JPH11184093A - Photosensitive composition, photosensitive liquid, photosensitive element and production of color filter or color proof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colored image forming material having high sensitivity, heat resistance and high resolving power by incorporating a photoinitiator, a monomer having one or more ethylenically unsatd. bonds, an alkali-soluble disperse resin and a colorant. SOLUTION: The photosensitive compsn. contains a bisacylphosphine oxide as a photoinitiator, a monomer having one or more ethylenically unsatd. bonds in the molecule, an alkali-soluble disperse resin and a colorant. The photoinitiator is, e.g. benzophenone and the amt. is preferably 0.01-25 wt.% of the total amt. of the solids in the photosensitive liq. The monomer is, e.g. trimethylolpropane triacrylate and the amt. is preferably 1-30 wt.% of the total amt. of the solids. The disperse resin preferably has an acid value of 20-300 and a wt. average mol.wt. of 1,500-200,000. The colorant is, e.g. an org. or inorg. pigment.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a color image forming material, a photosensitive liquid containing the same, a photosensitive element and a color filter (LCD, CCD) using the same, and a television, a computer or a video monitor. And a color forming layer which can be used for a liquid crystal display and an image scanner, or a color proof of a printing material (for plate proofing).

[0002]

2. Description of the Related Art Conventionally, when a colored image is formed, a photosensitive pattern is formed as an aqueous solution of dichromic acid such as gelatin, PVA, casein or other water-soluble synthetic resin to form a transparent pattern, and a dye is formed. The method is described in, for example, JP-B-52-17375 and JP-B-52-173765. This dyeing method has a drawback that a dyeing step is required, and since the dye is a dye, heat resistance is low, and there is discoloration due to light peculiar to dyeing or discoloration due to aging, so-called discoloration, and it is difficult to form a stable colored image. Was. Also, in a method of forming a four-color halftone dot (dot) by adhering a toner on a transparent resin pattern by a photopolymerization method or a photo-crosslinking method using a photosensitive resin, a pigment is used in a color proof method. Since dispersion is not possible, a pigment is adhesively formed on a pattern formed on halftone dots. This step still requires an independent dyeing step.

As a method of compensating for the drawbacks of these methods, recently, photosensitive materials in which a pigment is dispersed have been studied by various companies. In the case of a heavy chromium oxygen-based light-sensitive material, secondary aggregation of the pigment occurred, and the pigment dispersion could not be obtained as a stable liquid. In this regard, the photopolymerization method using a photosensitive resin has been manufactured as a photosensitive liquid having a stable pigment dispersion in this respect, and has now become mainstream.

[0004] This pigment-dispersed type photosensitive solution is more
Excellent in shortening the process, hue, heat resistance and fading.
For example, JP-A-1-152449 and JP-A-1-2549
No. 18 proposes a method of forming a colored pattern in which a pigment is dispersed. However, the main composition of this pigment-dispersed photosensitive liquid is as follows: (1) a polymer (including a reactive double bond), (2) a photoinitiator, a sensitizer, (3) a colorant (pigment), a monomer, and the like. Consists of The disadvantage of this photopolymerization method is that the photocuring rate is low in the presence of oxygen, unlike the photocrosslinking type. In the current exposure method of exposing in the presence of air without vacuum adhesion, the sensitivity u
Examples of the compound having the function of p include the selection of the polymer (1) (containing a reactive double bond), the photoinitiator (2), the sensitizer, and the monomer (3).

[0005] However, there is a limit to the sensitivity improvement by selecting only the sensitivity up, sensitizer and monomer by having a polymer double bond in a pigment-dispersed system in which light is shielded. In particular, when the amount of the photoinitiator is increased, the photoinitiator is colored by a specific color. For example, in the case of forming a color filter, a problem of color mixing of each of Blue, Green, and Red, a decrease in heat resistance, a decrease in light transmittance, Problems such as a decrease in resolution and stickiness due to an increase in the amount of monomer occur.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a stable colored image forming material having a long service life in which a pigment which does not require a dyeing step as described in the prior art is uniformly dispersed, and a photosensitive material containing the same. It is intended to provide a liquid, a photosensitive element using the same, a method for producing a color filter, and a color proof (for plate proofing) of a printing material.

More specifically, in the present invention, an alkali-developable photosensitive solution having high sensitivity, heat resistance and high resolution as a colored image forming material, a method for producing a photosensitive element and a color filter using the same, It provides a color proof (for proofreading) of printing materials.

[0008]

Means for Solving the Problems The present inventors have found that a photosensitive composition containing a new photoinitiator has high sensitivity and no yellowing when formed as a film on a substrate.
It has been found that the film has a low sublimation property and the stability of the film thickness and chromaticity is improved even when stored at a temperature of 200 ° C. or more and 300 ° C. or less for a certain period of time. The photosensitive composition of the present invention comprises (a) a photoinitiator
Bisacylphosphine oxide, (b) a monomer having at least one ethylenically unsaturated bond in the molecule, (c) an alkali-soluble dispersing resin, and (d) a colorant. The photosensitive element of the present invention is obtained by laminating the above-mentioned photosensitive composition layer on a support (or a film). A cushion layer having thermoplasticity is formed on the support film. The layers can also be stacked sequentially.

In the method for producing a color filter of the present invention, a film of the above-mentioned photosensitive composition is formed on a substrate and irradiated with actinic rays.
The step of forming a predetermined image by development is performed a predetermined number of times.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The photoinitiator of the component (a) is a bisacylphosphine oxide, a compound represented by the formula (1) or (2) alone or in combination with another photoinitiator. (1) and (2) are (1) bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide,
(2) bis (2,6-dimethoxybenzoyl) 2,4
It is a compound represented by-, 4-trimethylpentylphosphine oxide.

Other photoinitiators include, for example, benzophenone, Michler's ketone, [4,4'-bis (dimethylamino) benzophenone], benzyl, 2,2-
Diethoxyacetophenone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzyldimethyl ketal, α-hydroxyisobutylphenone, thioxanthone, 2-chlorothioxanthone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (Methylthio) phenyl] -2-morpholino-1-propanone, t-butylanthraquinone, 1-chloroanthraquinone, 2,3
-Dichloroanthraquinone, p-chloroanthraquinone, 3-chloro-2-methylanthraquinone, 2-ethylanthraquinone, octamethyloanthraquinone, 1,
4-naphthoquinone, 9,10-phenanthraquinone,
Alkyl-substituted or halogen-substituted anthraquinones such as 1,2-benzoanthraquinone, 2,3-benzoanthraquinone, 1,4-dimethylanthraquinone, and 2-phenylanthraquinone, or bis (cyclopentagenenyl) -bis- [2 , 6 difluoro-3- (pyr-1
-) Phenyl] -titanium nititanocene, 2,2-bis (o-chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 1-6-n-
Cumene (n-cyclopentagenenyl) iron-6-fluorophosphoric acid, dibenzosperon, 10-butyl-2-chloroacridone, 2-benzyl-2-dimethylamino-1-
(4-morpholinophenyl) -butan-1-one, and other sensitizers such as carbon tetrachloride, ω, ω, ω-tribromomethylphenylsulfone 7,8,9,10-tetraphenylsulfone, , 2,3,4-tetrahydroanthracene and the like are also used. In addition, "Light Sensitive Materials List Book" (edited by Photopolymer Society, published by Bunshin Publishing,
(Issued on March 31, 1996). The amount of the present compound to be used is preferably 0.01 to 25% by weight, more preferably 1 to 20% by weight, based on the total solid content in the photosensitive solution as the colored image forming material of the present invention. These photoinitiators are used in combination of one or more of the compounds represented by (1) and (2). The use amount of this component is preferably 0.01 to 25% by weight, more preferably 1 to 15% by weight, of the total solid content in the photosensitive composition of the present invention. .

Addition of an amine as an amine sensitizer is effective because the curing speed is increased and the effect of inhibiting polymerization of oxygen and the like is reduced. Such amines include butylamine, hexamethylenediamine, diethylenetriamine, triethylenetriamine,
Primary amines such as monoethanolamine, secondary amines such as diethylamine, dimethylaniline, diethanolamine, triethanolamine, triethanolamine triacrylate dimethyl-p-toluidine, pyridine, methyldiethanolamine, N, N'-dimethylcyclohexylamine Amines. The use amount of these amine sensitizers is preferably 0.01 to 17% by weight, and more preferably 2 to 10% by weight of the total solid content in the photosensitive solution as the colored image forming material of the present invention. Is more preferred. If the amount is too small, the photosensitivity tends to decrease. If the amount is too large, the adhesiveness tends to decrease, and the tackiness of the dried coating film tends to occur.

The monomer having one or more ethylenically unsaturated bonds in the molecule as the component (b) is, for example, trimethylolpropane triacrylate, trimethylolpropane diacrylate, triethylene glycol diacrylate, diethylene glycol diacrylate, tetraethylene Glycol diacrylate, hexamethylene glycol diacrylate, neopentyl glycol diacrylate, furfuryl acrylate, tetramethylol methane tetraacrylate, resorcinol diacrylate, p, p'-dihydroxydiphenyl diacrylate, spiro glycol diacrylate, cyclohexane dimethylol diacrylate , Bisphenol A diacrylate, polypropylene glycol diacrylate,
Pentaerythritol tetraacrylate, ethylene glycolated pentaerythritol tetraacrylate,
Polyfunctional monomers such as dipentaerythritol hexaacrylate, compounds having the same structure as the above methacrylate, methylenebisacrylamide, and urethane diacrylate. Further, ECH-modified phthalic acid diacrylate, tris (acryloxyethyl) isocyanurate, tris (methacryloxyethyl) isocyanurate, tris (2-hydroxyethyl) isocyanurate, polyethylene glycol dimethacrylate, tribromophenyl acrylate, EO-modified triacrylate Bromophenol acrylate, EO-modified tetrabromobisphenol dimethacrylate, etc.
Monomers and oligomers having a molecular weight of 100,000 cps or more may be used. In addition, "Photosensitive Material List Book" (edited by Photopolymer Society, published by Bunshin Publishing, March 31, 1996)
Date issued). At least one of these components (b) is used, and the amount of this component is preferably 1 to 30% by weight of the total solid content in the photosensitive composition. If the amount is too large, the development time tends to be too early, the developability decreases, and stickiness tends to occur. If the amount is too small, the sensitivity tends to decrease, and development tends to be difficult.

Also, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, 2-ethylhexyl methacrylate, alkyl methacrylate, cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, benzyl methacrylate, mono (2-methacryloyloxyethyl) acid phosphate, dimethyl methacrylate Monofunctional monomers such as quaternary aminoethyl methacrylate are exemplified.
These components can be used alone or in combination of two or more. The amount of the compound to be used is preferably 1 to 30% by weight, more preferably 1 to 25% by weight, based on the total solid content in the colored image forming material of the present invention.

The alkali-soluble dispersion resin of the component (c) is
Acid value is 20-300, weight average molecular weight is 1,500-2
It is preferable to be within the range of 00,000. For example,
Copolymer of styrene monomer and maleic acid or derivative thereof (hereinafter referred to as SM polymer) unsaturated monomer having carboxyl group such as acrylic acid or methacrylic acid and styrene monomer, methyl methacrylate And copolymers with other monomers such as alkyl methacrylates such as tert-butyl methacrylate and hydroxyethyl methacrylate, and alkyl acrylates having the same alkyl group.

The SM copolymer is styrene such as styrene, α-methylstyrene, m or p-methoxystyrene, p-methylstyrene, p-hydroxystyrene, 3-hydroxymethyl-4hydroxy-styrene, or a derivative thereof ( Styrene monomer) and maleic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, mono-isomaleate
-N-butyl propyl maleate, mono-maleic acid-
There are copolymers of maleic acid derivatives such as iso-butyl and mono-tert-butyl maleate (hereinafter referred to as copolymer (I)). Although not shown in the above structural formula, the copolymer (I) is a compound having a reactive double bond, such as an alkyl methacrylate such as methyl methacrylate or t-butyl methacrylate. There is a modified product (hereinafter referred to as copolymer (II)).

The SM copolymer (I) is represented by the following structural formula 1.

Embedded image (Wherein, R1 represents a hydrogen atom or a methyl group, R2 represents a hydrogen atom, a hydroxyl group, an alkyl group or an alkoxy group,
R3 represents a hydrogen atom or a hydroxyalkyl group;
And R8 each independently represent a hydrogen atom, a lower alkyl group or a group having a reactive double bond, and m and n represent 1
In the above integer, m ≧ n. )

The copolymer (II) is a copolymer (I)
Unsaturated alcohols such as allyl alcohol, 2-bran-1-ol-free furyl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, N- Unsaturated alcohols such as methylol acrylamide, glycidyl acrylate, glycidyl methacrylate, allyl glycidyl ether, α-ethyl glycidyl acrylate, crotonyl glycidyl ether, oxirane ring such as monoalkyl monoglycidyl itaconate and reactive double bond respectively. It can be produced by reacting with one epoxy compound. In this case, it is necessary that a carboxyl group necessary for performing alkali development remains in the copolymer.

The copolymer (I) obtained as described above
The epoxy compound having one of the above-mentioned oxirane ring and one reactive double bond in order to further increase the concentration of the reactive double bond to the one in which a reactive double bond is introduced by an unsaturated alcohol among I) And further increase the reactive double bond concentration (hereinafter referred to as copolymer (III)).

In the case of a polymer having a carboxyl group other than the SM polymer, the provision of a reactive double bond is preferable from the viewpoint of photosensitivity as described above. The synthesis of these copolymers (copolymers (I), (II), (III), etc.) is described in JP-B-47-25470, JP-B-48-85679, JP-B-51-21572 and the like. It can be carried out according to the method described.

The use amount of this component is preferably from 10 to 80% by weight, more preferably from 20 to 70% by weight, based on the total solid content in the photosensitive composition of the present invention.
If the amount of the component (c) is too small, the alkali developability tends to decrease.

As a coloring agent effective for the colored image forming material, an organic pigment and an inorganic pigment can be mentioned.

The organic pigments include, for example, azo pigments such as azo pigments and condensation pigments insoluble in solvents (including water), phthalocyanine pigments, other indigo pigments, anthraquinone pigments, perylene pigments, quinacridone pigments, methine azomethine pigments, and isoindone pigments. Linone type and the like can be mentioned.

The three primary colors Blue, Green, Re
As the organic pigment constituting d, Blue is a phthalocyanine pigment. For example, C.I. I. Pigme
ntBlue: 6 (CI No. 74160), C.I.
I. Pigment 60 (CI No. 6980)
0), and C.I. to improve color reproducibility. I. Pigmen
Mixing with t Violet 23 is used. Green
n is a green pigment and is a halogenated phthalocyanine pigment such as C.I. I. Pigment Green 7 (C.I.
I. No. 74260), C.I. I. Pigment G
reen36 (CI No. 74265), C.I. I.
Pigment Green 37 (CI No. 74)
255) In order to improve color reproducibility, for example, a yellow pigment C.I. I. Pigment Yellow 139 (C.I.
I. No. None), C.I. I. Pigment Yellow
ow83 (CI No. 21108) is used. Red is a quinacridone pigment or an anthraquinone red pigment. For example, C.I. I. Pigm
ent Red 209 (CI No. 7390)
5), C.I. I. Pigment Red 177 (C.I.
I. No. 65300), to improve color reproducibility,
as in the case of the yellow pigment C. reen. I.
Pigment Yellow 139, C.I. I. Pi
gment Yellow83 is used.

As these pigments and further usable pigments, any of the pigments described in JP-A-58-147704 can be selected. This is not the case.

Examples of the inorganic pigment include chromium oxide, ultramarine blue, cadmium yellow, cadmium red, cobalt green, cobalt blue, and graphite.

As organic pigments constituting cyan, magenta and yellow, which are complementary colors of the three primary colors, cyan is C.I. I. P
15: 3 (CI. No. 74160),
As magenta, C.I. I. Pigment 57: 3
(C.I. No. 15850: 1). I. Pigment Yellow 12 (CI.
No. 21090).

Colorants forming the black matrix include carbon black, titanium carbon, iron black and the like.

When these pigments are dispersed, they are dispersed by an ultrasonic disperser, a three-roll mill, a bead mill, a homogenizer, or the like. In a bead mill, beads such as zirconia are added to a container, and a pigment or the like is pulverized by high-speed rotation by a rotating rotor.

The photosensitive liquid for a colored image forming material of the present invention includes:
A polymerization inhibitor can be added to prevent a dark reaction. As the polymerization inhibitor, for example, hydroquinone,
P-methoxyphenol, 2,6-di-t-butyl-p
-Cresol, 2,2'-methylenebis (4-methyl-
6-t-butylphenol) cuperone, N nitrosophenylhydroxylamine, 2,5- (1,1-dimethylbutyl) hydroquinone, 2,5- (1,1,3,3
-Tetramethylbutyl) hydroquinone and the like. The compound is preferably used in an amount of 0.001 to 1% by weight, preferably 0.1 to 1% by weight, based on the total solid content in the color filter material of the present invention and the photosensitive solution as a color proof.
More preferably, it is used at 0.5% by weight. If the amount is too small, the polymerization inhibitor is ineffective, and if it is too large, the sensitivity is lowered.

The colored image-forming material of the present invention is made into a photosensitive solution by dissolving it in a solvent-free or suitable solvent to form a photosensitive solution, coating the solution on a support and drying. In the case of no solvent, it is possible by using a monomer as a diluent and adding as much as other substances dissolve. However, since the dark reaction is accelerated as compared with the case where the solvent is present, it is necessary to add a large amount of a polymerization inhibitor.

Further, for the purpose of dissolving in a solvent to form a photosensitive solution, the solvent optionally used includes:
Ketone solvents, cellosolve solvents, alcohol solvents,
Examples include ether solvents and non-polar solvents. Specifically, methyl ethyl ketone, acetone, cyclohexane, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, ethylene glycol monopropyl ether, ethylene glycol mono n-hexyl ether, ethylene glycol dimethyl ether, diethylene glycol ethyl ether , Triethylene glycol dimethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methyl-3-meth Xybutanol, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether propionate, N-methyl-2-pyrrolidone, N-hydroxymethyl-2-pyrrolidone, N-hydroxyethyl-2-pyrrolidone, methyl alcohol , Ethyl alcohol, isopropyl alcohol, tetrahydrofuran, dioxane, benzene, toluene, xylene, ethyl acetate and the like. These solvents may be used as a mixture of two or more kinds.

Such a solvent is preferably used in such an amount that the solid content of the colored image forming material is 10 to 60% by weight. If the amount of the solvent is too large, the stability of the dispersion tends to decrease. If the amount is too small, the effect of lowering the viscosity or the like may be low, or gelation may easily occur.

For forming a colored image, for example, when applying a photosensitive solution dissolved in a diluent or solvent for a color filter, the support may be a transparent glass plate, ie, a blue plate glass, mainly non-alkali, alumino. Silicate, quartz glass or the like is used. For other uses, an acrylic resin plate, a vinyl chloride resin plate, a copper plate, an aluminum plate, a nickel plate, a metal plate of stainless steel or the like is used.

The coating methods include roll coater coating, spin coater coating, spray coating, wool coater coating, dip coater (kiss coating) coating, curtain flow coater coating, wire bar coater coating, gravure coater coating, air knife coater coating, and extrusion coating. is there. After the photosensitive solution is applied on these supports by the above-described method, the applied solution is naturally dried or forcibly dried by heating to form a dried coating film having a thickness of several μm.

Alternatively, a film can be formed on the present support by directly applying it to a support and forming a photosensitive element without laminating the support directly, followed by lamination. This method is effective when the coating cannot be applied directly to the support. The method of coating the temporary support can be performed by the method described in the above-mentioned coating method.

As the temporary support used at this time, for example, a polyester film, a polyamide film, a polyimide film, a polypropylene film, a polystyrene film and the like can be used. It is applied to these films and dried by a usual method such as natural drying or forced drying. It is desirable to laminate a peelable cover film on the surface of the coating film in order to prevent dust and dirt from adhering to the coating film applied to the temporary support.

As the peelable cover film, for example, a polyethylene film, a Teflon film or a polypropylene film can be used. It is only necessary that the adhesive strength of the cover film is smaller than the adhesive strength of the temporary support.

As a method of laminating the photosensitive element obtained on the temporary support to the present support, peeling off the cover film and heat-pressing on the substrate which is the present support improves adhesion, More preferred.

The thickness of the colored image forming material in the method formed on the substrate surface in this way is determined depending on the application, but is usually used in the range of 0.1 to 500 μm.
When used for a color filter, it is used in the range of 0.1 to 5 μm.

The photosensitive layer, which is a dried coating film, is exposed by an exposure machine to cure the photosensitive portion. The exposing machine applicable to the composition of the present invention includes a carbon arc lamp, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, a fluorescent lamp, a tungsten lamp and the like. Further, by using an exposing machine in which these light sources are made parallel light for the purpose of preventing irregular reflection, the pattern accuracy can be improved.

[0042]

EXAMPLES Example 1 (Color Filter) First, a dispersion was prepared. The dispersion [1] was obtained by dispersing the resin (polymer A), which is the above-described copolymer, and a pigment in a bead mill with a solvent for 3 hours. Polymer A is a styrene-maleic acid resin having a molecular weight of 11,000, an acid value of 75, and (R1
Is a hydrogen atom, R2 is a hydrogen atom, and R3 is a residue obtained by esterifying a carboxyl group with 100% 2-hydroxyethyl methacrylate (Formula 1), and the ratio is 3/7. That is, 30% of the carboxylic acid remains in this portion.
R4 is the residue of a hydrogen atom / carboxylic acid and glycidyl methacrylate reactant (Formula 2). ). -CH2-CH2-O-CO-C (CH3) = CH2 (Formula 1) -CH2-C (OH) HO-CO-C (CH3) = CH2 (Formula 2) Also, as the three primary colors Blue at this time, Blue pigment is C.I.
I. Pigment Blue 15: 6 and C.I. I. Pig
ment 23, the ratio was 91: 9, and the solvent was γ.
-Butyrolactone was used. The composition of the blue pigment dispersion [1] was 37.5% resin, 15% pigment, and 50% solvent γ-butyrolactone. The dispersant was A-600 (Daiichi Kogyo) 2.5%. The average particle size is Horiba
-CAPA-700 Particle-Analyz
er and was 0.3 μm. The viscosity of the blue pigment dispersion [1] was measured with an E-type viscometer manufactured by Tokimec, and was found to be 44 m · Pa · S. As Green
Green pigment is also C.I. I. Pigment Green 36
And C. I. Pigment Yellow 139, at a ratio of 82:18, and dispersed in the same manner as for the blue pigment. The viscosity of the green pigment dispersion [1] is 48 m · Pa ·
It was S. The red pigment as the three primary colors Red is also C.I.
I. Pigment Green 177 and C.I. I. Pi
gment Yellow 139 with a ratio of 88:
The dispersion was performed in the same manner as the blue pigment. The viscosity of the green pigment dispersion [1] was 40 m · Pa · S. Dispersion of each of the three primary colors Blue, Green, Red [1]
And a photosensitive solution for a color filter was mixed with a stirrer to produce a color filter. Table 1 shows the formulation of the color filter photosensitive solution.

Table 1 Compound name Addition amount (parts by weight) [Resin] Polymer A 78 parts [Crosslinking agent] Trimethylolpropane triacrylate 30 parts [Photoinitiator] Bis (2,4,6-trimethylbenzoyl) phenylphosphine Oxide 8 parts Benzoin ethyl ether 8 parts [Sensitizer] Diethanolamine 4.5 parts [Solvent] N-methylpyrrolidone 5 parts γ-butyrolact 500 parts [Polymerization inhibitor] p-methoxyphenol 0.1 part [Surfactant] Perfluoroalkyl alkoxylate 0.01 parts [Colorant] 48 parts of each color dispersion [1]

The viscosities of the blue, green, and red photosensitive liquids of Blue, Green, and Red are respectively 24 m · Pa · S,
It was 27 m · Pa · S and 22 m · Pa · S. The obtained photosensitive solution was applied to a glass substrate (trade name: 7059, manufactured by Corning Incorporated) at 1200 rpm by a spinner (manufactured by Kyowa Riken Co., Ltd.) and dried. The dispersion stability as a pigment dispersion photosensitive liquid was very good. It was found that the film after coating and drying was also transparent, and the dispersion was stable. Next, the coating film was brought into close contact with a glass mask having a triangular mosaic pattern, and was exposed with an ultra-high pressure mercury lamp manufactured by Oak. Exposure is 200mJ / cm
^In step ² , a step tablet (21 steps) manufactured by Eastman Kodak Co. was also exposed simultaneously for sensitivity measurement. Next, development was performed by immersion development (bat development). Pattern (pixel)
There was no edge of the edge.

The composition of the developer is as follows. Table 2 Developer composition Compound weight% Triethanolamine 6% Isopropanol 0.5% Water 93.5% Total 100% The development temperature was 25 ° C and the development time was 70 seconds. The dry film thickness obtained after this development is 2.0 for each of blue, green and red.
μm, 2.1 μm and 1.9 μm. The resulting pattern was sufficiently usable as a color filter. At this time, the sensitivity of the Eastman Kodak Step Tablet is 7.5 for blue, green and red respectively.
Dan, 6, and 7. Clean oven CSO-
It was heated and cured at 260 ° C./1 hour with a 402 (manufactured by Kusumoto Chemicals). The color difference (ΔEab *) is 5.18,
5.4 and 5.11.

Example 2 (Color Filter) A test was conducted in the same manner as in Example 1 except that the dispersion [1] was used and the following formulation was used. Three primary colors Blue, Green,
The viscosities of the blue, green and red photosensitive liquids as Red are 24
m · Pa · S, 27 m · Pa · S, and 22 m · Pa · S, which were the same as in Example 1. As in Example 1, a coating step (1200 rpm), a drying step (80 ° C./10 minutes),
An exposure step (200 mJ / cm ² ) and a development step (development time: 70 seconds) were performed to form a color filter pattern. The developer is the same as in Example [1]. Similarly, the dry film thicknesses are 2.0 μm, 2.1 μm, and 2.2 for blue, green, and red as the three primary colors Blue, Green, and Red, respectively.
μm. The number of solid steps using the step tablet was 8, 7, and 7.5, respectively, for blue, green, and red. Clean oven CSO-402 (Kusumoto Kasei)
Heating and curing were performed at 60 ° C. for 1 hour. Color difference (ΔEab
*) Were 5.6, 5.8, and 5.5 for blue, green, and red, respectively.

Table 3 Compound name Addition amount (parts by weight) [Resin] 75 parts of polymer A [crosslinking agent] 30 parts of trimethylolpropane triacrylate [photoinitiator] bis (2,6-dimethoxybenzoyl) 2,4-, 4-trimethylpentyl phosphine oxide 8 parts Benzoin ethyl ether 8 parts [Sensitizer] diethanolamine 4.5 parts [Solvent] N-methylpyrrolidone 5 parts γ-butyrolactone 500 parts [Polymerization inhibitor] p-methoxyphenol 0.1 Parts [surfactant] perfluoroalkyl alkoxylate 0.01 part [colorant] each color dispersion [1] 48 parts

Comparative Example 1 (Color Filter) A dispersion was prepared in the same procedure as in Example 1. Table 4 shows the formulation of the photosensitive solution for the color filter. 2-Benzyl-2-dimethylamino-1- (4-morpholino-phenyl) butanone-1 was used as a photoinitiator.

Table 4 Compound name Addition amount (parts by weight) [Resin] 75 parts of polymer A [crosslinking agent] 30 parts of trimethylolpropane triacrylate [photoinitiator] 2-benzyl-2-dimethylamino-1- (4-morpholino) -Phenyl) butanone-1 8 parts Benzoin ethyl ether 8 parts [Sensitizer] diethanolamine 4.5 parts [Solvent] N-methylpyrrolidone 5 parts γ-butyrolactone 500 parts [Polymerization inhibitor] p-methoxyphenol 0.1 part [Surfactant] Perfluoroalkylalkoxylate 0.01 part [Colorant] 48 parts of each color dispersion [1] The measured viscosities are 24 m · Pa · S for blue, green and red, respectively. 27m ・ P
a · S and 22 m · Pa · S were the same as in Example 1. In the same manner as in Example 1, a coating step (1200 rpm), a drying step (80 ° C./10 minutes), and an exposure step (200 mJ / c)
m ² ), a development step (development time: 70 seconds) was performed, and a color filter pattern was formed. The developer is the same as in Example 1. Similarly, the dry film thickness after development is Blue, Gr
blue, green and red as eeen and Red are each 2.1 μm.
m, 2.2 μm and 2.2 μm. The number of steps was 5, 4.5, and 6.05, respectively, for blue, green, and red. Further, heating and curing were performed in a clean oven CSO-402 (manufactured by Kusumoto Kasei Co., Ltd.) at 260 ° C. for 1 hour. The color difference (ΔEab *) is 7.01, 7.2 for blue, green, and red, respectively.
8, 7.7.

Comparative Example 2 (Color Filter) A dispersion was prepared in the same procedure as in Example 1. Table 4 shows the formulation of the photosensitive solution for the color filter. 2-Methyl-1- [4- (methylthio) phenyl] as photoinitiator
-2-morpholino-1-propanone was used.

Table 5 Compound name Addition amount (parts by weight) [Resin] 75 parts of polymer A [crosslinking agent] 30 parts of trimethylolpropane triacrylate [photoinitiator] 2-methyl-1- [4- (methylthio) phenyl] 8-morpholino-1-propanone 8 parts Benzoin ethyl ether 8 parts [Sensitizer] diethanolamine 4.5 parts [Solvent] N-methylpyrrolidone 5 parts γ-butyrolactone 500 parts [Polymerization inhibitor] p-methoxyphenol 0. 1 part [Surfactant] Perfluoroalkyl alkoxylate 0.01 part [Colorant] 48 parts of each color dispersion [I] The measured viscosities are 24 m · Pa · for each of the three primary colors Blue, Green and Red. S, 27mP
a · S and 22 m · Pa · S were the same as in Example 1. In the same manner as in Example 1, a coating step (1200 rpm), a drying step (80 ° C./10 minutes), and an exposure step (200 mJ / c)
m ² ), a development step (development time: 70 seconds) was performed, and a color filter pattern was formed. Similarly, the dry film thickness after development is blue as Blue, Green, Red,
Green and red were 2.0 μm, 2.2 μm and 2.3 μm, respectively. The number of steps is 6 for each of blue, green and red.
5.5 and 6.5 steps. Clean oven CS
O-402 (manufactured by Kusumoto Chemicals) heated at 260 ° C for 1 hour,
Curing was performed. The color differences (ΔEab *) were 7.21, 7.48, and 7.80 for blue, green, and red, respectively.

Embodiment 3 (Color Proof) First, black of black ink, cyan of complementary colors, magenta,
A yellow dispersion [2] was prepared. Dispersion [2] uses Polymer A, and a pigment and a dispersant (Daiichi Kogyo Seiyaku Co., Ltd. A-600) are mixed in a bead mill (Driesberg G).
MBH Pearl Mill PML-H / V for lab) 1.5
Stirred for hours. At this time, the color pigment used was black as carbon black, carbon black, and cyan as a complementary color was C.I.
I. Pigment Blue 15: 3 (CI No. 7)
4160), and magenta uses C.I. I. Pigmen
tRed57: 3 (CI No. 15850), yellow is C.I. I. Pigment Yellow 12 (C.I.
I. No. 21090) was used. The dispersion was prepared with the same formulation as the color filter. The resin is 37.5%, the pigment (each color) is 12.5%, and the solvent is diglyme 50%.

Table 6 Compound name Addition amount (parts by weight) [Resin] Polymer A 75 parts [Crosslinking agent] Trimethylolpropane triacrylate 30 parts [Photoinitiator] Bis (2,4,6-trimethylbenzoylyl) phenylphosph Hinoxide 8 parts Benzoin ethyl ether 8 parts [Sensitizer] Diethanolamine 4.5 parts [Solvent] N-methylpyrrolidone 5 parts γ-butyrolactone 500 parts [Polymerization inhibitor] p-methoxyphenol 0.1 part [Surfactant Perfluoroalkyl alkoxylate 0.01 part [Coloring agent] Dispersion of each color [2] 48 parts Black, cyan, magenta, yellow dispersion [2]
The measured viscosities are 60 mPa · S and 55 mPa
・ S, 62m ・ Pa ・ S, 58m ・ Pa ・ S. Table 6 shows the formulation of the photosensitive solution for color proofing. Black, cyan, magenta, and color proof photosensitive liquids
Each viscosity of yellow is 30m ・ Pa ・ S, 33m
・ Pa ・ S, 38m ・ Pa ・ S, 32m ・ Pa ・ S.

Each of the four photosensitive solutions was applied to a 75 μm thick polyethylene terephthalate (PET) film using a wire bar and dried to a dry film thickness of 2 μm. The PET film support has been previously subjected to an anchoring (undercoat layer) treatment. The anchor solution is an ionomer resin (solid content 27.5 wt%) 100
Part and polypropylene emulsion (solid content 30wt%)
A solution consisting of 100 parts, in which a dry coating film of 1 μm was formed. PET on which the four photosensitive layers are formed
And a color separation screen positive film (using 195 lines / inch) made of the same image and superimposed in vacuum at 190 mJ / cm ² with an oak plate making exposure machine (Jetprinter JP2000 ultra-high pressure mercury lamp 2KW). did. Development was performed in the same manner as in Example 1 to obtain a halftone image of four colors. Next, the black support on which the halftone dot image was obtained was brought into close contact with art paper, and a pressure of 4.5 kg / cm ^{2 was applied} between a pair of nip rolls heated to 85 ° C. at a speed of 50 cm / min. After passing through, the support was peeled off. A black image was transferred to the art paper. A colored image was transferred in the order of cyan, magenta and yellow by the same method, and a color proofing image was obtained on art paper. The finish on art paper has the same gradation as the actual printed matter, indicating that it can be used as a color proof.

Photoinitiator bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2
Example 1 using 6-dimethoxybenzoyl) 2,4-, 4-trimethylpentylphosphine oxide
2, the characteristics of Comparative Examples 1 and 2 are summarized in Table 7 in FIG.

Table 7 shows that bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2
By using 6-dimethoxybenzoyl) 2,4-, 4-trimethylpentylphosphine oxide, an effect as a photoinitiator was observed.

[0057]

The sensitivity is increased by adding the compound as a photoinitiator of the present invention. In addition, since there is no yellowing of the initiator at the time of photocuring, there is an effect that the value of the color difference ΔEab * is reduced.

[0058]

[Brief description of the drawings]

FIG. 1 is a table summarizing the characteristics of Examples 1 and 2 and Comparative Examples 1 and 2.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI // C09D 4/00 C09D 4/00

Claims (6)

[Claims] 1. A photoinitiator bisacylphosphine oxide, (b) at least one monomer having an ethylenically unsaturated bond, (c) an alkali-soluble dispersing resin, (d)
A photosensitive composition containing a coloring agent. (A) the photoinitiator is bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and bis (2,6-dimethoxybenzoyl) 2,4-,
2. The photosensitive composition according to claim 1, which is at least one selected from 4-trimethylpentylphosphine oxide. 3. A photosensitive solution containing the photosensitive composition according to claim 1. 4. A photosensitive element having a support comprising a layer containing a colored image forming material prepared by using the photosensitive solution according to claim 3. 5. The photosensitive element according to claim 4, wherein a peelable cover film is laminated on the layer containing the colored image forming material. 6. A colored image forming material is formed as a film on a substrate by using the photosensitive liquid according to claim 3 or the photosensitive element according to claim 4 or 5, and is irradiated with actinic rays imagewise. A method of manufacturing a color filter or a color proof, wherein a step of photocuring portions and removing unexposed portions by development is repeatedly performed on colored image forming materials of a plurality of different colors to form pixels.