JPH09179296A - Photopolymerizable composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably and efficiently produce a color filter excellent in image developability by incorporating an ethylenic compd. having a specified structure. SOLUTION: This compsn. contains a compd. having at least one ethylenically unsatd. double bond, a photopolymn. initiator and a coloring material. The compd. having at least one ethylenically unsatd. double bond is a compd. having an oxycyclohexyloxyphenyl or oxycyclohexyloxycyclohexyl skeleton. This ethylenic compd. preferably has two or more ethylenically unsatd. double bonds at which polymn. is induced in the presence of the photopolymn. initiator. An org. polymer may be added as a binder to this compsn.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a photopolymerizable composition. More specifically, it relates to a photopolymerizable composition which can be suitably used for a photosensitive lithographic printing plate, an etching resist, a color proof, a color filter and the like.

[0002]

2. Description of the Related Art A color filter generally has three different hues of red, green and blue on the surface of a transparent substrate such as glass or plastic sheet provided with a black matrix.
It is manufactured by forming a stripe-shaped or mosaic-shaped color pattern having a width of 10 to 50 μm with an accuracy of several μm. Typical methods for producing a color filter 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. Of these methods, a photopolymerizable composition containing a color material is applied on a transparent substrate provided with a black matrix, and image exposure, development, and heat curing are repeated to form a color filter image. The method is widely used because it has high accuracy in the position of the color filter pixel and film thickness, 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, a photopolymerization initiation system, and a solvent. As the compound having at least one ethylenically unsaturated double bond (hereinafter referred to as “ethylenic compound”), a (meth) acrylate compound of polyphenol glycidyl ether has been conventionally used (JP-A-7-13331, JP-A-4-13331). 34
No. 0965) is used for a color filter. In addition, in this specification, "(meth) acry" is synonymous with "methacry" or "acry", and for example, "(meth) acrylate" is "methacrylate or acrylate".
Is synonymous with

[0004]

However, since the photopolymerizable composition for a color filter contains about 30% of a color material, this color material shields light during exposure, which results in image formation. There was a problem that the sex and sensitivity were not sufficient. An object of the present invention is to solve the above-mentioned conventional problems, and to provide a photopolymerizable composition having high sensitivity and excellent in image forming property, which is particularly suitable for color filter applications.

[0005]

Accordingly, the object of the present invention is to provide a photopolymerizable composition containing a compound having at least one ethylenically unsaturated double bond, a photopolymerization initiator and a color material. It is easily achieved by a photopolymerizable composition characterized in that the compound having at least one ethylenically unsaturated double bond is oxycyclohexyloxyphenyl or a compound having an oxycyclohexyloxycyclohexyl skeleton. Hereinafter, the present invention will be described in detail.

The compound having at least one ethylenically unsaturated double bond having an oxycyclohexyloxyphenyl or oxycyclohexyloxycyclohexyl skeleton (hereinafter referred to as "ethylenic compound A") used in the present invention is a photopolymerization initiator. A compound having two or more ethylenically unsaturated double bonds in which the polymerization is induced in the presence thereof is preferable, and specifically, any one of the partial structures represented by the following general formulas (1) to (4) Compounds having two or more in the molecule are preferred. The ethylenic compound improves adhesion to a transparent substrate and image forming property.

[0007]

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Y is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent (a substituent is a hydroxyl group,
An alkyloxy group having 1 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, an acyl group having 2 to 15 carbon atoms, a (meth) acroyloxy group, an acyloxy group, B
Indicates a halogen atom of r or Cl. ), An aryl group having 6 to 15 carbon atoms, an allyl group having 3 to 10 carbon atoms, a hydroxyl group, and an alkyloxy group having 1 to 10 carbon atoms, R ⁴ is a hydrogen atom,
It represents an alkyl group having 1 to 10 carbon atoms, and X represents a halogen atom such as Cl or Br. )

Specific examples of the ethylenic compound (A) include polyhydroxybenzenes such as hydroquinone, resorcin, and pyrogallol, bisphenol A derivatives such as bisphenol A and brominated bisphenol A, and aromatic polyhydroxy compounds such as novolac. And a polyglycidyl ether compound obtained by addition-reacting the nuclear hydrogenation product with 1,2 epoxycyclohexane under a quaternary ammonium condition, and then further subjecting epichlorohydrin to an addition reaction under an alkaline condition, (meth) acrylic acid, etc. Of the unsaturated monocarboxylic acid or unsaturated monocarboxylic acid chloride obtained by the addition reaction with a quaternary ammonium salt as a catalyst, or a polyhydroxybenzene such as hydroquinone, resorcinol or pyrogallol, or a vinyl chloride. Phenol A, bisphenol A derivatives such as brominated bisphenol A, aromatic polyhydroxy compounds such as novolak, and 1,2 epoxycyclohexane adducts of their hydrogenation in the nucleus and glycidyl (meth) acrylate, the following [T-1 ] Or [T-2]
Epoxy (meth) acrylates having the same structure as "SYN
THETIC COMMUNICATION, 24 (2
1) having two or more substituents represented by the general formulas (1) to (4), which are obtained by addition reaction using an acid or alkali catalyst described in “3009-3019 (1994)” An ethylenic compound is mentioned, More specifically, for example, the following (A-1), (A-2), (B-
1), (B-2), etc. can be mentioned. As the hydrogenation reaction, those using Raney Ni catalyst described in JP-A-3-107160 and the like and those using catalysts such as rhodium and platinum can be appropriately selected and used.

[0010]

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(In the formula, q represents an integer of 1 to 5, and R¹
~ R^Four, Z, Y, m are the same as above, R ^Ten, R¹¹Is hydrogen field
Child, an alkyl group having 1 to 15 carbon atoms, an alkyl group having 1 to 15 carbon atoms
Rukyloxy group, aryl group having 6 to 15 carbon atoms, carbon number
7 to 15 aralkyl groups, or R^Ten, R¹¹Each other
Via divalent atoms such as rubylene group, oxygen atom, sulfur atom, etc.
May combine with each other to form a cyclic structure, and U has 1 carbon atom
An alkylene group optionally having a substituent of
As the substituent, an alkyl group, a phenyl group, Br, Cl
Represents a halogen group. ), Oxygen atom, sulfur atom, sulfur atom
Honyl group, amino group, C1-C15 monoalkyl group
It represents a mino group or an aryl group having 6 to 15 carbon atoms. )

[0012]

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(Wherein R ^{1 to} R ⁴ , R ^{10 to} R ¹¹ , Z,
Y, m, q and U are the same as above. )

[0014]

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(Wherein q, R ^{1 to} R ⁴ , X, Y, U,
m, R ¹⁰ and R ¹¹ are the same as above. )

[0016]

[Chemical 6]

(Where q, R ^{1 to} R ⁴ , X, Y, U,
m, R ¹⁰ and R ¹¹ are the same as above. ) And the like, and more specific examples include

[0018]

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[0019]

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[0020]

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[0021]

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And the like. On the other hand, as the ethylenic compound used in the present invention, in addition to the ethylenic compound (A), the solubility of the non-image area during development is increased,
An ethylenic compound (B) other than the ethylenic compound (A) can be used in combination for the purpose of forming a high quality image.

Specific examples of the ethylenic compound (B) include an addition reaction of a polyglycidyl ether compound other than the ethylenic compound (A) with an unsaturated monocarboxylic acid or an unsaturated monocarboxylic acid chloride, or Ethylenic compounds obtained by the addition reaction of a polyhydroxy compound with an epoxy monounsaturated carboxylic acid ester, or a hydrogenation product in the nucleus of these compounds, or an addition reaction of an aliphatic polyhydroxy compound with an unsaturated carboxylic acid ( Ester reaction), which is an ethylenic compound, and specific examples thereof 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 divinyl phthalate, 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 composition of the present invention, an organic polymer substance may be added as a binder for the purpose of improving film-forming property and developability. Examples of the organic polymer substance include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, propyl (meth) acrylic acid, butyl (meth) acrylic acid,
2-ethylhexyl (meth) acrylic acid, hydroxyethyl (meth) acrylic acid, hydroxypropyl (meth)
(Meth) such as acrylic acid, benzyl (meth) acrylic acid
Alkyl ester of acrylic acid; Phenyl ester which may have a substituent of (meth) acrylic acid such as hydroxyphenyl (meth) acrylic acid and methoxyphenyl (meth) acrylic acid; acrylonitrile; vinyl acetate,
Vinyl salts such as vinyl versatate, vinyl propionate, vinyl cinnamate, vinyl pivalate; styrene, α-
Copolymer of methyl-styrene, polyether of epichlorohydrin and bisphenol A, soluble nylon,
Examples thereof include polyvinyl alkyl ether, polyamide, polyurethane, polyethylene terephthalate isophthalate, acetyl cellulose, polyvinyl formal, and polyvinyl butyral. In this specification,
"(Meth) acrylic" means "acrylic or methacrylic"
Is shown. The same applies to “(meth) acrylate”.

The film strength of the obtained 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. ] It is also possible to react with an epoxy (meth) acrylate having a structure of to form a photopolymerizable organic polymer substance.

[0028]

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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 such an organic polymer substance 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-slip in the image area will occur during development, and conversely, if the Mw of the organic polymer material is significantly high, defective removal of the non-image area will tend to occur during development. .

As the photopolymerization initiator used in the photopolymerizable composition of the present invention, one 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 above 400 nm
Examples of the photopolymerization initiation system that absorbs ultraviolet light having a wavelength of less than to generate radicals include Fine Chemical, 199
Vol. 1, No. 1, March 1, 1st year. 4, p. 16 ~
P. 26, dialkyl acetophenone type, benzyl dialkyl ketal type, benzoin, benzoin alkyl ether type, thioxanthone derivative, acylphosphine oxide type, etc., and others, JP-A-58-40302.
The hexaarylbiimidazole type, the s-trihalomethyltriazine type described in JP-B No. 45-37377 and the titanocene type described in JP-A No. 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 are combined with an addition-polymerizable ethylenic saturated double bond-containing compound having an amino group or a urethane group (JP-A-4-221958, JP-A-4-221958). 4-21
9756 each gazette) etc. are mentioned.

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.
Sensitizing dye having absorption at 500 nm, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (o-chlorophenyl) -4 , 4 ', 5,5'-Tetra (p-carboethoxyphenyl) biimidazole, 2,2'-bis (o-chlorophenyl) -4,4', 5,5'-tetra (p-bromophenyl) bi Hexaarylbiimidazoles such as imidazole, 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetra (o, p-dichlorophenyl) biimidazole, and 2-mercaptobenzthiazole, 2 -Mercaptobenzoxazole,
A composite photopolymerization initiator composed of an organic thiol compound such as 2-mercaptobenzimidazole, or a wavelength of 400-
Sensitizing dyes having absorption at 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, di-cyclopentadienyl-
A composite photopolymerization initiator comprising a titanocene compound such as Ti-bis-2,3,4,5,6-pentafluorophenyl-1-yl and a dialkylaminophenyl compound such as ethyl p-diethylaminobenzoate and Michler's ketone Can be mentioned.

Examples of the dyes which sensitize the above hexabiimidazole include 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.
Further, among these photopolymerization initiation systems sensitive to the visible light region, those having a high sensitivity in the ultraviolet region together with visible light are used as a photopolymerization initiation system for a light source in the ultraviolet light region. Is also good.

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 photopolymerization initiation system,
Hexaarylbiimidazole, a photopolymerization initiation system containing titanocene is preferred because it shows high sensitivity, in particular, if the photopolymerization initiation system containing titanocene, compared to the photopolymerization initiation system containing hexaarylbiimidazole Since it shows high sensitivity with a small amount and is stable even under high drying conditions, it is even more preferable for a color filter resist having a high color material concentration as in the present invention.

The content of the photopolymerization initiator composition is 0.1 to 40% by weight, preferably 0.1 to 40% by weight based on the total solid content of the photopolymerizable image forming material (photopolymerizable image forming material containing no color material). Is 0.2 to 30% by weight, more preferably 0.2 to 20
The content of the ethylenic compound is 20 to 99% by weight, preferably 50 to 95% by weight, and more preferably 60% by weight based on the total solid content of the photopolymerizable image forming material.
Is about 90% by weight, and the content of the organic polymer is
0 to 80% by weight, preferably 10 to 70% by weight, and more preferably 20% by weight based on the total solid content of the photopolymerizable image forming material.
６０60% by weight.

Known color materials for photopolymerizable compositions can be used as the color material used in the present invention, but black color materials are used for the color filter resist for the black matrix, and color materials for red, green and blue are used. A color material corresponding to the filter resist is used. Examples of black color materials include MA-7 and MA-10 manufactured by Mitsubishi Chemical Corporation.
0, MA-220, # 5, # 10, or C manufactured by Degus Co.
color Black FW200, Color Bl
ack FW2, carbon black such as Printex V, JP-A-5-311109, JP-A-6-11
Graphite described in Japanese Patent No. 613, etc., Japanese Patent Application Laid-Open No. 4-32221
9. Daiiro Seika Kogyo Co., Ltd.'s Daipyroxide color black # 9550, and inorganic black pigments described in JP-A-3-274503 and the like, and azo black dyes described in JP-A-2-216102 and the like. Examples thereof include organic black pigments, and black pigments in which organic color materials such as red, green, blue, yellow, cyan, and magenta are mixed.

Specific examples of color materials corresponding to red, green and blue include Victoria Pear Blue (42595), Auramine 0 (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.)
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 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 resist is based on the total solid content.
It is in the range of 50 to 90% by weight, preferably 60 to 80% by weight.

On the other hand, the color material pixels formed of red, green and blue resists are 1.0 μm or less, preferably 0.3 to 0.
In order to form color material pixels having a light transmission density of 1.1 or more, preferably 1.3 or more, a coating film formed to have a film thickness of 9 μm, more preferably 0.5 to 0.8 μm The amount of the red, green, and blue color materials contained in the composition is 50 to 90% by weight, preferably 6% by weight based on the total solid content.
It is in the range of 0 to 80% by weight. The transmission densities of black, green, blue and red can be obtained by measuring with Macbeth densitometer TR-927 and using optical filters corresponding to the respective colors.

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, dichloro. Methine, ethyl acetate, methyl lactate,
Ethyl lactate, methanol, ethanol, propanol,
Butanol, tetrahydrofuran, etc. are mentioned. The coating solution is prepared using these solvents so that the concentration of the color filter resist (the total of the color material and the photopolymerizable image forming material) is in the range of 5 to 50% by weight, preferably 10 to 30% by weight. Be liquefied.

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. Such a transparent substrate may be subjected to corona discharge treatment, ozone treatment, thin film formation treatment of various polymers such as silane coupling agent and urethane polymer, etc., as necessary to improve physical properties such as surface adhesiveness. It can be carried out.

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 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, flow coater, die coater, roll coater, or spray, 5
15 at a temperature of 0 to 200 ° C., preferably 80 to 180 ° C.
Seconds to 10 minutes, preferably 30 seconds to 5 minutes, more preferably at a temperature of 120 to 160 ° C. for 15 seconds to 10 minutes,
Preferably, the coloring material photopolymerizable layer is formed by drying for 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.
１1 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. On the other hand, when the drying temperature is extremely low, the sensitivity is lowered and the image formation becomes difficult. Next, a negative photomask for colorant pixels is placed on this colorant photopolymerizable layer, and image exposure is performed through the photomask using a light source such as ultraviolet 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. Contains an alkaline agent and, if necessary, a surfactant for the purpose of improving image quality and shortening development time,
It is 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.

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.

As the low molecular weight compound having a hydroxyl group or a carboxy group, 1-naphthol, 2-naphthol,
Examples include pyrogallol, benzoic acid, succinic acid, and glutaric acid. Further, the neutral developer contains a surfactant such as the anionic surfactant and the nonionic surfactant described above, and, if necessary, the same water solubility as the above for the same purpose as described above. Is an aqueous solution containing the organic solvent, the 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 and ultrasonic development.
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 curing treatment may be performed at an exposure amount equal to or higher than the appropriate exposure amount, preferably 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 produced in this way has ITO (transparent electrode) formed on it in this state 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.

As a light source used for image exposure, 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, and an argon ion laser, Y
Laser light sources such as an AG laser, an excimer laser, and 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 color filter resist of the present invention containing a black color material, red on the transparent substrate,
The black matrix is formed by adopting the same method as the method of forming the green and blue pixel images. 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 a black stripe or red, green, and blue color material pixel images are formed on a transparent substrate using the color filter resist according to the present invention, a developed image of the color filter resist and the transparent substrate is formed. 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 by 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.

[0057]

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. Synthesis Example 1 (Synthesis of E-1) Bisphenol A (11.4 g) and 1,2-epoxycyclohexane (9.8 g) were installed in a cooling / condensing device (500 ml).
In a 3-necked flask, and stir at 100 ° C for 15
After reacting for a time, the following dialcohol compound (D-1)

[0058]

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Was synthesized. Next, a solution prepared by mixing 10 g of the dialcohol compound (D-1) and 177 g of epichlorohydrin was added to 3.7 g of tetramethylammonium hydrojansulfate, 168 g of potassium hydroxide and 1 part of water.
The mixture was added dropwise to 20 g of a mixed solution under reaction conditions of 20 ° C. or lower over 1 hour with stirring, further stirred at 20 ° C. or lower for 5 hours, and stirred at room temperature for 5 hours, and then the following diglycidyl ether compound (D-2).

[0060]

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Was synthesized. Then, to 25 g of the diglycidyl ether compound (D-2), 7.2 g of acrylic acid, 0.2 g of tetramethylammonium chloride and 0.02 g of paramethoxyphenol were added, and the mixture was reacted at 80 ° C. for 10 hours with stirring to obtain the objective. The ethylenic compound E-1 was synthesized.

Synthesis Example 2 (Synthesis of E-2) To 25 g of the diglycidyl ether compound (D-2), 8.1 g of acrylic acid chloride, 20 g of toluene, 0.2 g of tetramethylammonium chloride and 0.04 g of paramethoxyphenol were added. After reacting at 80 ° C. for 15 hours while stirring, the reaction product returned to room temperature is neutralized with an aqueous sodium carbonate solution, the toluene layer is dried over sodium sulfate, and then evaporated to evaporate the target compound (E- 2) was synthesized.

Examples 1 to 10 and Comparative Examples 1 to 4 The following types and blends of (i) and (ii) were adopted as the photopolymerization initiation system composition, and the following α was used as the organic polymer substance. The compounds shown in Table 1 were used, and a photopolymerizable composition for forming a black matrix containing a black coloring material was prepared with the following composition, and further 3 parts by weight based on the photopolymerizable composition. A coating solution was prepared by dispersing for 17 hours using a paint shoeker containing zirconia beads having a diameter of 0.5 mm.

[Black Coloring Material Photopolymerizable Coating Solution Composition] Photopolymerization initiator composition: described in Table 1 Organic polymer substance: described in Table 1 ethylenic compound: described in Table 1 coating solvent (cyclohexanone): 500 Parts by Weight Black Pigment (Carbon Black (“MA-2 manufactured by Mitsubishi Chemical Corporation”
20 ")): Addition rate (pigment concentration) is shown in Table 1.

[Photopolymerization Initiating System Composition]

[0066]

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[0067]

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[Organic polymer substance]

[0069]

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The prepared black colorant-containing photopolymerizable coating solution was applied to a glass substrate (Corning No. 7059) by a wire bar coater so that the dry film thickness shown in Table 1 was obtained, and the drying temperature was adjusted. It was dried at 150 ° C. for 1 minute. Then, using a negative photomask for a black matrix, which is repeated at a pitch of 30 μm in width and 330 μm in length and 110 μm in width, it was exposed by a 2 kW high-pressure mercury lamp at an appropriate exposure amount shown in Table 1, and then 0.15 wt% potassium carbonate and 0 0.5% by weight of nonionic surfactant (Nippon Emulsifier: New
col B-15) is used for the developing solution consisting of an aqueous solution, and it is immersed for 60 seconds at 25 ° C., followed by 4 kg / cm 2.
^After spray-washing with the water-washing spray of No. 2 and developing treatment to form a black matrix, the sample was heat-cured by heat treatment at 200 ° C. for 7 minutes. Moreover, the evaluation shown in Table 1 was performed by the same method.

[0071]

[Table 1]

The description of each item in Table 1 is as follows. [Ethylene compound]

[0073]

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[0074]

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[0075]

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[Pigment Concentration] Ratio of pigment contained in the solid content of the black colorant photopolymerizable coating liquid. Pigment concentration = pigment weight / total solids weight

[Appropriate Exposure Amount] The Ugra 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 developed to obtain the Ugla 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] After applying the coloring material photopolymerizable layer coating liquid on the glass substrate and drying by the same method as described above,
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.

[Transmission Density] The transmission density (ABS) of the sample was measured using a Macbeth densitometer. Further, the film thickness of the photosensitive layer of the sample was measured by α-step manufactured by Tencor Instruments Inc. and described in [].

[0080]

As described in detail above, the photopolymerizable composition of the present invention contains an ethylenic compound having a specific structure and thus has excellent image developability. To be able to manufacture.

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Claims (4)

[Claims] 1. A photopolymerizable composition containing a compound having at least one ethylenically unsaturated double bond, a photopolymerization initiator and a color material, wherein the compound has at least one ethylenically unsaturated double bond. Is a compound having an oxycyclohexyloxyphenyl or oxycyclohexyloxycyclohexyl skeleton, and a photopolymerizable composition. 2. The compound having at least one ethylenically unsaturated double bond is a compound having at least one partial structure represented by the following general formulas (1) to (4). The photopolymerizable composition according to 1. Embedded image Y is a hydrogen atom or C1 to C2 which may have a substituent.
An alkyl group of 0 (a hydroxyl group as a substituent, a carbon number of 1 to 1)
0 alkyloxy group, C2-10 alkyloxycarbonyl group, C2-15 acyl group, (meth)
An acroyloxy group, an acyloxy group and a halogen atom are shown. ), An aryl group having 6 to 15 carbon atoms, and 3 to 1 carbon atoms
0 represents an allyl group, a hydroxyl group, and an alkyloxy group having 1 to 10 carbon atoms, R ⁴ represents a hydrogen atom and an alkyl group having 1 to 10 carbon atoms, and X represents a halogen atom. ) 3. A light transmission density of 1.1 or more when a coating film is formed to have a dry film thickness of 1 μm or less, which contains a red, green or blue material as a color material. The photopolymerizable composition according to 1 or 2. 4. A color material containing a black material and having a light transmission density of 2.5 or more when a coating film having a dry film thickness of 1 μm or less is formed. A photopolymerizable composition.