JPH0973171A - Photosensitive colored composition and production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photosensitive colored compsn. for a color filter having high energy transducing efficiency, capable of reducing the number of processes without using a photomask and used for direct writing. SOLUTION: This photosensitive colored compsn. for a color filter used for direct writing with visible light laser contains a photosetting resin compsn., a coumarin sensitizer, a polymn. initiator and a colorant as essential components. The photosetting resin compsn. consists of a photosetting resin (a) having photosensitive groups which are crosslinked or polymerized by irradiation with light and ionic groups, an ethylenically unsatd. compd. (b) and at least one kind of binder (c) having ionic groups and the compsn. is based on the component (a) or a mixture of the components (a), (b). The amt. of the photosensitive groups is 0.2-7.0mol/kg in the total amt. of the components (a), (b), (c) and the amt. of the ionic groups is 0.2-3.5mol/kg.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photosensitive coloring composition for a color filter used in a display device such as a liquid crystal and a novel color filter using the photosensitive coloring composition by direct drawing with a visible light laser. Manufacturing method.

[0002]

2. Description of the Related Art Conventionally, a colored photoresist for a color filter is generally formed by forming a colored pattern by exposing ultraviolet light in a pattern through a photomask. However, since the sensitivity of the colored photoresist in the conventional method using ultraviolet light is generally several tens to several hundreds mj / cm ² , there is a problem that a high output light source is required and the energy conversion efficiency for recording is poor. . In addition, since it is usually necessary to form at least three colors of red, blue, and green as the coloring pattern, a photomask is formed to match the pattern of each color, and a photo on the resist film for each color is formed. There is a problem that a mask needs to be installed and a lot of man-hours are required for the work.

Therefore, the inventors of the present invention have conducted intensive studies on a direct writing method using a visible light laser in order to develop a method which has good energy conversion efficiency and can reduce the number of steps without using a photomask. It was found that the above object can be achieved by using a specific photosensitive coloring composition containing an agent and exposing a resist film obtained from this composition in a pattern with a visible light laser.

Conventionally, regarding a photopolymerization initiator system effective for visible light, for example, a system in which hexaarylbiimidazole and p-dialkylaminobenzylidene ketone or dialkylaminochalcone are combined (USP 3,652,
275, JP-A-54-155292, and a system in which camphorquinone and a dye are combined (JP-A-48-084318).
No.), a system in which a diphenyliodonium salt and Michler's ketone are combined (GB2,020,297A), a system in which an S-triazine compound and a merocyanine dye are combined (JP-A-54-151024), an S-triazine compound and thiapyrylium. A system in which a salt is combined (JP-A-58-4003)
No. 02) and the like, but these initiator systems have the ability to initiate light rays in the visible region, but none of them have sufficient sensitivity in a photosensitive coloring composition containing a colorant, resulting in a photosensitive coloring. There is also a problem in terms of compatibility with the resin component in the composition.

As a result of various studies, the inventors of the present invention have used a coumarin type sensitizer as a sensitizer, and in particular, a photopolymerization initiator system combining a coumarin type sensitizer and a titanocene compound as a polymerization initiator. Has been found to be excellent in sensitivity and compatibility with resin components in the photosensitive coloring composition, and has completed the present invention.

[0006]

Means for Solving the Problems That is, the present invention is as follows.
[A] (a) A photocurable resin containing a photosensitive group that can be crosslinked or polymerized by irradiation with light, and an ionic group, (b)
It comprises at least one component of an ethylenically unsaturated compound and (c) an ionic group-containing binder, and mainly comprises a component (a) or a mixture of a component (b) and a component (c). And the total amount of components (a), (b) and (c) is 0.2 to 7.0 mol / kg and the amount of ionic groups is 0.2 to 3.5 mol / kg. Photosensitive coloring for a color filter for direct drawing with a visible light laser, which contains a certain photocurable resin component, [B] coumarin-based sensitizer, [C] polymerization initiator and [D] colorant as essential components A composition is provided.

[0007] The present invention also provides: (1) a step of forming a photosensitive coating from the photosensitive coloring composition according to the above item 1 on a transparent substrate, (2) a step of forming a cover coat layer on the photosensitive coating, if necessary, (3) ) A step of curing the exposed portion of the photosensitive coating by exposing the photosensitive coating to visible light laser in a pattern, and (4) a step of removing the photosensitive coating in the non-exposed portion by a developing treatment to form a color pattern. ,
And (5) A method of manufacturing a color filter, which further comprises a step of heating as necessary.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The composition of the present invention comprises the following [A],
A photosensitive coloring composition for a color filter, which comprises the components [B], [C] and [D] as essential components.

Photocurable resin component [A] Consists of at least one of the following components (a), (b) and (c), the component (a) or the component (b) and the component (c).
It is a photocurable resin component containing a mixture of components as a main component and containing a photosensitive group and an ionic group.

Photocurable resin (a) The resin (a) is a photocurable resin containing a photosensitive group that can be crosslinked or polymerized by irradiation with light, and an ionic group.
A portion which is substantially insoluble or hardly soluble in an alkali aqueous solution or an acid aqueous solution through a crosslinking reaction or a polymerization reaction by irradiation of light, and a portion which is not exposed is an alkali when the ionic group is an anionic group. A resin that is soluble in an aqueous solution and is soluble in an aqueous acid solution when the ionic group is a cationic group. The photosensitive group is a group that can be crosslinked or polymerized by irradiation with light in the presence of a sensitizer [B] and a polymerization initiator [C], and specific examples thereof include (meth) acryloyl group [CH ₂ = CR-CO- (in the formula, R represents a hydrogen atom or a methyl group)], a cinnamoyl group, an allyl group, an azido group, a cinnamylidene group and the like.

The amounts of the ionic group and the photosensitive group in the resin (a) can be varied over a wide range depending on the type and molecular weight of the resin (or binder) serving as the substrate, but generally the ionic group 0.2 to 0.2 in both cases where the functional group is an anionic group (eg, carboxyl group) or a cationic group (eg, tertiary amino group or onium base)
3.5 mol / kg resin, preferably 0.3-2.0 mol / k
g within the range of resin, and the photosensitive group is 0.2 to
7.0 mol / kg resin, preferably 0.7-4.5 mol / k
g It is suitable to be included in the amount of resin.

The resin (a) is generally 1,000 to
100,000, preferably 3,000 to 50,000
It is preferable that the glass transition temperature (Tg) is 0 ° C. or higher, particularly 5 to 70 ° C., because the coating film does not exhibit tackiness.

Specific examples of the resin (a) will be described below.

(A) Anionic photocurable resin containing a (meth) acryloyl group as a photosensitive group: The photocurable resin is
For example, it can be produced by adding a glycidyl group-containing unsaturated compound to a high acid value acrylic resin. The high acid value acrylic resin used in that case is, for example, an α, β-ethylenically unsaturated acid such as acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid as an essential component, and (meth) Acrylic acid esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-hydroxyethyl ( (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, etc. and styrene,
It is obtained by copolymerizing at least one unsaturated monomer selected from (meth) acrylonitrile and (meth) acrylamide. Here, the α, β-ethylenically unsaturated acid generally has an acid value of high acid value acrylic resin of 40.
It can be used in an amount such that it ranges from ˜650, preferably from 60 to 500. The number average molecular weight and glass transition temperature (Tg) of the high acid value acrylic resin are the same as the above number average of the photocurable resin obtained by adding a glycidyl group-containing unsaturated compound to the high acid value acrylic resin. The molecular weight and the Tg are appropriately adjusted.

On the other hand, specific examples of the glycidyl group-containing unsaturated compound added to the above high acid value acrylic resin include glycidyl acrylate and glycidyl methacrylate.

The above-mentioned addition reaction of the high acid value acrylic resin and the glycidyl group-containing unsaturated compound is carried out according to a method known per se, for example, using a catalyst such as tetraethylammonium bromide at 80 to 120 ° C. for 1 to 5 hours. It can be easily carried out by reacting.

The present photocurable resin can also be produced by adding a reaction product of a hydroxyl group-containing polymerizable unsaturated compound and a diisocyanate compound to an acrylic resin having a hydroxyl group.

Examples of the hydroxyl group-containing polymerizable unsaturated compound include 2-hydroxyethyl acrylate and 2
-Hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, N-methylol acrylamide and the like are mentioned, and as the diisocyanate compound,
Examples thereof include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate and lysine diisocyanate.

(B) Photocurable resin containing a cinnamoyl group as a photosensitive group: This photocurable resin comprises, for example, an acrylic resin containing a hydroxyl group and a substituted or unsubstituted cinnamic acid halide. In the presence of a base, for example
It can be produced by reacting in a pyridine solution. The hydroxyl group-containing acrylic resin used at that time is the α, β-ethylenically unsaturated acid and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and the like described in the above item (a). It can be obtained by using a hydroxyl group-containing polymerizable unsaturated compound as an essential component and copolymerizing these with at least one other unsaturated monomer.

The substituted or unsubstituted cinnamic acid halide is generally 6 to 180 parts by weight, preferably 30 to 100 parts by weight per 100 parts by weight of the above-mentioned hydroxyl group-containing acrylic resin.
It can be used in an amount such that it is in the range of 140 parts by weight.

The substituted or unsubstituted cinnamic acid halide that can be used is a cinnamic acid halide which may have 1 to 3 substituents selected from a nitro group and a lower alkoxy group on the benzene ring. And more specifically, cinnamic acid chloride, p-nitrocinnamic acid chloride, p
-Methoxycinnamic acid chloride, p-ethoxycinnamic acid chloride and the like can be mentioned.

(C) Photocurable resin containing an allyl group as a photosensitive group: This photocurable resin is, for example, the high acid value acrylic resin used in (a) above, and allyl glycidyl ether.

[0023]

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Or by adding a reaction product of a (meth) allyl alcohol and a diisocyanate compound to a hydroxyl group-containing acrylic resin.

The addition reaction of the above-mentioned high acid value acrylic resin and allyl glycidyl ether can be carried out in the same manner as the method described in the above item (a).

In the composition of the present invention, as the photocurable resin (a), it is possible to use a conventionally known cationic resin in addition to the anionic resin.

Examples of such a cationic resin include resins obtained by adding a reaction product of a hydroxyl group-containing polymerizable unsaturated compound and a diisocyanate compound to an acrylic resin having a hydroxyl group and a tertiary amino group: A tertiary amino group-containing resin obtained by reacting an epoxy resin with a secondary amine and then reacting the remaining epoxy group with a polymerizable unsaturated monocarboxylic acid or a hydroxy group-containing unsaturated compound; a glycidyl group-containing unsaturated compound And a tertiary amino group-containing unsaturated compound are copolymerized with another polymerizable unsaturated monomer to obtain a resin obtained by reacting a polymerizable unsaturated monocarboxylic acid or a hydroxyl group-containing polymerizable unsaturated compound. Tertiary amino group-containing resin; Epoxy resin reacted with polymerizable unsaturated monocarboxylic acid or hydroxyl group-containing unsaturated compound Tertiary amino compound epoxy groups remaining, thioether, an onium salt group-containing resin obtained by onium chloride in the presence of a phosphine with a carboxylic acid;
And the like.

The resin (a) can be used alone or in combination of two or more kinds.

Ethylenically unsaturated compound (b) The ethylenically unsaturated compound (b) is a compound containing at least one ethylenically unsaturated double bond in its chemical structure, and undergoes addition polymerization when exposed to visible light. Examples thereof include monomers, dimers, trimers and other oligomers having a function of insolubilizing exposed portions.

Examples of the ethylenically unsaturated compound as described above include unsaturated carboxylic acids, and esters of unsaturated carboxylic acids with divalent or higher valent aliphatic or aromatic polyhydroxy compounds.

Examples of unsaturated carboxylic acids include acrylic acid, methacrylic acid, crotonic acid, α-methylcrotonic acid and itaconic acid.

Examples of the aliphatic polyhydroxy compound include ethylene glycol, diethylene glycol, triethylene glycol, neopentyl glycol, propylene glycol, 1,2-butanediol and 1,6-.
Examples thereof include dihydric alcohols such as hexanediol, trihydric alcohols such as trimethylolethane, trimethylolpropane and glycerol, and tetrahydric or higher alcohols such as pentaerythritol and dipentaerythritol.

Examples of the aromatic polyhydroxy compound include hydroquinone, catechol, resorcinol,
Examples include pyrogallol.

Specific examples of the ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid include, for example, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, propylene glycol diacrylate, Acrylic esters such as trimethylolpropane triacrylate, trimethylolethane triacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, trimethylol Propane trimethacrylate, trimethylol ether Methacrylic acid esters such as tritrimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, tetramethylene glycol dimethacrylate; crotonic acid esters such as ethylene glycol dicrotonate and pentaerythritol dicrotonate; ethylene glycol Itaconic acid esters such as diitaconate and propylene glycol diitaconate; maleic acid esters such as ethylene glycol dimaleate, pentaerythritol dimaleate, and trimethylolpropane dimaleate.

Specific examples of the ester of an aromatic polyhydroxy compound and an unsaturated carboxylic acid include hydroquinone diacrylate, hydroquinone dimethacrylate, hydroquinone dicrotonate, resorcinol diacrylate and pyrogallol triacrylate.

Ionic Group-Containing Binder (c) The binder has an anionic or cationic ionic group, and has good compatibility with an ethylenically unsaturated compound; It satisfies performances such as sufficient adhesiveness, formation of a tough film resistant to friction, and easy development. The amount of ionic groups is preferably in the range of 0.2 to 10 mol / kg.

Specific examples of such a binder include an ethylenically unsaturated acid (eg, acrylic acid, methacrylic acid, maleic acid, crotonic acid, itaconic acid, etc.) as an essential component, and this (meth) acrylic Alkyl ester of acid (as the alkyl group, methyl group, ethyl group, 2-ethylhexyl group, lauryl group, etc.) or other (meth) acrylic acid ester, other unsaturated monomer (for example, styrene, acrylonitrile, vinyl chloride, chloride) Vinylidene, butadiene, etc.), an acrylic multi-component copolymer, wherein at least one monomer such as styrene, vinyl alkyl ether, isobutylene, vinyl chloride, maleic acid diester, and maleic anhydride copolymer and its partial ester Chemically modified polymer; having carboxyl copolymer in the side chain Acidic cellulose modified product; tertiary amino group-containing ethylenically unsaturated monomer (for example, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth ) Acrylate and the like) as an essential component, and an acrylic multi-component copolymer obtained by appropriately combining this with the above-mentioned alkyl ester of (meth) acrylic acid, and other unsaturated monomers; and the like.

The photocurable resin component [A] is mainly composed of the above-mentioned component (a) or a mixture of the component (b) and the component (c), and the component (a) alone and the component (b). Ingredients and (c)
A mixture with components, a mixture of components (a) and (b),
It can be a mixture of the components (a) and (c), or a mixture of the components (a), (b) and (c),
The total amount of components (a), (b) and (c) is 0.2 to 7.0 mol / kg, and the amount of ionic groups is 0.2.
It should be ~ 3.5 mol / kg. If the total amount of photosensitive groups is less than 0.2 mol / kg, the curability due to light irradiation will be insufficient, while if it exceeds 7.0 mol / kg, the physical properties of the cured film obtained will be poor. On the other hand, if the total amount of ionic groups is less than 0.2 mol / kg, a film residue is likely to occur at the time of development, while if it exceeds 3.5 mol / kg, the coating film in the exposed area is easily dissolved in the developer during development. Become.

In the case where the photocurable resin component [A] is a mixture of the component (b) and the component (c), the component (b) /
The blending ratio of the component (c) is usually 80/20 to 80 by weight.
It is within the range of 20/80.

Coumarin type sensitizer [B] Examples of the coumarin type sensitizer [B] include 3-substituted coumarins and 3,4-substituted coumarins. This is a compound that is excited by absorbing light (visible light) in the wavelength region of 400 to 700 nm and interacts with the photocurable resin [A] and the polymerization initiator [C]. Here, "interaction" includes energy transfer and electron transfer from the excited sensitizer [B] to the photocurable resin [A] or the polymerization initiator [C].

As typical examples of 3-substituted coumarins, compounds represented by the following formulas can be mentioned (Japanese Patent Laid-Open No. Sho 6-62).
1-97650).

[0042]

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[0043]

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[0044]

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[0045]

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[0046]

[Chemical 6]

[0047]

[Chemical 7]

[0048]

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Examples of 3,4-substituted coumarins include compounds represented by the following formula (I).

[0050]

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(In the formula, R ¹ and R ² are the same or different and each represents a lower alkyl group such as methyl, ethyl, propyl, isopropyl and butyl; R ³ is a hydrogen atom, or methyl, ethyl, propyl and isobroprole. , Lower alkyl groups such as butyl, methoxymethyl, methoxyethyl, ethoxyethyl, propoxyethyl, methoxypropyl,
Alkoxyalkyl groups such as ethoxypropyl and propoxypropyl, hydroxyalkoxyalkyl groups such as hydroxymethoxyethyl, hydroxyethoxyethyl, hydroxyproxyethyl, hydroxymethoxypropyl, hydroxyethoxypropyl and hydroxypropoxypropyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, eth Represents an alkoxycarbonylalkyl group such as chiticarbonylethyl, propoxycarbonylpropyl and butoxycarbonylbutyl. ) Specific examples of the above compound include 3,4-substituted coumarins represented by the following structural formula (see Japanese Patent Application No. 3-223759).

[0052]

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[0053]

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Polymerization Initiator [C] This initiator [C] is decomposed by the action of a sensitizer upon irradiation with light and initiates a crosslinking reaction or a polymerization reaction of the photosensitive group.

As such a polymerization initiator, a substance which decomposes by the interaction with the above-mentioned sensitizer [B], more specifically, a cleavage reaction of itself, or a hydrogen abstraction reaction from another molecule, It is a compound that generates an active group for the crosslinking reaction or the polymerization reaction of the photosensitive group.

Specific examples of such a polymerization initiator include:
The following can be mentioned. For example, aromatic carbonyl compounds such as benzophenone, benzoin methyl ether, benzoin isopropyl ether, benzyl, xanthone, thioxanthone, and anthraquinone; acetophenone, propiophenone, α-hydroxyisobutylphenone, α, α′-dichloro-4-phenoxyacetophenone, Acetophenones such as 1-hydroxy-1-cyclohexylacetophenone and acetophenone;
Benzoyl peroxide, tert-butyl-peroxybenzoate, tert-butyl-peroxy-2-ethylhexanoate, tert-butyl hydroperoxide, ditertiary butyl diperoxyisophthalate, 3,3 ', 4,4' -Organic peroxides such as tetra (tertiarybutylperoxycarbonyl) benzophenone; diphenylhalonium salts such as diphenyliodonium bromide and diphenyliodonium chloride; organic halides such as carbon tetrachloride, carbon tetrabromide, chloroform and iodoform; Heterocyclic and polycyclic compounds such as 3-phenyl-5-isoxazolone, 2,4,6-tris (trichloromethyl) -1,3,5-triazinebenzanthrone; 2,2'-azo (2 4-dimethyl barre Nitrile), 2,2-azobisisobutyronitrile, 1,1′-azobis (cyclohexane-1-carbonitrile), 2,2′-azobis (2-methylbutyronitrile) and other azo compounds; iron- Iron-Arene Complex: European Patent 152
377); titanocene compounds (Japanese Patent Laid-Open No. 63-
221110); bisimidazole compounds; N-arylglycine compounds; acridine compounds; aromatic ketone / aromatic amine combinations; and the like.

Among the above-mentioned polymerization initiators, the titanocene compound is a particularly preferable compound because it shows high activity for crosslinking or polymerization in combination with the coumarin-type sensitizer in the composition of the present invention containing a colorant. .

Preferred examples of the titanocene compound include those represented by the following general formula.

[0059]

[Chemical 12]

In the formula, the two R ^{4 s} are each independently cyclopentadienyl (preferably cyclopentadienyl or methylcyclopentadienyl) unsubstituted or substituted by 1 to 2 methyl groups. ), And R ⁵ and R ⁶ are each independently the following formula:

[0061]

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[In the formula, R ⁷ is a fluorine atom, —CF ₃ or —
CF ₂ CH ₃ is represented, and R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are
Each independently _{fluorine, -CF 3, -CF 2 CH 3} , a hydrogen atom, an alkyl group of C ₁ -C _18, alkoxy group or

[0063]

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[Indicates].

Specific examples of the titanocene compound include:
For example, the compounds shown below can be mentioned.

[0066]

[Chemical 15]

Colorant [D] As the colorant [D], a pigment and a dye can be mentioned. However, since the heat resistance, the chemical resistance, the solvent resistance, the liquid crystal resistance and the light resistance are required, the pigment is selected. desirable. Further, since an appropriate spectrum and transparency are required, it is necessary to select an organic pigment having a large absorption coefficient of visible light and an average primary particle diameter sufficiently small with respect to visible light. . From the viewpoint of transparency, it is desirable that 95% by weight or more of the pigment particles have a particle diameter of 300 nm or less, preferably 120 nm or less. A sand mill, a kneader or 2
It is effective to reduce the particle size of the pigment by a known method using this roll or the like to improve the transparency and the absorption coefficient.

As a pigment suitable as the coloring agent [D], a material having various resistances is referred to as a color index (C.I.
I. ) Indicate by number.

C. I. Yellow pigment 24, 83, 86, 9
3, 94, 108, 109, 110, 117, 125,
137, 138, 147, 153, 154, 166, 1
68 C.I. I. Orange pigment 36, 43, 51, 55, 5
9, 61 C.I. I. Red pigment 97, 122, 123, 149, 1
68, 177, 178, 180, 187, 190, 19
2,209,215,216 or 217,220,2
23, 224, 226, 227, 228, 240 C.I. I. Violet pigment 19, 23, 29, 30,
37, 40, 50 C.I. I. Blue pigment 15, 15: 1, 15: 3, 15:
4, 15: 6, 22, 60, 64 C.I. I. Green pigment 7, 36 C.I. I. Brown pigment 23, 25, 26 C.I. I. Black Pigment 7 The composition of the present invention contains the above-mentioned components [A], [B], [C] and [D] as essential components, and the blending amount of each component is not particularly limited. Usually, it is suitable that it is within the following range.

That is, the coumarin type sensitizer [B] is added in an amount of 0.1 to 10 relative to 100 parts by weight of the photocurable resin component [A].
It is suitable that the amount is preferably 0.3 to 5 parts by weight from the viewpoint of the photosensitivity of the coating film formed and the solubility of the sensitizer [B] in the composition.

Further, the polymerization initiator [C] is 0.1 to 25 parts by weight, preferably 0.1 to 100 parts by weight of the component [A].
It is suitable that the amount is from 2 to 10 parts by weight in view of the photosensitivity of the coating film and the storage stability of the resulting composition.

Further, with respect to 100 parts by weight of the component [A],
Colorant [D] is 20 to 120 parts by weight, preferably 40 to
The amount of 90 parts by weight is suitable from the viewpoints of coloring property and transparency of the formed film.

The composition of the present invention is an essential component [A],
In addition to the components [B], [C] and [D], an organic solvent, a neutralizing agent, water, a pigment dispersant, a coating surface adjusting agent and the like may be contained if necessary.

The above-mentioned organic solvent is used for the purpose of adjusting fluidity and viscosity, and the composition of the present invention can be used in both organic solvent type and aqueous type. As this organic solvent,
For example, ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), esters (ethyl acetate,
Butyl acetate, methyl benzoate, methyl propionate, etc.), ethers (tetrahydrofuran, dioxane,
Dimethoxyethane, etc.), cellosolves (methyl cellosolve, ethyl cellosolve, diethylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, etc.), aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.), halogenated carbonization Examples thereof include hydrogen (chloroform, trichlorethylene, dichloromethane, etc.), alcohols (ethyl alcohol, benzyl alcohol, etc.), and others (dimethylformamide, dimethylsulfone oxime, etc.).

The above-mentioned neutralizing agent is used for neutralizing a part of the ionic groups in the photocurable resin component [A] when the composition of the present invention is made into a water dispersion or water solubilization. When an anionic group such as a carboxyl group is introduced into the component [A], it is neutralized with an alkali (neutralizing agent), and when a cationic group such as an amino group is introduced. , An acid (neutralizing agent) is used for neutralization. Examples of the alkali neutralizing agent used in that case include alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; alkylamines such as triethylamine, diethylamine, monoethylamine, diisopropylamine, trimethylamine and diisobutylamine; Alkyl alkanolamines such as dimethylaminoethanol; alicyclic amines such as cyclohexylamine; alkali metal hydroxides such as caustic soda and caustica; ammonia and the like. Examples of the acid neutralizer include monocarboxylic acids such as formic acid, acetic acid, lactic acid and butyric acid. These neutralizing agents can be used alone or as a mixture. The amount of the neutralizing agent used is generally in the range of 0.2 to 1.0 equivalent, and preferably 0.3 to 0.8 equivalent per mol of the ionic group contained in the component [A].

The composition of the present invention can be prepared by a conventionally known method. For example, a part of the photocurable resin component [A], a colorant [D] with a solvent and / or a pigment dispersant is used. The colorant paste may be dispersed to prepare a colorant paste, and this and the remaining components may be mixed uniformly. When the composition of the present invention is an aqueous composition, for example, a part of the photocurable resin component [A] is neutralized in advance, and a part of the neutralized product, solvent and / or
Alternatively, the colorant may be dispersed with a pigment dispersant to prepare a colorant paste, and this, the remaining neutralized product, and the remaining components may be uniformly mixed. The aqueous composition usually has a pH of 4 to 10.
Is preferably within the range.

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

In the method for producing a color filter of the present invention, step (1) is a step of forming a photosensitive coating film obtained from the above-mentioned photosensitive coloring composition for color filters on a transparent substrate.

As the method for forming the photosensitive coating on the transparent substrate, (a) the photosensitive coloring composition is applied on the transparent substrate by the dipping method, spraying method, spin coating method, silk screen method, roll coating method or curtain. A method of applying by a flow coating method and drying, (b) a method of performing electrodeposition coating using a water-based composition as a photosensitive coloring composition and a transparent substrate having a transparent conductive layer as a transparent substrate, ) A cover coat layer is formed on the substrate that has been subjected to easy peeling treatment in advance,
After the photosensitive coloring composition is coated on the cover coat layer and dried, the cover coat layer and the photosensitive coating layer on the substrate which has been subjected to the easy peeling treatment are transferred onto the transparent substrate to form a transparent substrate. Examples thereof include a method of forming a photosensitive film and a cover coat layer.

Examples of the transparent substrate in the method (a) include transparent glass, a transparent resin substrate, and a transparent substrate having a transparent conductive layer in the method (b).
As the transparent substrate having the transparent conductive layer, a thin film of transparent metal, indium oxide, tin oxide or the like is formed on the surface of a transparent substrate such as transparent glass or transparent resin substrate by a sol-gel method, sputtering, vapor deposition method, CVD method. A substrate obtained by forming the substrate can be used.

In the substrate subjected to the easy peeling treatment in the method (c), the substrate before the easy peeling treatment may be any substrate having a smooth surface and capable of being subjected to the easy peeling treatment, such as glass and resin. A substrate, a metal plate, etc. can be mentioned. This easy peeling treatment of the substrate is easy by forming a coating film on the substrate surface with a treatment agent such as a silicone resin, a silane coupling agent, a fluororesin, or a fluorosurfactant that forms a coating with a very small surface energy. Can be done. The thickness of this treated film is not particularly limited, but normally it is preferably about 0.001 to 0.1 μm. The coating can be formed by a known coating method such as dip coating or spin coating. By performing the easy peeling treatment, the transfer can be performed more easily and the productivity can be significantly improved. After forming the easily peelable treated coating, the coating may be cured by heating, actinic ray irradiation or the like, if necessary.

In the step (1), the photosensitive coating obtained from the photosensitive coloring composition is applied to the above (a), (b) or (c).
It is formed on the transparent substrate by the method described above. The film thickness of the photosensitive film is not particularly limited, but is usually 0.
It is preferably in the range of 5 to 5 μm.

In addition, after the coating layer of the photosensitive coloring composition is formed on the transparent substrate by the method (a), (b) or (c), the coating layer is coated so as not to interfere with the next operation. It is necessary to remove the organic solvent and water in the layer and harden it to a degree more than touch dry.

In the above method (b), the conditions for electrodeposition coating vary depending on the type of paint and the type of pattern, but when coating by the constant voltage method, the applied voltage is 10 to 150 V
180 seconds, current density 25-150mA / d in case of constant current method
The m ² is generally about 10 to 180 seconds.

In the above method (c), the cover coat layer is formed on the substrate which has been subjected to the easy peeling treatment in advance. The cover coat layer is non-photosensitive and is substantially non-adhesive at room temperature and does not contain oxygen. It is made of a material with a blocking ability. Therefore, its glass transition temperature is 20 ° C. or higher, and further 30 to
It is preferably in the range of 80 ° C, particularly 40 to 70 ° C.

The oxygen barrier property of the cover coat layer is 5 × 10 ⁻¹² cc · cm / cm ² · sec · cmHg or less, particularly 1 × 10 ⁻¹² cc · cm / cm ² · sec as the oxygen gas permeability of the film. -It is preferably cmHg or less. Oxygen gas permeability here is ASTMstan
It is a value measured according to the method described in dards D-1434-82 (1986).

Further, it is desirable that the cover coat layer should be substantially soluble in the developing solution. If it is not soluble in the developer, the cover coat must be peeled off before development, which is disadvantageous in terms of productivity. As the film-forming resin for forming the cover coat that satisfies such conditions, for example,
Examples thereof include polyvinyl alcohol, partially saponified polyvinyl acetate or a mixture thereof, or a mixture of polyvinyl alcohol and a vinyl acetate polymer. These are preferable because they are excellent in film forming property and have good solubility in an aqueous developer such as water, diluted alkaline water, diluted acid water and the like.

The cover coat layer can be formed by applying a solution such as an aqueous solution of the film-forming resin to a substrate which has been subjected to easy peeling treatment in advance and drying. The thickness of the cover coat layer is usually 0.5 to 5 μm, preferably 1 to 3 μm.

In the method (c), the photosensitive coloring composition is applied onto the cover coat layer obtained as described above and dried to form a photosensitive coating layer, which is then subjected to easy peeling treatment. The cover coat layer and the photosensitive coating layer formed on the above substrate are transferred onto the transparent substrate to form the photosensitive coating layer and the cover coating layer on the transparent substrate. In this case, the transfer operation can be performed more easily and reliably by providing an adhesive layer on the transparent substrate that receives the cover coat layer and the photosensitive film by the transfer, and the production in the color filter manufacturing can be performed. You can greatly improve the property.

The above-mentioned adhesive is not particularly limited, and conventionally known thermoplastic, thermosetting, photocurable, pressure-sensitive adhesive and the like can be used. Adhesive is spray method, roll coater method,
The adhesive layer can be provided on the transparent substrate by a printing method, a spin coater method or the like, which is usually applied in an amount of about 0.1 to 3 μm.

In the method of the present invention, the step (2) is a step of forming a cover coat layer on the photosensitive film as the case requires, and in the case of the methods (a) and (b) of the above step (1) Is a process that is performed as necessary, and
In the case of the method (2), the cover coat layer is formed in the step (1), and thus the step (2) is unnecessary.

In order to form the cover coat layer on the photosensitive film in the step (2), a solution such as an aqueous solution of the film-forming resin used in the method (c) of the step (1) is applied onto the photosensitive film. It may be applied and dried. The thickness of the cover coat layer is usually 0.5 to 5 μm, further 1 to 3 μm
It is preferably within the range.

In the method of the present invention, the step (3) is a step of exposing the photosensitive coating in a pattern with a visible light laser to cure the exposed portion of the photosensitive coating. Light sources for visible light laser exposure include ultra-high pressure, high pressure, medium pressure and low pressure mercury lamps, chemical lamps, carbon arc lamps, xenon lamps, metal halide lamps, fluorescent lamps, tungsten lamps,
Among the light sources obtained by each light source such as sunlight, various visible light rays obtained by cutting ultraviolet rays with an ultraviolet cut filter or various lasers having an oscillation line in the visible light area can be used. Of these, an argon laser having an oscillation line at 488 nm or 514.5 nm is preferable. The exposure amount of the visible light laser may be appropriately selected depending on the type of the photosensitive film and the like, and is usually in the range of 0.1 to 20 mj / cm ² .

In the method of the present invention, the step (4) forms a color pattern by removing the photosensitive film in the non-exposed portion from the photosensitive film which has been patterned and exposed and cured in the step (3) by developing treatment. It is a process to do.

The developing treatment is carried out by washing with an aqueous alkali solution when the photosensitive film in the non-exposed area is anionic and with an aqueous acid solution when it is cationic. The alkaline aqueous solution is usually caustic soda,
An aqueous solution of a basic substance such as sodium carbonate, caustic potash, or ammonia is used, and an aqueous solution of an acid such as acetic acid, formic acid, or lactic acid is usually used as the acid aqueous solution. When the cover coat layer is present on the photosensitive film, the cover coat layer is also dissolved and removed during the development process.

In the method of the present invention, the step (5) is a step of heating and further curing the color pattern formed in the above step (4), and is carried out if necessary.

A desired color pattern of one color can be formed by the above steps (1) to (5). In the present invention, after the step (4) or the step (5), the steps (1) to (5) are performed a necessary number of times using a photosensitive coloring composition of different colors on a transparent substrate having a color pattern formed thereon. A color filter can be manufactured by repeatedly forming a multicolored color pattern. Red, blue, and green are generally used as the colors of the multicolored color pattern, and a black black matrix that does not transmit light other than the above is generally formed.

[0098]

By using the photosensitive coloring composition of the present invention, a color filter can be manufactured by direct drawing with a visible light laser. Further, the photosensitive coloring composition of the present invention has good sensitivity to visible light laser and good energy conversion efficiency.

Further, since a colored pattern can be formed by direct drawing, it is not necessary to prepare a photomask for each color pattern or to install a photomask on the resist film for each color, which significantly reduces the number of working steps. be able to.

[0100]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the examples, "parts" and "%" all indicate "parts by weight" and "% by weight" unless otherwise specified. Production Example 1 Methyl methacrylate 10 parts, ethyl acrylate 35
Parts, 55 parts of acrylic acid, azobisisobutyronitrile 2
11 parts of a monomer mixture liquid under a nitrogen gas atmosphere.
It was added dropwise to 90 parts of isobutyl alcohol kept at 0 ° C. over 3 hours. After dropping, after keeping at 110 ° C for 1 hour,
A mixed solution containing 1 part of azobisdimethylvaleronitrile and 10 parts of isobutyl alcohol was added dropwise over 1 hour, and the mixture was kept for 5 hours to obtain a high acid value acrylic resin.
Next, 80 parts of glycidyl methacrylate is added to this solution,
Add 0.1 parts of hydroquinone and 0.8 parts of tetraethylammonium bromide, and add 1 while blowing air.
The reaction was carried out at 10 ° C for 5 hours, and the photocurable resin solution 1 (carboxyl group concentration 1.1 mol / kg resin, unsaturated group concentration 3.1
3 mol / kg resin, resin Tg-2 ° C., solid content 64%) were obtained.

Example 1 The photocurable resin solution 1 obtained in Production Example 1 and other components were uniformly dispersed according to the formulation shown in Table 1 below to give red, green and
Each blue and black photosensitive coloring composition was obtained. The photocurable resin component in each composition has a photosensitive group concentration of 6.81 mol / kg and a carboxyl group concentration of 0.55 mol / kg. The average particle size of the pigment in each composition is as follows:
60 nm, green pigment: 90 nm, blue pigment: 80 nm, black pigment: 5
0 nm, and 95% by weight or more of all pigments have a particle size of 12
It was 0 nm or less.

Polyvinyl alcohol (degree of polymerization: 1,70) was formed on a polyethylene terephthalate film having a thickness of 75 μm.
0, Tg 65 ° C, oxygen permeability 2 × 10 ^-14 cc ・ cm / cm ²・ se
A 12% aqueous solution of c · cmHg) was uniformly applied by a roll coating method so as to have a dry film thickness of 2 μm, and dried at 80 ° C. for 10 minutes to obtain a cover coat transfer film. The red photosensitive coloring composition was applied onto the cover coat layer of this film by a roll coating method so that the dry film thickness was 2 μm, and dried at 80 ° C. for 10 minutes to form a transfer type red photosensitive coating layer. Formed.

The surface of the photosensitive coating layer was brought into close contact with a glass plate heated to 80 ° C. by a thermal laminating method, and then the polyethylene terephthalate film was peeled off to form a red photosensitive coating with a cover coat on the glass plate.

Further, 1.5 mj / cm ² was formed on this photosensitive film by a direct drawing method with an argon ion laser having a wavelength of 488 nm.
The pattern was exposed under the irradiation conditions of. Then 1 at 30 ℃
% Aqueous sodium carbonate solution for 60 seconds to develop, wash with water, dry and dry to obtain a red color pattern.

Next, instead of the red photosensitive coloring composition, the green photosensitive coloring composition shown in Table 1 below was used to form a transfer type green photosensitive coating layer on the cover coat transfer film. This green photosensitive coating layer surface is adhered to the glass plate having the above red color pattern, and then the polyethylene terephthalate film is peeled off to form a green photosensitive coating with a cover coat on the glass plate having a red color pattern. Then, in the same manner as above, exposure, development, washing with water, draining and drying were performed to obtain a color pattern of green in addition to red.

Next, the same steps as described above are repeated using the blue and black photosensitive coloring compositions to form red, green, blue and black color patterns on the glass plate, and to prepare a multi-color pattern suitable for color filters. A color pattern of colors was obtained.

Line / space (L / L) of the pattern of each color
S) is 10 for red, green and blue color patterns.
0 μm / 20 μm, and 20 μm / 100 μm for a black color pattern (black matrix).

[0108]

[Table 1]

(Note) in Table 1 has the following meanings.

(* 1) Titanocene compound (T-1):

[0111]

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(* 2) Sensitizer (A-1):

[0113]

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Production Example 2 1,000 parts of propylene glycol monomethyl ether was placed in a flask equipped with a stirrer, a reflux condenser, a monomer dropping device, a thermometer, and a nitrogen gas blowing device, and 120 ° C. while introducing nitrogen gas. While heating to this temperature and maintaining this temperature, 464 parts of ethyl methacrylate, 265 parts of methyl acrylate, 80 parts of acrylic acid, 92 parts of 2-hydroxyethyl methacrylate, 99 parts of 2-hydroxypropyl methacrylate and 60 parts of t-butyl peroxyoctoate. The mixed solution was added dropwise over 2 hours, and further maintained at this temperature for 2 hours, and then 5 parts of powdery 2,2'-azobisisobutyronitrile was gradually added over 30 minutes as an additional catalyst. Then, the mixture was kept at this temperature for 2 hours for aging to obtain a number average molecular weight of about 16,500, carboxy. Group concentration 1.1 mol / kg resin, Tg point 48 ° C., about solids 66
% Ionic group-containing resin solution 2 was obtained.

Example 2 The ionic group-containing resin solution 2 obtained in Production Example 2 and other components were uniformly dispersed according to the formulation shown in Table 2 below, and red,
Each of the green, blue and black photosensitive coloring compositions was obtained. The photocurable resin component in each composition has a photosensitive group concentration of 3.
It has a concentration of 54 mol / kg and a carboxyl group concentration of 0.77 mol / kg. The average particle diameter of each pigment in each composition is: red pigment: 70 nm, green pigment: 80 nm, blue pigment: 90 nm, black pigment: 60 nm, and all pigments have a particle diameter of 120 nm or less at 95% by weight or more. It was

The red photosensitive coloring composition obtained as described above was applied onto a glass plate (100 × 100 × 1.1 mm) by a spin coating method so as to have a dry film thickness of about 2 μm, and then at 80 ° C. After drying for 10 minutes at room temperature,
The 12% aqueous solution of polyvinyl alcohol used for the cover coating was applied by spin coating to a dry film thickness of about 2 μm and dried at 80 ° C. for 10 minutes to form a red photosensitive film layer and cover coat on the glass plate. Layers were formed.

Next, this photosensitive film was patternwise exposed by an argon laser having a wavelength of 488 nm by a direct writing method under an irradiation condition of 1.5 mj / cm ² . Then, a 1% sodium carbonate aqueous solution at 30 ° C. was sprayed for 60 seconds to develop, wash with water, drain and dry to obtain a red color pattern.

Then, a green photosensitive coating layer and a cover coat layer from the green photosensitive coloring composition are formed on the glass plate on which the red color pattern has been formed in the same manner as described above, and exposure, development, washing with water and draining are performed. After drying, a green color pattern was obtained on the glass plate in addition to red.

Then, the same steps as described above are repeated using the blue and black photosensitive coloring compositions to obtain red, green and
Blue and black color patterns were formed on a glass plate to obtain a multicolored color pattern suitable for a color filter.

The (L / S) of each color pattern was the same as in Example 1.

[0121]

[Table 2]

(Note) in Table 2 has the following meanings.

(* 3) Titanocene compound (T-2):

[0124]

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(* 4) Sensitizer (A-2):

[0126]

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Production Example 3 40 parts of methyl methacrylate, 40 parts of butyl acrylate
, A mixture of 20 parts of acrylic acid and 2 parts of azobisisobutyronitrile in a nitrogen atmosphere.
It was added dropwise to 90 parts of propylene glycol monomethyl ether (hydrophilic solvent) kept at 10 ° C. for 3 hours.
After the dropping, the mixture was aged for 1 hour, a mixed solution containing 1 part of azobisdimethylvaleronitrile and 10 parts of propylene glycol monomethyl ether was added dropwise over 1 hour, and the mixture was aged for 5 hours to obtain a high acid value acrylic resin (acid value 155 ) A solution was obtained. Next, 24 parts of glycidyl methacrylate, 0.12 part of hydroquinone and 0.6 part of tetraethylammonium bromide were added to this solution, and the mixture was reacted at 110 ° C. for 5 hours while blowing air to react with the photocurable resin (concentration of carboxyl group: 0. 89 mol / kg, unsaturated group concentration 1.35 mol / kg, Tg point 20 ° C, number average molecular weight about 2
A solids solution 55.6% solids solution was obtained.

Example 3 To 180 parts (solid content 100 parts) of the photocurable resin solution 3 obtained in Production Example 3 was added 6 parts triethylamine to sufficiently neutralize, and then anthraquinone red (C.I. .1
77) 51 parts and disazo yellow (C.I.83)
Add 9 parts and disperse the pigment with a paint shaker. Add 15 parts benzyl alcohol and sensitizer (A-3) to this.
(* 5) 1 part and a titanocene compound (T-3) (* 6) 7 parts as a polymerization initiator were uniformly mixed. Next, deionized water was added to this product to adjust the solid content concentration to 15% to obtain a red electrodeposition coating bath (pH 6.5).

In the production of the above red electrodeposition coating bath, each color electrodeposition coating bath was obtained in the same manner except that the following pigments were used.

Green electrodeposition coating bath: Disazo yellow (C.I.
I. 83) 6 parts and phthalocyanine green (C.
I. 36) 54 parts, blue electrodeposition coating bath: phthalocyanine blue (C.I.
5: 6) 48 parts and dioxazine violet (C.
I. 23) 12 parts, black electrodeposition coating bath: carbon black 60 parts.

The photocurable resin component in each electrodeposition coating bath has a photosensitive group concentration of 1.35 mol / kg and a carboxyl group concentration of 0.89 mol / kg. The average particle size of each pigment in each electrodeposition coating bath is: red pigment: 70 nm, green pigment: 90
nm, blue pigment: 80 nm, black pigment: 50 nm, and 95% by weight or more of all pigments had a particle size of 120 nm or less.

Using the above red electrodeposition coating bath, transparent IT
Glass plate with O film (indium-tin oxide film) (100 x 1
00 × 1.1mm) as an anode, and bath temperature 25 ℃ at 45mA / cm ²
Was applied for 3 minutes for electrodeposition coating. The obtained electrodeposition coating film is washed with water and dried at 80 ° C. for 5 minutes to 2.0.
A non-sticky, smooth photosensitive film having a thickness of μm was obtained. This photosensitive film was irradiated with an argon laser beam having a wavelength of 488 nm in a pattern by a direct drawing method under the condition of an exposure amount of 1.5 mj / cm ² , and then developed for 1 minute using a 1% sodium carbonate aqueous solution at 30 ° C. It was washed with water to obtain a red color pattern.

Next, using the green and blue electrodeposition coating baths, the transparent ITO film-coated glass plate on which the above red color pattern was formed, was repeatedly subjected to the same steps as above to carry out the red, green and blue color patterns. Was formed. Then, using a black electrodeposition coating bath, electrodeposition coating was performed under the same conditions as above on a glass plate with a transparent ITO film on which red, green and blue color patterns were formed, and then argon laser light was applied in the same manner as above. The black color pattern is cured by irradiating under the conditions, and the red, green, blue and black color patterns are transparent I
It was formed on a glass plate with a TO film to obtain a multicolored color pattern suitable for a color filter. (L / of the pattern of each color
S) was the same as in Example 1.

(* 5) Sensitizer (A-3):

[0135]

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(* 6) Titanocene compound (T-3):

[0137]

[Chemical 21]

Production Example 4 (for comparison) A monomer mixture containing 10 parts of methyl methacrylate, 90 parts of acrylic acid and 2 parts of azobisisobutyronitrile was added to 90 parts of isobutyl alcohol kept at 110 ° C. under a nitrogen gas atmosphere. Was added dropwise over 3 hours. After dropping
After maintaining at 110 ° C. for 1 hour, a mixed solution containing 1 part of azobisdimethylvaleronitrile and 10 parts of isobutyl alcohol was added dropwise over 1 hour, and the mixture was kept for 5 hours to obtain a high acid value acrylic resin. Next, 20 parts of glycidyl methacrylate, 0.1 part of hydroquinone and 0.8 part of tetraethylammonium bromide were added to this solution, and the mixture was reacted at 110 ° C. for 5 hours while blowing air,
A photocurable resin solution 4 having a solid content of 55% was obtained. The obtained resin had a carboxyl group concentration of 9.2 mol / kg resin and an unsaturated group concentration of 1.17 mol / kg resin.

Comparative Example 1 64% photocurable resin solution 1 obtained in Production Example 1 in the formulation shown in Table 1 of each photosensitive coloring composition prepared in Example 1
Instead of using 78 parts of, 55 parts of 55% photocurable resin solution 4 obtained in Production Example 4 was used in the same manner,
Red, green, blue and black photosensitive coloring compositions were obtained. The photocurable resin component in each composition has a photosensitive group concentration of 4.
It has a concentration of 85 mol / kg and a carboxyl group concentration of 4.6 mol / kg. The average particle size of the pigment in each composition was 70 nm for the red pigment, 90 nm for the green pigment, 80 nm for the blue pigment, and 60 nm for the black pigment. .

Hereinafter, using each of the photosensitive coloring compositions obtained as described above, the same steps as in Example 1 were carried out to prepare a multicolor color pattern. Was also dissolved and a good pattern could not be formed.

Comparative Example 2 In the formulation shown in Table 2 of each photosensitive coloring composition prepared in Example 2, the amount of the 66% ionic group-containing resin solution obtained in Production Example 2 was changed from 106 parts to 45 parts. Then, the same procedure was performed except that the amount of trimethylolpropane triacrylate was changed from 30 parts to 70 parts to obtain red, green, blue and black photosensitive coloring compositions. The photocurable resin component in each composition has a photosensitive group concentration of 8.26 mol / kg and a carboxyl group concentration of 0.33 mol / kg. The average particle size of the pigment in each composition is as follows: red pigment: 80 nm, green pigment: 9
0 nm, blue pigment: 80 nm, black pigment: 50 nm, and 95% by weight or more of all pigments had a particle size of 120 nm or less.

The following steps were carried out in the same manner as in Example 1 by using each of the photosensitive coloring compositions obtained as described above to prepare a multicolor color pattern. Due to an increase in internal stress of the colored pattern coating film, the colored pattern cured coating film was also peeled off from the substrate due to an external force during development, and the color pattern could not be formed.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location G03F 7/027 511 G03F 7/027 511 7/029 7/029 7/031 7/031 (72) Inventor Nakatani ▲ Sakae ▼ Product 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd.

Claims (10)

[Claims] 1. A photocurable resin containing [A] (a) a photosensitive group that can be crosslinked or polymerized by irradiation with light, and an ionic group, (b) an ethylenically unsaturated compound, and (c) an ionic group. Containing at least one component of a binder containing,
Component (a) or a mixture of component (b) and component (c) as a main component, and the total amount of components (a), (b) and (c) is 0. .2-7.0
Mol / kg, photocurable resin component having an ionic group content of 0.2 to 3.5 mol / kg, [B] coumarin sensitizer, [C] polymerization initiator and [D] colorant A photosensitive coloring composition for a color filter, which is contained as a component, for direct drawing with a visible light laser. 2. The photosensitive coloring composition according to claim 1, wherein the polymerization initiator is a titanocene compound. 3. The photosensitive coloring composition according to claim 1, wherein the photocurable resin component [A] is an anionic resin obtained by adding a glycidyl group-containing unsaturated compound to a high acid value acrylic resin. 4. A coloring agent [D] in a photosensitive coloring composition.
Has a particle size distribution of more than 95% by weight of the coloring agent [D] is 300
The photosensitive coloring composition according to any one of claims 1 to 3, which has a wavelength of not more than nm. 5. (1) A step of forming a photosensitive coating from the photosensitive coloring composition according to claim 1 on a transparent substrate, (2) If necessary, a cover coat layer is formed on the photosensitive coating. And (3) a step of curing the exposed portion of the photosensitive coating by exposing the photosensitive coating to a visible light laser in a pattern, and (4) subsequently developing to remove the photosensitive coating from the non-exposed portion and color. A method of manufacturing a color filter, comprising: a step of forming a pattern; and (5) a step of further heating if necessary. 6. After the step of (4) forming a color pattern or (5) the step of heating if necessary, a photosensitive coloring composition of different colors is used on a transparent substrate having a color pattern formed thereon, The method for producing a color filter according to claim 5, wherein steps (1) to (5) are repeated a required number of times to form a multicolored color pattern. 7. A photosensitive coating composition is formed on a substrate by applying the photosensitive coloring composition onto the substrate by a dipping method, a spray method, a spin coating method, a silk screen method, a roll coating method or a curtain flow coating method. The method for producing a color filter according to claim 5, wherein the method is performed by 8. A substrate on which a photosensitive coating is formed is a transparent substrate having a conductive layer, and the photosensitive coloring composition [A] is an aqueous composition having an anionic group, which is obtained by an anion electrodeposition coating method. The method for producing a color filter according to claim 5, wherein a photosensitive coating is formed on the substrate. 9. In the step (1) of forming a photosensitive coating from the photosensitive coloring composition according to claim 1 on a substrate, a cover coat layer is formed on a substrate which has been subjected to easy peeling treatment in advance, and After the photosensitive coloring composition is coated on the cover coat layer and dried, the cover coat layer and the photosensitive coating layer on the substrate which has been subjected to the easy peeling treatment are transferred onto another transparent substrate to form a transparent substrate. The method for producing a color filter according to claim 5, wherein a photosensitive film and a cover coat layer are formed on the substrate, and then the steps (3) to (5) are performed. 10. After the step of (4) forming a color pattern and (5) the step of heating if necessary, a photosensitive coloring composition of different colors is used on the transparent substrate on which the color pattern is formed. 10. The method for producing a color filter according to claim 9, wherein the steps (1), (3), (4) and (5) are repeated a required number of times to form a multicolor color pattern.