minimum absorbance (ODmin) of 700 nm light was measured.

[Pigment Concentration] Ratio of pigment contained in the solid content of the black colorant photopolymerizable coating liquid. Pigment concentration = weight of pigment / weight of total solids [elution rate] Glass substrate (Corning No. 705)
9) Apply the photopolymerizable coating liquid with the color material removed to a dry film thickness of 2
Apply it with a wire bar to a size of 2 μm, and apply 2 at 80 ° C.
After drying for a minute to form a photopolymerizable layer, the sample was dried at 2K.
w All surfaces are exposed by a high-pressure mercury lamp at appropriate exposure amounts shown in Tables 1 to 5, and then the sample is placed in a PGMAc solvent at 25 ° C.
Immersion treatment for 5 minutes at 100 ° C.
The amount of the photopolymerizable layer eluted per cm ² was measured by a gravimetric method, and this value was divided by the weight of the photopolymerizable layer of the sample before immersion,
The dissolution rate was calculated. Note that F indicates that this evaluation was not performed. A: Elution rate of 5% by weight or less B: Elution rate of 5 to 15% by weight C: Elution rate of 15 to 50% by weight D: Elution rate of 50% by weight or more [Development image adhesiveness] On a glass substrate by the same method as described above. After applying the black colorant photopolymerizable coating liquid to the above and drying it, and further applying and drying the polyvinyl alcohol aqueous solution, using a negative photomask of the black matrix, 2 Kw
The sample was exposed with a high-pressure mercury lamp at an appropriate exposure amount, and then the sample was immersed in an alkali developing solution, rubbed with a sponge 5 times, and washed with water to form an image. After that, in a state where the sample was not dried, H of various weights was applied on the sample.
The tip of the pencil of B was placed and moved at a speed of 20 cm per minute to examine whether a squeegee mark due to lead was generated on the image, and the developed image adhesiveness was evaluated according to the following criteria. The more squeegee marks are produced with a lightly weighted pencil, the more likely an uneven pattern will occur in the image, such as brush unevenness or spray unevenness, when processed with an automatic processor, and in extreme cases, the entire image will be brushed, sprayed, etc. It becomes easy to peel off by the physical stimulation of. Note that F indicates that this evaluation was not performed. A: No squeegee trace was observed even when a weight of 50 g was applied. B: A squeegee trace was seen under a load of 30 g or more. C: A squeegee mark was observed under a load of 20 g or more. D: A squeegee trace was observed even with a load of 10 g or less.

[Adhesiveness of Thermosetting Image] When an image formed on a glass substrate was cut with a cutter in a matrix shape at a pitch of 2 mm, a cellophane tape was attached thereto, and then the cellophane tape was peeled off. The lack of the pixel image generated in 1) was visually observed and evaluated according to the following criteria. In addition,
F indicates that this evaluation was not performed.

A: Peeling of the black image from the glass substrate due to peeling of cellophane tape was 1% or less. B: 1-2% of the black image was peeled off by the cellophane tape peeling. C: 2 to 5% of the black image was peeled off by the cellophane tape peeling. D: 5% or more of the black image was peeled off by the cellophane tape peeling.

[Coating Solvent Spoiler] A sample on which a black matrix image was formed was immersed in a polyamide used as a protective layer of a color filter or N-methylpyrrolidone (NMP) which is a coating solvent of polyimide at 25 ° C. for 10 minutes.
After soaking for a minute, the surface of the matrix was observed with a microscope of 400 times, and changes due to swelling, dissolution, etc. of the matrix surface by the coating solvent were evaluated according to the following criteria. In addition, F
Indicates that this evaluation was not performed.

A: No deformation due to the coating solvent was observed. B: 1 to 5% of the pixels were deformed. C: 5 to 10% of the pixels were deformed. D: 10% or more of the pixels were deformed.

[Image Quality] A black colorant photopolymerizable layer coating liquid was applied onto a glass substrate and dried by the same method as described above.
Further, an aqueous polyvinyl alcohol solution was applied and dried, and then exposed at an appropriate exposure amount using a Ugula test chart, and developed to form a color material image. The fine line image in the color material image was observed under a microscope of 400 times, and the image quality was evaluated based on the line width of the finest fine line reproduced, according to the following criteria. The finer the fine line, the better the image quality. Note that F indicates that this evaluation was not performed.

A: A fine line having a line width of 10 μm or less is reproduced. B: A fine line having a line width of 10 to 15 μm is reproduced. C: A fine line having a line width of 15 to 25 μm is reproduced. D: A fine line having a line width of 25 μm or more is reproduced.

[0106]

[Table 1]

[0107]

[Table 2]

[0108]

[Table 3]

[0109]

[Table 4]

[0110]

[Table 5]

Example 25 The same evaluation as in Example 10 was carried out except that an inorganic coloring material (“Black # 9550” manufactured by Dainichiseika Co., Ltd.) was used as the black coloring material. Similar results were obtained.

Examples 26 to 49, Comparative Examples 12 to 22 A glass substrate (No. 7059, manufactured by Corning Incorporated) having a width of 3
A photopolymerizable coating solution containing a red colorant having the following composition is shown in Tables 6 to 10 using a substrate in which a black matrix having a thickness of 0.2 μm and repeating at a pitch of 0 μm, a length of 330 μm and a width of 110 μm is formed of chromium. A wire bar coater was applied to obtain a dry film thickness, and the coating was dried at the drying temperatures shown in Tables 6 to 2 for 2 minutes. Next, with a width of 80 μm,
Using a negative photomask for a stripe pattern that repeats at a pitch of 30 μm, a 6 Kw high-pressure mercury lamp was used to produce the results shown in Table 6-
After exposure with an appropriate exposure amount shown in 10, development and heat treatment were performed under the same conditions as in Example 1. The sample was evaluated by the same evaluation method as in Example 1, and the results are shown in Tables 6 to 10. However, the absorbance was 450 nm.

[Red-Coloring Material-Containing Photopolymerizable Coating Solution Composition] Photopolymerization initiation system: described in Tables 6 to 10 organic polymer substance: described in Tables 6 to 10 ethylenic compound: described in Tables 6 to 10 (PGMAc): 140 parts by weight Red pigment (Rionogen Red GD (manufactured by Toyo Ink Mfg. Co.) / Rionogen Orange R (manufactured by Toyo Ink Mfg. Co.)
(= 13: 5 (weight ratio))): Addition rates are shown in Tables 6 to 10.

[0114]

[Table 6]

[0115]

[Table 7]

[0116]

[Table 8]

[0117]

[Table 9]

[0118]

[Table 10]

Examples 50 and 51 Evaluations were made in the same manner as in Example 35 except that the following green pigment (Example 50) or blue pigment (Example 51) was used in place of the red pigment. As a result, the same results as in Example 35 were obtained.

Green pigment: Rionol Green 2YS (manufactured by Toyo Ink Mfg. Co., Ltd.) / Rionogen Yellow 3G (manufactured by Toyo Ink Mfg. Co., Ltd.) (= 9: 17 (weight ratio)) Blue pigment: Rionol Blue ES (Toyo Ink Mfg. Co., Ltd.) (Manufactured by Toyo Ink Mfg. Co., Ltd.) / (Rionogen Violet RL) (= 13.5: 3.5 (weight ratio)) Example 52 In Example 4, the black coloring material was removed from the glass substrate. A coating liquid having the same composition as in Example 10 except for the above was applied using a wire bar coater to a dry film thickness of 0.2 μm, dried at 120 ° C. for 2 minutes, and then 1000 mJ / cm ^{2 with} a high pressure mercury lamp of ² Kw. A black matrix image was formed in the same manner except that a transparent substrate on which a photo-curable adhesive layer was formed by exposure was used. Both improved to the evaluation value A.

Example 53 In the same manner as in Example 12 except that the organic polymer substance was removed, a black colorant photopolymerizable coating solution was applied, dried, and exposed with a mask at an appropriate exposure amount. After that, the sample was immersed in a 15 wt% isopropyl alcohol aqueous solution for 20 minutes.
After soaking for 2 seconds and rubbing with a sponge 5 times, a black matrix image was obtained. When the image quality and the thermosetting image adhesiveness were evaluated in the same manner as in Example 12 using this black matrix image, the evaluation result of B was obtained.

[0122]

As described above in detail, since the color filter resist of the present invention is excellent in transparency, solvent resistance and adhesion to a substrate, a high quality color filter can be easily formed at low cost. it can. In particular, the color filter resist of the present invention is useful as a color filter resist for a black matrix, which is inexpensive in manufacturing cost, excellent in light-shielding property, solvent resistance, and adhesiveness to a substrate.

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[Procedure amendment]

[Submission date] January 26, 1996

[Procedure Amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0035

[Correction method] Change

[Correction content]

Particularly preferred ethylenic compound (A)
As for the viscosity at 25 ° C is 100 ps or more,
Of which the viscosity is 1000 ps or more. If this viscosity is significantly lower than 100 ps , the developed image adhesion will be reduced.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0097

[Correction method] Change

[Correction content]

[Ethylene Compound] a: Cocondensation monomer of bisphenol A and epichlorohydrin (“VR-60” manufactured by Showa High Polymer Co., Ltd., solid, melting point: 70-80 ° C.) b: Bisphenol A and epichlorohydrin Co-condensation polymer type monomer (Showa Polymer Co., Ltd. "SP-1509"
Viscosity: 10000 ps / 25 ° C) c: Copolymerization monomer of bisphenol A and epichlorohydrin ("SP-5003" manufactured by Showa High Polymer Co., Ltd.)
Viscosity: 1700-2000 ps / 25 ° C) d: Copolycondensate monomer of bisphenol A and epichlorohydrin ("SP-2600" manufactured by Showa High Polymer Co., Ltd.)
Viscosity: 200-250 ps / 25 ° C) e: Novolac-based monomer (Showa Polymer Co., Ltd. "SP-4
010 "Viscosity: 170-200 ps / 25 ° C) f: Bisphenol A-based monomer (" A "manufactured by Shin-Nakamura Chemical Co., Ltd.
-BPE-4 "Viscosity: 1100 ps / 25 ° C) g: Dipentaerythritol hexaacrylate (" DPE-6A "manufactured by Kyoeisha Chemical Co., Ltd.) h: Trimethylolpropane triacrylate (" TMPT "manufactured by Shin Nakamura Chemical Co., Ltd.) i: Tetramethylol methane triacrylate ("A-TMM-3" manufactured by Shin Nakamura Chemical Co., Ltd.) j: Tetramethylol methane tetraacrylate ("A-TMM-T" manufactured by Shin Nakamura Chemical Co., Ltd.) k: Polyethylene glycol diacrylate (Shin Nakamura Chemical Co., Ltd. "9AG" manufactured by the company) 1: Dipentaerythritol-based monomer ("DPCA-30" manufactured by Nippon Kayaku Co., Ltd.) m: Trimethylol-based monomer ("TM" manufactured by Kyoeisha Chemical Co., Ltd.)
P-6EO-3A "): Polyester monomer (" M-61 "manufactured by Toyo Gosei Co., Ltd.
00 ”) o: Polyester monomer (“ M-80 ”manufactured by Toyo Gosei Co., Ltd.
60 ") p: Urethane-based monomer (" U-4H "manufactured by Shin-Nakamura Chemical Co., Ltd.)
A ") [Black colorant photopolymerizable coating liquid composition] Photopolymerization initiation system: described in Tables 1 to 5 organic polymer substance: described in Tables 1 to 5 ethylenic compound: described in Tables 1 to 5 coating solvent ( PGMAc): 140 parts by weight Black pigment (carbon black (“MA-7” manufactured by Mitsubishi Chemical Co., Ltd.)): Addition rates are shown in Tables 1-5. (Corning No. 705
9) is applied by a wire bar coater to the dry film thickness shown in Tables 1 to 5, and dried for 2 minutes at the drying temperature shown in Tables 1 to 5, and further the polyvinyl alcohol aqueous solution is dried to a film thickness of 2 μm. Was applied and dried by the same method. Next, using a negative photomask for a black matrix which is repeated at a pitch of 330 μm in width and 330 μm in width with a width of 30 μm, a 2 Kw high-pressure mercury lamp was used to expose with an appropriate exposure amount shown in Tables 1 to 5, and then 0.5 wt% of diethanolamine was used. , 0.05 wt% phenoxyethanol, 0.
Immersion in an aqueous solution containing 5% by weight of anionic surfactant (“Perex NBL” manufactured by Kao Corporation) at 25 ° C., development treatment by rubbing 5 times with a sponge to form a black matrix, and then 200 ° C., 7 It was heat-cured by heat treatment for 1 minute. The sample was evaluated by the following evaluation methods, and the results are shown in Tables 1-5.

Claims (8)

[Claims] 1. A color filter resist comprising a photopolymerizable composition containing a color material, a photopolymerization initiation system and an ethylenic compound, wherein an aromatic polyglycidyl ether compound and an unsaturated monocarboxylic acid are used as the ethylenic compound. A color filter resist comprising a compound having two or more ethylenically unsaturated double bonds obtained by an addition reaction or an addition reaction between an aromatic polyhydroxy compound and an epoxy monocarboxylic acid ester. 2. The color filter resist according to claim 1, wherein the aromatic polyglycidyl ether compound is a cocondensation product of bisphenol A and epichlorohydrin. 3. The color filter resist according to claim 1, further comprising an ethylenic compound,
A color filter resist comprising a compound having two or more ethylenically unsaturated double bonds obtained by an addition reaction of an aliphatic polyhydroxy compound and an unsaturated monocarboxylic acid. 4. The color filter resist according to claim 1, wherein the photopolymerizable composition excluding the color material is applied to a transparent substrate to a dry film thickness of 2 μm and dried. , Full exposure with proper exposure amount, 25 ℃
A color filter resist having an elution rate of 50% by weight or less when immersed for 5 minutes in propylene glycol monomethyl ether acetate. 5. The color filter resist according to any one of claims 1 to 4, wherein the photopolymerizable composition contains a copolymer to which 2 to 50 mol% of epoxy (meth) acrylate is added. Is a color filter resist. 6. The color filter resist according to claim 5, wherein the copolymer uses a monomer containing 10 to 80 mol% of a phenyl group. 7. The color filter resist according to claim 1, wherein the photopolymerizable composition contains a black material, and a coating film formed to a dry film thickness of 1 μm or less is 400 to 700 nm. The minimum absorbance in the range of 2.
A color filter resist for producing a black matrix, which is 0 or more. 8. The color filter resist according to claim 1, wherein the photopolymerizable composition contains a red, green or blue material and is formed to a dry film thickness of 1 μm or less. , A maximum absorbance in the range of 400 to 700 nm is 1.1 or more, a color filter resist for producing red, green or blue color material pixels.