JPH0996719A - Photopolymerizable composition for color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a photopolymerizable compsn. for a color filter having high sensitivity without applying an oxygen blocking layer by using a radical generating agent and a specified compd. as a sensitizer into a photopolymn. initiator. SOLUTION: This photopolymerizable compsn. for a color filter contains a photopolymn. initiator and a coloring material by >40wt.% of the whole solid content in the photopolymerizable compsn. The photopolymn. initiator contains a radical generating agent and a compd. expressed by formula as a sensitizer. In formula, R<1> , R<2> are 1-10C alkyl groups which may have substituents R<3> , R<4> are hydrogen or 1-10C alkyl groups which may have substituents, R<5> is a hydrogen atom, 1-10C alkyl group or 1-10C alkoxy group, R<6> is a hydrogen atom, 1-10C alkyl group or 6-15C aryl group, Y is a hydrogen atom, cyano group, 1-10C alkyl group, 1-10C alkoxy group, 2-10C alkoxycarbonyl group or 2-15C acyl group.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a photopolymerizable composition for color filters. More specifically, it relates to a photopolymerizable composition used for producing an optical color filter used in a color television, a liquid crystal display device, a camera and the like.

[0002]

2. Description of the Related Art A color filter is usually formed on a transparent substrate such as a glass or plastic sheet provided with a black matrix on the surface thereof in a stripe pattern with a width of 10 to 50 μm and a mosaic pattern of 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 merits and demerits, such as poor heat resistance, poor pattern positional accuracy, high production cost, and poor productivity, and each method is used 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 is widely used 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.

In the photopolymerizable composition used in such a pigment dispersion method, in addition to the color material, an organic polymer substance,
It contains a compound having at least one ethylenically unsaturated double bond (hereinafter referred to as “ethylenic compound”), a photopolymerization initiation system, and a solvent. As a photopolymerization initiation system,
A compound in which a triazine compound or a triazine compound and an imidazole compound are used in combination (JP-A-6-20191)
3), a combination of Michler's ketone and an imidazole compound (JP-A-5-173320),
Or “Fine Chemical” March 1, 1991, Vo
l. 20, no. 4, p. 16-26, dialkyl acetophenone type, benzyl dialkyl ketal type,
Benzoin-based, benzoin alkyl ether-based, thioxanthone derivatives and the like are used for color filters (JP-A-4-190362 and JP-A-5-30).
3012, JP-A-6-25188, etc.).

[0005]

However, the sensitivity of the conventional photopolymerizable composition for a color filter is not sufficient, and it is necessary to apply a high-output light source or an oxygen barrier layer such as a polyvinyl alcohol layer. It was a problem. Especially,
The photopolymerizable composition for the black matrix has a problem of low sensitivity. The present invention solves the above conventional problems,
It is an object of the present invention to provide a photopolymerizable composition for a color filter having high sensitivity without coating an oxygen barrier layer.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors of the present invention contain a compound having at least one ethylenically unsaturated double bond, a copolymerization initiation system and a color material. In the photopolymerizable composition, a radical generator and a specific sensitizer are combined as a photopolymerization initiation system, and it has been found that a highly sensitive photopolymerizable composition can be obtained even at a high color material solid content concentration. Reached

Accordingly, the gist of the present invention is to provide a photopolymerizable composition containing a compound having at least one ethylenically unsaturated double bond, a photopolymerization initiation system and a color material, wherein the photopolymerization initiation system is a radical. A compound represented by the following general formula (I) is contained as a generator and a sensitizer, and the color material is contained in an amount of 40% by weight or more based on the total solid content in the photopolymerizable composition. Photopolymerizable composition for color filter

[0008]

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(Where R is¹, R²May have a substituent
An alkyl group having 1 to 10 carbon atoms (wherein the substituent is hydroxy
Group, halogen atom, alkoxy group having 1 to 10 carbon atoms, charcoal
Acyl group having 2 to 10 primes, Aryl group having 6 to 15 carbon atoms
Xy group or alkyloxycarbonyl having 2 to 15 carbon atoms
Group) and R^Three, R^FourIs a hydrogen atom or carbon number 1
10 represents an alkyl group, but R¹And R^Four, R²And R^Three
Are directly bonded to each other or via a sulfur atom or an oxygen atom.
May combine with each other to form a ring, R^FiveIs hydrogen atom, charcoal
Alkyl group having 1 to 10 primes or Alco having 1 to 10 carbons
A xy group; ⁶Is a hydrogen atom, an alkane having 1 to 10 carbon atoms
A kill group or an aryl group having 6 to 15 carbon atoms is shown.^Five
And R⁶At direct bond with each other or via sulfur atom, oxygen atom
May combine with each other to form a ring, and Y is a hydrogen atom or cyano.
Group, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms
Lucoxy group, alkoxycarbonyl group having 2 to 10 carbon atoms
Or an acyl group having 2 to 15 carbon atoms).

Hereinafter, the present invention will be described in detail. The ethylenic compound used in the present invention is preferably one having at least two ethylenic unsaturated bonds in which the polymerization is induced in the presence of the photopolymerization initiator composition, specifically, polyglycidyl. Ethylenic compound (A) having two or more ethylenically unsaturated double bonds obtained by addition reaction of ether compound and unsaturated monocarboxylic acid or addition reaction of polyhydroxy compound and epoxy monocarboxylic acid ester However, an ethylenic compound containing two or more ethylenically unsaturated double bonds, which is obtained by an addition reaction (ester reaction) of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid together with the ethylenic compound (A). It is preferable to use the compound (B) in combination. The ethylenic compound (A) has a function of improving the adhesiveness to the transparent substrate and the developability.

Specific examples of the ethylenic compound (A) include polyhydroxybenzenes such as hydroquinone, resorcinol and pyrogallol, bisphenol A, polybisphenol A, bisphenol A derivatives such as brominated bisphenol A and polybrominated bisphenol A. , An aromatic polyhydroxy compound such as novolak, and a polyglycidyl ether compound obtained by the addition reaction of epichlorohydrin with their nuclear hydrogenation products under alkaline conditions, and an unsaturated monocarboxylic acid such as (meth) acrylic acid
Ethylenic compounds obtained by addition reaction using a primary ammonium salt or the like, or polyhydroxybenzenes such as hydroquinone, resorcinol and pyrogallol, bisphenol A, polybisphenol A, brominated bisphenol A, polybrominated bisphenol A
, Bisphenol A derivatives, etc., aromatic polyhydroxy compounds such as novolak, and their nuclear hydrogenated products and glycidyl (meth) acrylates, [T-1] or [T
-2] and the like epoxy (meth) acrylate,
"Synthetic Communication,
24 (21) "3009-3019 (1994) and the like, two substituents represented by the general formula (II) or (III), which are obtained by addition reaction using an acid or alkali catalyst described in The ethylenic compounds having the above are listed, and more specifically, for example, the following [M-1] and [M-
2], [M-3], [M-4], [M-5], [M-
6], [M-7], [M-8], [M-9], [M-1
0], [M-11], [M-12], [M-13],
[M-14] and the like can be mentioned. Further, as the hydrogenation reaction, one using a Raney Ni catalyst described in JP-A-3-107160 or the like and one using a catalyst such as rhodium or platinum can be appropriately selected and used.

[0012]

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[0013]

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[0014]

[Chemical 6]

[0015]

[Chemical 7]

[0016]

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In particular, in the case of using an ethylenic compound (A) of a copolycondensation type of bisphenol A or a bisphenol A derivative, a hydrogenated product thereof in the nucleus, and epichlorohydrin, in the case of other ethylenic compounds, In comparison, it is preferable because it has excellent image adhesion to the substrate during development (developed image adhesion). Particularly preferred ethylenic compound (A) has a viscosity of 100 p at 25 ° C.
and those having a viscosity at 25 ° C. of 1000 ps or more. If this viscosity is significantly lower than 100 ps,
The developed image adhesion decreases.

On the other hand, the ethylenic compound (B) has the function of increasing 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 the polyglycidyl ether compound or the polyhydroxy compound is reacted with the unsaturated monocarboxylic acid, the unsaturated monocarboxylic acid is reacted. It is also possible to add a saturated monocarboxylic acid together with a carboxylic acid to control the physical properties such as viscosity of the ethylenic compound. Preferred ethylenic compound (A) and ethylenic compound (B)
The usage ratio of and is, by weight ratio, the ethylenic compound (A):
Ethylenic compound (B) = 100: 0 to 10:90, preferably 90:10 to 20:80, more preferably 8
It is 0:20 to 30:70.

Other examples of ethylenic compounds that can be used in combination include acrylamides such as ethylenebisacrylamide, allyl esters such as diallyl phthalate, vinyl group-containing compounds such as divinylphthalate, unsaturated divalent carboxylic acids and dihydroxy compounds. Polyester obtained by polycondensation reaction with, a polyamide obtained by polycondensation reaction of unsaturated divalent carboxylic acid and diamine, divalent carboxylic acid having an unsaturated bond in the side chain, for example itaconic acid, propylidene succinic acid, Condensation polymers of ethylidene malonic acid and the like and dihydroxy or diamine compounds, polymers having functional groups having a reactive activity such as a hydroxy group and a methyl halide group in the side chain, for example, polyvinyl alcohol, poly (2-hydroxyethyl methacrylate) ), With polyepichlorohydrin, etc. Acrylic acid, methacrylic acid, polymers obtained by a polymer reaction of an unsaturated carboxylic acid such as crotonic acid.

In the color filter resist according to the present invention, for the purpose of improving the film forming property and developing property of the resist,
Organic polymeric substances can be added as binders.
Examples of the organic polymer substance include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth)
Alkyl ester of (meth) acrylic acid such as acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, benzyl (meth) acrylate; hydroxyphenyl (meth ) Acrylate, phenyl ester which may have a substituent of (meth) acrylic acid such as methoxyphenyl (meth) acrylate; acrylonitrile; vinyl acetate, vinyl versatate, vinyl propionate, vinyl cinnamate, vinyl pivalate, etc. Acid vinyls; copolymers of styrene, α-methyl-styrene, etc., polyethers of epichlorohydrin and bisphenol A, soluble nylons, polyvinyl alkyl ethers, polyamides, polyurethanes, polyethylene Terephthalate isophthalate, cellulose acetate and polyvinyl formal, and polyvinyl butyral. In this specification, “(meth) acryl” indicates “acryl or methacryl”. The same applies to “(meth) acrylate”.

Film strength of the resulting coating film, resistance to coating solvent,
Among the above organic polymer substances, those having a carboxylic acid group are used for the purpose of enhancing the adhesiveness to a substrate, and a part or all of the carboxylic acid group is converted to glycidyl (meth) acrylate, [T-1] or [T-2 ] It is also possible to react with an epoxy (meth) acrylate having a structure of to form a photopolymerizable organic polymer substance.

In the present invention, as particularly preferable organic polymer substances, styrene, α-methylstyrene, benzyl (meth) acrylate, hydroxyphenyl (meth) acrylate, methoxyphenyl (meth) are used for the purpose of enhancing the adhesion to the substrate. ) Acrylate, hydroxyphenyl (meth) acrylamide, hydroxyphenyl (meth)
Containing a comonomer having a phenyl group such as acrylsulfoamide in an amount of 10 to 80 mol%, preferably 20 to 70 mol%, more preferably 30 to 60 mol%,
Copolymer containing other (meth) acrylic acid in an amount of 2 to 50% by weight, preferably 5 to 40% by weight, more preferably 5 to 30% by weight, or 2 to 50% based on all copolymerized monomers. Desirably, the reaction product has a mole%, preferably 5 to 40 mol%, and more preferably 10 to 30 mol% epoxy (meth) acrylate added thereto.

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. .

As the radical generator used in the present invention, any radical generator can be used as long as it has a property of generating active radicals by causing some action with the photoexcited sensitizer. For example, a titanocene compound,
Hexaarylbiimidazole, halogenated hydrocarbon derivatives, organic thiol compounds, diaryliodonium salts, and organic peroxides can be mentioned.

Of these, a titanocene compound is particularly preferable. The titanocene compound is disclosed in JP-A-59-
152396, JP-A-61-151197, JP-A-63-10602, JP-A-63-41
No. 484, No. 2-291, No. 3-1
JP-A-2403, JP-A-3-20293, JP-A-3-27393, JP-A-3-52050,
JP-A-4-221958, JP-A-4-21975
No. 6, JP-A-3-27393 and the like can be used.
Cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-
Pentafluorophenyl-1-yl, dicyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophenyl-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6 -Trifluorophenyl-1-yl, di-
Cyclopentadienyl-Ti-bis-2,6-di-fluorophenyl-1-yl, di-cyclopentadienyl-T
i-bis-2,4-di-fluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3
4,5,6-Pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,5
6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluoro- 3- (Bil-1-yl) -phen-1-yl (hereinafter referred to as “compound R-1”) and the like can be mentioned. As the sensitizer used in the present invention, any substance having an action of absorbing light to generate razyl in the radical generator in the presence of a radical generator can be used. Those having a structure are preferable.

[0027]

Embedded image

(Where R¹, R²May have a substituent
An alkyl group having 1 to 10 carbon atoms (wherein the substituent is hydroxy
Group, halogen atom, alkoxy group having 1 to 10 carbon atoms, charcoal
Acyl group having 2 to 10 primes, Aryl group having 6 to 15 carbon atoms
Xy group or alkyloxycarbonyl having 2 to 15 carbon atoms
Group) and R^Three, R^FourIs a hydrogen atom or carbon number 1
10 represents an alkyl group, but R¹And R^Four, R²And R^Three
Are directly bonded to each other or via a sulfur atom or an oxygen atom.
May combine with each other to form a ring, R^FiveIs hydrogen atom, charcoal
Alkyl group having 1 to 10 primes or Alco having 1 to 10 carbons
A xy group; ⁶Is a hydrogen atom, an alkane having 1 to 10 carbon atoms
A kill group or an aryl group having 6 to 15 carbon atoms is shown.^Five
And R⁶At direct bond with each other or via sulfur atom, oxygen atom
May combine with each other to form a ring, and Y is a hydrogen atom or cyano.
Group, an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 10 carbon atoms
Lucoxy group, alkoxycarbonyl group having 2 to 10 carbon atoms
Or represents an acyl group having 2 to 15 carbon atoms). The sensitizer is public
It can be synthesized by a known method, for example, dialkyl
It has a cyanomethyl group equivalent to aminobenzaldehyde.
Of reacting with a compound to be reacted in the presence of a piperidine catalyst
(Formula (1)) and the like can be mentioned.

[0029]

Embedded image Specific examples of the sensitizer include, for example,

[0030]

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[0031]

[Chemical 12]

[0032]

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And the like. In the photopolymerization initiation system of the present invention, a radical chain transfer agent such as an alkylamino compound and an aromatic mercapto compound is further added to the total weight of the photopolymerization initiation system in order to improve sensitivity and stability of the photosensitive solution over time, if necessary. The content can be 5 to 50% by weight, preferably 10 to 30% by weight.

Examples of the alkylamino compound include compounds having a dialkylaminophenyl group and alkylamine compounds described in JP-A-6-19240 and JP-A-6-19249, and specifically, dialkyl As a compound having an aminophenyl group, p-
Examples include compounds such as ethyl dimethylaminobenzoate and dialkylaminophenylcarbaldehydes such as p-diethylaminobenzcarbaldehyde and 9-jurolidylcarbaldehyde, and examples of alkylamine compounds include triethanolamine, diethanolamine and triethylamine. Of these, compounds having a dialkylaminophenyl group are more sensitive and preferred.

Examples of the aromatic mercapto compound include 2-mercaptobenzthiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzthiazole described in JP-A-59-56403.
Mercaptobenzimidazole, 2-mercaptonaphthothiazole, 2-mercaptonaphthoxazole, 2-
Examples include mercaptonaphthoimidazole and the like.

The content of the photopolymerization initiation system is 0.1 to 40% by weight based on the total solid content of the photopolymerizable image-forming material (the portion of the photopolymerizable composition of the present invention excluding the color material). Preferably 0.2 to 30% by weight, more preferably 0.2 to 20
% By weight, and the weight ratio of the addition rate of the sensitizer to the addition rate of the radical generator is 3: 2 to 1: 4, preferably 1: 1 to
The ratio is 1: 3, and if the ratio of the sensitizer is remarkably increased, the sensitivity is lowered. On the contrary, if the ratio of the radical generator is remarkably increased, defective removal of the non-image area is likely to occur during development. The content of the ethylenic compound is 20 to 99% by weight, preferably 50, based on the total solid content of the photopolymerizable image forming material.
To 95% by weight, more preferably 60 to 90% by weight, and the content of the organic polymer substance is 0 to 80% by weight, preferably 1 to the total solid content of the photopolymerizable image forming material.
It is 0 to 70% by weight, more preferably 20 to 60% by weight.

The color material used in the present invention is a black color material for a black matrix, and includes red, green,
For blue, a corresponding color material is used, and in any case, a pigment is preferably used. As a black color material,
For example, MA-7, MA-100, MA- manufactured by Mitsubishi Chemical Corporation.
220, # 5, # 10, or Degus Color
Black FW200, Color Black F
Carbon black such as W2 and Printex V, graphite described in JP-A-5-311109, JP-A-6-11613, etc., inorganic described in JP-A-4-322219, JP-A-3-274503, etc. Black pigment,
Examples thereof include organic black pigments such as azo black dyes described in JP-A-2-216102 and the like, and black pigments mixed with organic color materials such as red, green, blue, 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 (the above (). The numbers inside mean color index (C.I.)).

Regarding other pigments (C.I.)
In the case of, 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 composition of the present invention are as follows. That is, the black matrix formed of the black color filter resist has a dry film thickness of 1.0 μm or less, preferably 0.3 to 0.9 μm, and more preferably 0.5 to 0.8 μm. In order to form a black matrix having a light transmission density of 2.5 or more, preferably 3.0 or more, the content of the black color material contained in the photopolymerizable composition is the total solid content. On the other hand, it is in the range of 40 to 90% by weight, preferably 50 to 80% by weight.

On the other hand, the color material pixels formed of red, green and blue color filter resists are 1.0 μm or less, preferably 0.3 to 0.9 μm, more preferably 0.5 to 0.
The above-mentioned red contained in the photopolymerizable composition in order to form a color material pixel having a light transmission density of 1.1 or more, preferably 1.3 or more, of a coating film formed to a film thickness of 8 μm, The amount of green and blue color materials added is in the range of 40 to 90% by weight, preferably 50 to 80% by weight, based on the total solid content. The above transmission densities of black, red, green and blue are Macbeth densitometer TR-9.
It is obtained by measuring with No. 27 and using an optical filter corresponding to each color.

The color filter resist, which is the target of the developing solution of the present invention, forms a high-quality black matrix image or color material pixel in such a state that the content of the color material is high, and is applied on each pixel. A coloring material photopolymerizable layer or a protective layer made of polyamide, polyimide, or the like that provides solvent resistance to a coating solvent and high adhesion to a transparent substrate is particularly preferable. Such a color filter resist is applied as a coating solution prepared by using an appropriate solvent.

Solvents used for coating the color filter resist according to the present invention include methyl cellosolve, ethyl cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, toluene, chloroform, dichloromethane. , Ethyl acetate, methyl lactate,
Ethyl lactate, methanol, ethanol, propanol,
Butanol, tetrahydrofuran, etc. are mentioned.

The coating liquid contains these solvents and has a color filter resist (total of color material and photopolymerizable image forming material) concentration of 5 to 50% by weight, preferably 10 to 30%.
The solution is prepared so as to be in the range of weight%. Next, a method for producing a color filter using the photopolymerizable composition for a color filter of the present invention will be described. Examples of the transparent substrate for the color filter 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, in order to improve the physical properties such as the adhesiveness of the surface, corona discharge treatment, ozone treatment, thin film formation of various polymers such as silane coupling agent and urethane polymer, if necessary. Processing etc. can be performed. The thickness of the transparent substrate is 0.05 to 10 mm,
In particular, it is preferable to be in the range of 0.1 to 7 mm. Further, when a thin film forming treatment of various polymers is performed, the film thickness is preferably in the range of 0.01 to 10 μm, particularly 0.05 to 5 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 pixel images of red, green and blue. 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 color filter resist containing a color material of one color of red, green and blue is spinner-coated.
After coating with a coating device such as a wire bar, a flow coater, a die coater, a roll coater, or a spray, 5
15 at a temperature of 0 to 200 ° C., preferably 80 to 180 ° C.
The coloring material photopolymerizable layer is formed by drying at a temperature of 120 to 160 ° C. for 15 seconds to 10 minutes, preferably 30 seconds to 5 minutes, for 10 seconds to 10 minutes, preferably 30 seconds to 5 minutes. Here, the film thickness of the photopolymerizable layer obtained by applying and drying the coating solution of the color filter resist is preferably 0.2 to 2 μm, more preferably 0.5.
˜1 μm.

Here, the higher the drying temperature, the higher the adhesion to the transparent substrate and the higher the resist sensitivity.
On the other hand, if it is too high, the photopolymerization initiator composition is decomposed, and thermal polymerization is induced to easily cause development failure. Further, if the drying temperature is extremely low, the sensitivity is lowered and it becomes difficult to form an image. next,
A negative photomask for colorant pixels is placed on the colorant photopolymerizable layer, and image exposure is performed through the photomask using a light source such as ultraviolet light or visible light. At this time, if necessary, in order to prevent the sensitivity of the photopolymerizable layer from being lowered by 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 a developing solution to form a first color material pixel image on the transparent substrate. If necessary, the sensitivity of the photopolymerizable layer or the γ
The exposed sample is 70 to 200 ° C for the purpose of increasing the value (gradation).
15 seconds to 20 minutes, preferably 30 at 80 to 150 ° C
Heat treatment for 10 seconds to 10 minutes can be performed.

The developing solution used in the developing treatment is preferably an alkaline developing solution or a neutral developing solution containing a surfactant. The alkaline developer is, for example, an inorganic alkaline agent such as sodium carbonate, potassium carbonate, sodium silicate, potassium silicate, sodium hydroxide, potassium hydroxide, or an organic alkali agent such as diethanolamine, triethanolamine, or a tetraalkylammonium hydroxide salt. An aqueous solution containing an alkaline agent and, if necessary, a surfactant, a water-soluble organic solvent, a low-molecular compound having a hydroxyl group or a carboxylic acid group, etc. for the purpose of improving image quality and shortening development time.

As the surfactant of the developing solution, an anionic surfactant having a sodium naphthalenesulfonate group, a sodium group of benzenesulfonate, a nonionic surfactant having a polyalkyleneoxy group, and a cation having a tetraalkylammonium group are used. Examples of the water-soluble organic solvent include ethanol, propylene 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,
Examples include pyrogallol, benzoic acid, succinic acid, and glutaric acid. Further, the neutral developing solution contains a surface activity such as the above-mentioned anionic surfactant and nonionic surfactant, and if necessary, for the same purpose as described above,
It is an aqueous solution containing the same water-soluble organic solvent as described above, a low molecular weight compound having a hydroxyl group or a carboxylic acid group, and the like.

The development treatment is usually carried out at a development temperature of 20 to 40 ° 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 applied on the sample, or durability of a protective layer such as polyamide or polyimide against a coating solvent, or a transparent substrate such as a glass substrate. For the purpose of enhancing the adhesiveness with
The heat curing treatment may be performed at 0 to 250 ° C. for 5 to 60 minutes, or the light exposure may be performed at an appropriate exposure amount or more, preferably an exposure amount 1 to 10 times the appropriate exposure amount. .

Subsequently, the other two color filter resists of red, green, and blue are coated and dried on the sample in the same manner as described above, and then the sample is applied to a negative for a color material pixel. Using a photomask, exposure, development, and optionally heat or photo-curing treatment are repeated in the same manner as described above to form pixels of three colors between black matrices to produce a color filter.

The color filter manufactured in this manner has ITO (transparent electrode) formed on the color filter as it is and is used as a part of a component of a color display. Alternatively, a top coat layer of polyamide, polyimide or the like may be provided for the purpose of enhancing durability. Light sources used for image exposure include xenon lamps, halogen lamps, tungsten lamps, high pressure mercury lamps, metal halide lamps,
Examples thereof include lamp light sources such as medium-pressure mercury lamps and low-pressure mercury lamps, and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, and nitrogen lasers. 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 using the color filter resist according to the present invention containing a black color material, the same method as that for forming red, green and blue pixel images on a transparent substrate is used. A black matrix is formed by adopting the 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.

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, but the method of forming the black matrix after forming the red, green and blue pixel images is also adopted. It is possible. Further, when the color filter resist according to the present invention is used to form a black stripe or red, green, or blue color material pixel image on a transparent substrate, a developed image of the color filter resist and the transparent substrate is obtained. For the purpose of enhancing the adhesiveness and / or the adhesiveness of the thermosetting image, a photocurable adhesive layer obtained by photocuring a photopolymerizable composition containing no color material can be provided on the transparent substrate.

The photopolymerization initiator composition contained in the photopolymerizable composition used in the photocurable adhesive layer, the ethylenic compound, and the organic polymer substance optionally used are the same as those in the present invention. It can be appropriately selected and used from the constituent components of such a color filter resist, and such a photocurable adhesive layer is obtained by using the photopolymerizable composition in a dry film thickness of 0 by the same method as described above. After being coated on a transparent substrate so as to be in the range of 0.01 to 2 μm, preferably 0.02 to 1 μm, the exposure amount is 1 to 10 times the appropriate exposure amount of the coated photopolymerizable composition layer. It can be formed by exposing and photo-curing.

Furthermore, a black stripe formed on a transparent substrate using the color filter resist according to the present invention, or a resist image such as red, green, and blue color material pixels from the transparent substrate over time. For the purpose of preventing the occurrence of defects such as peeling and 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.

[0060]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to the following Examples unless it exceeds the gist. Examples 1 to 16 and Comparative Examples 1 to 4 Carbon black (“MA-220” manufactured by Mitsubishi Chemical Corporation) of the types and amounts shown in Table 1 below, an organic polymer and 400 parts by weight of cyclohexanone were mixed, The mixture was placed in a paint shaker containing 3.6 times by weight of 0.5 mm zirconia beads and dispersed for 17 hours. A coating liquid was prepared by adding 400 parts by weight of a sensitizer, a radical generator, an ethylenic compound and, if necessary, a chain transfer agent and cyclohexanone to the obtained dispersion liquid in the types and amounts shown in Table 1 below.

[0061]

Embedded image

[0062]

[Chemical 15]

[0063]

Embedded image

[Radical Generator] R-1: Dicyclopentadienyl-Ti-bis-2,6
-Difluoro-3- (pyrr-1-yl) -phen-1-
IL [chain transfer agent] X-1: ethyl p-dimethylaminobenzoate

The prepared black colorant-containing photopolymerizable coating solution was applied onto a glass substrate (Corning No. 7059) by a wire bar coater so that the dry film thickness was 0.9 μm, and the drying temperature was 150. It was dried at ℃ for 1 minute. Next, using a negative photomask for a black matrix which is repeated at a pitch of 330 μm in length and 110 μm in width with a width of 30 μm, it was exposed with a 2 Kw high-pressure mercury lamp at an appropriate exposure amount shown in Table 1, and then with 0.25 wt% potassium carbonate. 3% by weight of nonionic surfactant (Nippon Emulsifier: Newc
ol B-10), a developing solution containing an aqueous solution is used for immersion for 30 seconds at 25 ° C., and then 2 Kg / cm ²
After washing with water and developing treatment to form a black matrix, the sample was heat-cured by heat treatment at 200 ° C. for 7 minutes. Also,
The evaluation shown in Table 1 was performed by the same method.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[Transmission Density] Macbeth Densitometer TR-927
Was used to measure the transmission density (ABS) of the sample. Further, the film thickness of the photosensitive layer of the sample was measured by a step manufactured by Tencor Instruments Inc., and is described in []. [Concentration of color material] The ratio of the pigment contained in the solid content of the black color material photopolymerizable coating liquid. Color material concentration = Color material weight / Total solids weight

[Appropriate Exposure Amount] The Ugula test chart was placed on a sample, exposed with a 2 Kw high-pressure mercury lamp while changing various exposure amounts on the chart, and then subjected to development treatment to obtain the Ugula test chart. The amount of exposure when the thinnest positive line of the image and the thin line of the negative have the same line width. In addition, F indicates that an image was not formed because the photosensitive layer was completely dissolved in the developing process or was not dissolved at all.

[Image Quality] By a method similar to the above, after applying the coating material for the photopolymerizable layer of the coloring material on the glass substrate and drying it,
Exposure was performed with an appropriate exposure amount using a Ugura test chart, and development processing was performed using a standard developing solution to form a color material image. The fine line image in the color material image was observed with 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. 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.

Example 17 In the photopolymerizable composition of Example 4, the radical generator was 2,
2'-bis (o-chlorophenyl) -4,4 ', 5
When a photopolymerizable composition was prepared in the same manner as in Example 4 except that 5'-tetra-o, p-dichlorophenylbiimidazole was used, the same exposure sensitivity as 700 mJ was obtained.
/ Cm ² .

[0073]

As described in detail above, the photopolymerizable composition for a color filter of the present invention contains a benzylidene type sensitizing dye having a specific structure and a titanocene compound as a radical generator, whereby the exposure sensitivity is improved. It is possible to select a color filter stably and efficiently at a high line speed with high image quality and excellent image reproducibility.

Claims (6)

[Claims] 1. An ethylenically unsaturated double bond at least
Contains one compound, photopolymerization initiation system and color material
In the photopolymerizable composition, the photopolymerization initiation system is used as a radical generator and a sensitizer as follows.
The color material contains a compound represented by the general formula (I),
40% by weight or more based on the total solid content of the polymerizable composition
Photopolymerization for color filters characterized by being
Composition. [Chemical 1](In the formula, R¹, R²Is a carbon number of 1 to 1 which may have a substituent.
10 alkyl groups (wherein the substituents are hydroxyl, halogen
Atom, alkoxy group having 1 to 10 carbon atoms, 2 to 10 carbon atoms
Acyl group, aryloxy group having 6 to 15 carbon atoms or charcoal
Is an alkyloxycarbonyl group having a prime number of 2 to 15)
Show, R^Three, R^FourIs a hydrogen atom or an alkyl group having 1 to 10 carbon atoms
Indicates a kill group, but R¹And R^Four, R²And R^ThreeAre each other
Directly bonded or bonded via a sulfur atom or an oxygen atom
May form a ring, R^FiveIs a hydrogen atom, having 1 to 10 carbon atoms
Represents an alkyl group or an alkoxy group having 1 to 10 carbon atoms.
Then R ⁶Is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, or
An aryl group having 6 to 15 carbon atoms is shown.^FiveAnd R⁶And each other
Directly bonded or bonded via a sulfur atom or an oxygen atom
A ring may be formed, and Y is a hydrogen atom, a cyano group, or the number of carbon atoms.
1-10 alkyl group, C1-C10 alkoxy
Group, an alkoxycarbonyl group having 2 to 10 carbon atoms or carbon
(Indicates an acyl group of 2 to 15) 2. The photopolymerizable composition for a color filter according to claim 1, wherein the weight ratio of the sensitizer to the radical generator is 3: 2 to 1: 4. 3. The color filter according to claim 1, wherein an addition reaction product of a polyglycidyl ether compound and an unsaturated carboxylic acid is used as the compound having at least one ethylenically unsaturated double bond. Photopolymerizable composition. 4. A compound having a substituent represented by the following general formula (II) or (III) as a compound having at least one ethylenically unsaturated double bond, wherein: Photopolymerizable composition for color filters. Embedded image (In the formulas (II) and (III), m represents an integer of 0 to 6,
R ⁷ and R ⁸ represent a hydrogen atom or a halogen atom, and R ⁹ represents an alkylene group having 1 to 10 carbon atoms which may have a substituent (the substituent may have a hydroxyl group, a halogen atom or a hydroxyl group. Good alkyl group having 1 to 10 carbon atoms, alkoxy group having 1 to 10 carbon atoms, aryl group having 6 to 15 carbon atoms, 7 carbon atoms
An aralkyl group having 15 to 15 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and an acyloxy group having 2 to 10 carbon atoms. ), And R ¹⁰ is a hydrogen atom or a C 1 -C 1 which may have a hydroxyl group.
It represents an alkyl group having 10 to 10 carbon atoms, an aryl group having 6 to 15 carbon atoms, an aralkyl group having 7 to 15 carbon atoms or an alkenyl group having 2 to 10 carbon atoms, and R ¹¹ represents a hydrogen atom or a methyl group. ) 5. A coating film containing a red, green or blue material as a color material and having a dry film thickness of 1 μm or less has a light transmission density of 1.1 or more. The photopolymerizable composition for a color filter described. 6. The color filter according to claim 1, wherein the coating material containing a black material as a color material and having a dry film thickness of 1 μm or less has a light transmission density of 2.5 or more. Photopolymerizable composition.