JPH09127693A - Aqueous photosensitive colored composition and production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aq. colored photoresist having high sensitivity, excellent in developer resistance and favorable from the viewpoint of environmental protection and saving of resources by using a photopolymerizable water- dispersible resin as a resin component and a specified photopolymn. initiator. SOLUTION: This colored compsn. contains a photopolymerizable water- dispersible resin (a) having polymerizable unsatd. groups and acid groups, an ethylenically unsatd. compd. (b), a coloring pigment (c), a photopolymn. initiator (d) made of a mixture of a thioxanthone compd. with an acetophenone compd. and/or a P-contg. initiator and a pigment dispersing agent (e). The resin (a) is a water-dispersible photosetting resin having polymerizable unsatd. groups capable of polymn. (crosslinking) by irradiation with active light and acid groups. When the resin is irradiated with light, it is made practically insoluble or slightly soluble in an aq. alkali soln. as a developer by a polymn. reaction. The unexposed part of the resin is soluble in the alkali developer.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a water-based photosensitive coloring composition having a wide developing width suitable for a color filter used in a display device such as a liquid crystal, and a method for producing a color filter using this photosensitive coloring composition. .

[0002]

2. Description of the Related Art
Generally, a photosensitive coloring composition for a color filter (hereinafter, may be abbreviated as “colored photoresist”) is formed into a film by coating or the like, and is exposed to actinic rays such as ultraviolet rays in a pattern through a pattern mask, A colored pattern is formed by developing.

Acetophenone, 1-hydroxylcyclohexyl-phenyl ketone, benzyl dimethyl ketal, etc. are generally used as a photopolymerization initiator in this colored photoresist, but in a colored photoresist containing many pigments, These photopolymerization initiators have low sensitivity, and require a considerably large amount of exposure and exposure time during exposure, resulting in poor productivity. Further, since it is usually necessary to form at least three colors of red, blue, and green as the coloring pattern, film formation, exposure, and development are performed for each color, so the coloring pattern formed first is developed. Will be received many times. For this reason, it is necessary to have excellent developer resistance, but there is a problem in that quality defects such as poor developer resistance due to insufficient curing of image lines are likely to occur. Generally, the colored photoresist is an organic solvent diluted type, and an aqueous colored photoresist is required from the viewpoint of environmental protection and resource saving.

Therefore, the present inventors have found that a colored photoresist containing a large amount of pigment has high sensitivity, excellent curability, excellent developer resistance, and is water-based from the viewpoint of environmental protection and resource saving. As a result of intensive research to obtain a photoresist, a photopolymerizable water-dispersible resin was used as a resin component,
It was also found that the above object can be achieved by using a specific photopolymerization initiator.

[0005]

That is, the present invention provides:
(A) a photopolymerizable water-dispersible resin having a polymerizable unsaturated group and an acid group, (b) an ethylenically unsaturated compound, (c) a color pigment, (d) a thioxanthone compound, and an acetophenone compound and / Alternatively, the present invention provides an aqueous photosensitive coloring composition characterized by containing a photopolymerization initiator comprising a mixture with a phosphorus-containing initiator and (e) a pigment dispersant.

[0006] The present invention also provides: (1) a step of forming a photosensitive coating from the photosensitive coloring composition according to claim 1 on a transparent substrate, (2) a step of forming a cover coat layer on the photosensitive coating, if necessary, (3) ) A step of exposing the photosensitive coating to actinic rays in a pattern to cure the exposed portion of the photosensitive coating, (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 for manufacturing a color filter, which further comprises a step of heating if necessary.

[0007]

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), (d) and (e) as essential components.

Photopolymerizable having a polymerizable unsaturated group and an acid group
The functional water-dispersible resin (a) The resin (a) is a water-dispersible photocurable resin containing a polymerizable unsaturated group and an acid group that can be polymerized (crosslinked) by irradiation with actinic rays. Polymerization reaction by light irradiation,
A portion which is substantially insoluble or hardly soluble in an alkaline aqueous solution which is a developing solution and which is not exposed is soluble in the alkaline developing solution.

The polymerizable unsaturated group is a polymerization initiator (d).
Is a group capable of being polymerized (crosslinked) by irradiation with an actinic ray in the presence of, for example, a (meth) acryloyl group [CH ₂ ═CR—CO— (wherein R is a hydrogen atom or a methyl group). )], Cinnamoyl group, allyl group, azido group, cinnamylidene group and the like.

The amount of the polymerizable unsaturated group and the acid group in the resin (a) can be varied over a wide range depending on the kind and the molecular weight of the resin, but the amount of the polymerizable unsaturated group is determined by the photopolymerization. In general, from the viewpoint of the properties and the physical properties of the cured film,
~ 7.0 eq / kg resin, preferably 0.7-4.5 eq
The amount of acid groups is preferably 0.2 and the amount of acid groups is 0.2.
~ 3.5 eq / kg resin, preferably 0.3-2.0 eq
It is suitable that the content of the resin is within the range of / kg resin from the viewpoint of water dispersibility, developability and water resistance.

The resin (a) is generally 5,000 to
500,000, preferably 10,000 to 100,0
The number average molecular weight can be within the range of 00, and the glass transition temperature (Tg) thereof is preferably 0 ° C. or higher, particularly within the range of 5 to 70 ° C., since the coating film does not exhibit tackiness. .

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

(A) An emulsion in which a polymerizable unsaturated group is introduced later into an aqueous emulsion having an acid group: First, an unsaturated acid monomer and a vinyl monomer copolymerizable with the monomer are copolymerized by various known emulsion polymerization methods. An aqueous emulsion having a polymerized and acid group is prepared. Then, the alkali-developable polymerizable unsaturated group-containing aqueous emulsion of the present invention is obtained by subjecting this aqueous emulsion having an acid group to an addition reaction with a compound having a polymerizable unsaturated group and an epoxy group in one molecule. . Emulsion polymerization uses water as a medium to disperse and emulsify monomers with an emulsifier,
It is carried out by adding a water-soluble polymerization initiator and heating at 50 to 90 ° C. It is also possible to work at room temperature with a redox initiator. As the emulsifier, anion activators such as sulfates of higher alcohols and alkyl sulfonates, and nonionic activators such as various alkyl ethers, alkyl esters and alkyl allyl ethers of polyoxyethylene are used. In addition, polyvinyl alcohol may be used in combination as a stabilizer (protective colloid) for the emulsion. As the polymerization initiator, hydrogen peroxide, ammonium persulfate, cumene hydroperoxide, water-soluble redox initiator or the like is used.

The unsaturated acid monomers used in emulsion polymerization include monobasic acid monomers such as acrylic acid, methacrylic acid and crotonic acid; dibasic acid monomers such as fumaric acid, citraconic acid and itaconic acid and their half-esterified products;
Hydroxy group-containing (meth) such as 2-hydroxyethyl (meth) acrylate and hydroxypropyl (meth) acrylate
Examples thereof include half-esterified products of acrylic acid esters with dibasic acids such as succinic acid, phthalic acid, tetrahydrophthalic acid, and hexahydrophthalic anhydride. If the amount of the unsaturated acid monomer used is small, the solubility in alkaline water will decrease, and if it is too large, the water resistance will deteriorate. Therefore, the resin acid value is preferably 20 to 780, and more preferably 80 to 150.

The monomer copolymerizable with the unsaturated acid monomer is selected so that the polymer emulsion has desired physical and chemical properties (for example, elasticity, rigidity, chemical resistance, etc.). For example, unsaturated amide monomers such as acrylamide, methacrylamide, diacetone acrylamide, maleic acid diamide, crotonic acid amide, itaconic acid diamide, fumaric acid diamide; styrenes, (meth) acrylonitrile, vinyl acetate, vinyl chloride; Α-olefins such as isobutene; dienes such as butadiene; vinyl ethers such as ethyl vinyl ether; methyl acrylate, ethyl acrylate,
N-propyl acrylate, isopropyl acrylate, butyl acrylate (n-, i-, t-), hexyl acrylate, 2-ethylhexyl acrylate, n-acrylate
Octyl, decyl acrylate, lauryl acrylate, stearyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, n methacrylate
-Propyl, isopropyl methacrylate, butyl methacrylate (n-, i-, t-), hexyl methacrylate,
2-ethylhexyl methacrylate, octyl methacrylate, decyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, etc. Acrylic acid or methacrylic acid having 1 to 18 carbon atoms (1-2
4) an alkyl ester or a cycloalkyl ester;
C2 of acrylic acid or methacrylic acid such as methoxybutyl acrylate, methoxybutyl methacrylate, methoxyethyl acrylate, methoxyethyl methacrylate, ethoxybutyl acrylate, and ethoxybutyl methacrylate
~ 18 alkoxyalkyl ester; 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate,
2- or 3-hydroxypropyl methacrylate, hydroxybutyl acrylate, C ₂ -C ₈ hydroxyalkyl esters of acrylic acid or methacrylic acid such as hydroxyethyl methacrylate; N- vinylpyridine, N-
Examples thereof include nitrogen-containing monomers such as vinylcarbazole and N-vinylpyrrolidone. These can be used alone or in combination of two or more.

Among the monomers copolymerizable with the above unsaturated acid monomer, the use of an unsaturated amide monomer means that the unsaturated amide monomer is very well soluble in water, and the polymer is also soluble in water. Due to its extremely high distribution on the surface of emulsion particles, it plays a role as a so-called thickener or protective colloid for emulsion particles, and unlike conventional protective colloids, it is copolymerized with hydrophobic monomers and firmly fixed inside the particles. Therefore, it is particularly preferable. Therefore, the emulsion particles obtained by copolymerizing the unsaturated amide monomer are extremely stable, and in particular, have very high resistance to chemical and mechanical operations when the third component is added. When the amount of the unsaturated amide monomer used is large, the amount of the water-soluble polymer portion is large, the viscosity is remarkably high, and it becomes difficult to obtain a high-concentration polymer emulsion. On the other hand, if the amount is too small, the polymer emulsion having the above characteristics cannot be obtained. Therefore, the unsaturated amide monomer is usually used in the range of 0 to 50% by weight, preferably 2 to 40% by weight in the monomer component.

Next, an aqueous emulsion having an acid group is added,
A compound having a polymerizable unsaturated group and an epoxy group in one molecule (hereinafter, this compound is referred to as “unsaturated epoxy monomer”) undergoes an addition reaction, and this reaction is usually performed with hydroquinone, hydroquinone monomethyl ether, benzoquinone and the like. 1 to 1 at 50 to 90 ° C in the presence of the polymerization inhibitor of
This is done by heating for 0 hours. The reaction can be smoothly carried out by using an epoxy ring-opening catalyst. Examples of the epoxy ring-opening catalyst include cyclic nitrogen compounds such as 2-ethylimidazole, pyridine and picoline, 4
Examples thereof include a tertiary ammonium salt, a tertiary sulfonium salt, a tertiary amine, and an amine hydrochloride. The amount used is preferably 0.01 to 25 mol% based on the epoxy group.

The unsaturated epoxy monomer added to the aqueous emulsion having an acid group includes glycidyl methacrylate, glycidyl acrylate, methyl glycidyl methacrylate, methyl glycidyl acrylate, allyl glycidyl ether, α-ethyl glycidyl ether, crotonyl glycidyl ether, and glycidyl. Crotonate, itaconic acid monoalkyl ester monoglycidyl ester, fumaric acid monoalkyl ester monoglycidyl ester, maleic acid monoalkyl ester monoglycidyl ester, Cyclomer M100 (manufactured by Daicel Chemical Industries, Ltd.), Cyclomer A200 (Daicel Chemical ( Co., Ltd.) and the like. These are used in the reaction either alone or in combination of two or more.

The amount of the unsaturated epoxy monomer added is preferably 0.1 to 0.9 equivalent based on the acid group. When the amount of the unsaturated epoxy monomer added is 0.1 equivalent or less, the curability of the emulsion is extremely lowered. On the other hand, if it is added in excess of 0.95 equivalents, the acid value will be low, and the developability of the resulting film with respect to an alkaline developer after exposure and the storage stability of the emulsion will be reduced.

(B) Water-dispersible resin obtained by introducing a polymerizable unsaturated group into a high acid value acrylic resin and then neutralizing it: Resin (a) is, for example, a high acid value acrylic resin containing the above unsaturated epoxy. It can be produced by adding a monomer, followed by neutralization and water dispersion. The high acid value acrylic resin used at that time is, for example, α, such as acrylic acid, methacrylic acid, itaconic acid, maleic acid or fumaric acid.
β-ethylenically unsaturated acids and esters of (meth) acrylic acid, 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,
It can be obtained by using 2-hydroxypropyl (meth) acrylate as an essential component and optionally copolymerizing other polymerizable unsaturated monomers such as styrene, (meth) acrylonitrile and (meth) acrylamide. Here, the α, β-ethylenically unsaturated acid has a high acid value acrylic resin generally having an acid value of 40 to 650, preferably 60 to 50.
It can be used in an amount such that it is in the range of 0. Further, the number average molecular weight and glass transition temperature (Tg) of the high acid value acrylic resin are such that the resin obtained by adding an unsaturated epoxy monomer to the high acid value acrylic resin has the above number average molecular weight and Tg. It is adjusted appropriately.

On the other hand, as the unsaturated epoxy monomer added to the high acid value acrylic resin, those exemplified as the unsaturated epoxy monomer in the section of the emulsion (a) can be used.

The above-mentioned addition reaction between the high acid value acrylic resin and the unsaturated epoxy monomer is carried out according to a method known per se, for example, by using a catalyst such as tetraethylammonium bromide at 80 to 120 ° C. for 1 to 5 hours. This can be done easily.

The resulting addition reaction product is then neutralized with a basic compound and dispersed in water by a conventional method. As the basic compound, sodium hydroxide, an alkali metal hydroxide such as potassium hydroxide, morpholine, triethylamine,
Examples include amines such as dimethylethanolamine and di-n-butylamine, and ammonia. The degree of neutralization is not limited as long as the addition reaction product can be dispersed in water, but it is usually used in a ratio of 0.1 to 1.2 equivalents to 1 equivalent of acid groups in the addition reaction product. It

Further, a hydroxy group is previously introduced into a high acid value acrylic resin, and a polymerizable unsaturated group-containing monoisocyanate compound which is an adduct of a hydroxyl group-containing polymerizable unsaturated compound and a diisocyanate compound is introduced into this resin. The resin emulsion (a) can also be obtained by carrying out an addition reaction, neutralizing the addition reaction product, and dispersing it in water.

The hydroxyl group-containing polymerizable unsaturated compound includes, for example, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, N-methylol acrylamide, and the diisocyanate compound. Non-yellowing type is preferable, for example, isophorone diisocyanate, xylylene diisocyanate,
Hexamethylene diisocyanate, lysine diisocyanate and the like can be mentioned.

The above-mentioned hydroxyl group-containing high acid value acrylic resin is a hydroxyl group-containing polymerizable resin such as α, β-ethylenically unsaturated acid and 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate. Esters of (meth) acrylic acid containing a saturated compound as an essential component and having no hydroxyl group as necessary,
It can be obtained by copolymerizing another polymerizable unsaturated monomer.

The resin emulsion (a) is obtained by reacting a hydroxyl group-containing high acid value acrylic resin with a substituted or unsubstituted halide of cinnamic acid in the presence of a base, for example, in a pyridine solution. Can also be produced by neutralizing and dispersing in water. Examples of the hydroxyl group-containing high acid value acrylic resin used at this time include the same resins as the hydroxyl group-containing high acid value acrylic resin that undergoes an addition reaction with the polymerizable unsaturated group-containing monoisocyanate compound.

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

Examples of the substituted or unsubstituted cinnamic acid halide that can be used include cinnamic acid halides that may have 1 to 3 substituents selected from a nitro group and a lower alkoxy group on the benzene ring. Included, and more specifically,
Cinnamic acid chloride, p-nitrocinnamic acid chloride,
Examples thereof include p-methoxycinnamic acid chloride and p-ethoxycinnamic acid chloride.

Among the resin emulsions (a), an emulsion obtained by introducing a polymerizable unsaturated group into the aqueous emulsion (a) having the acid group (a) can reduce the content of the organic solvent to zero or reduce the environment. It is preferable in terms of protection and resource saving. Of these, a resin emulsion obtained by using an unsaturated epoxy monomer, particularly glycidyl acrylate or glycidyl methacrylate, for introducing a polymerizable unsaturated group is preferable.

The resin (a) may be a single resin or a mixture of two or more resins. Ethylenically unsaturated compound (b) The ethylenically unsaturated compound (b) has at least one ethylenically unsaturated double bond in its chemical structure, preferably 2
A compound containing more than one, when exposed to visible light,
Examples thereof include monomers, dimers, trimers and other oligomers having a function of insolubilizing the exposed portion by addition polymerization.

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

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 Methacrylic acid esters such as tantrimethacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate and tetramethylene glycol dimethacrylate; crotonic acid esters such as ethylene glycol dicrotonate and pentaerythritol dicrotonate; ethylene Itaconic acid esters such as glycol diitaconate and propylene glycol diitaconate; and 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.

Coloring Pigment (c) As the coloring pigment (c), a coloring pigment excellent in heat resistance, chemical resistance, solvent resistance, liquid crystal resistance and light resistance is desirable. Further, since an appropriate spectrum and transparency are required, it is necessary to select an organic pigment which has a large absorption coefficient of visible light and has 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 has a particle diameter of 300 nm or less, preferably 120 nm or less.
It is effective to reduce the particle size of the pigment by a known method using a kneader or a roll mill to improve transparency and absorption coefficient.

As pigments suitable for use as the coloring pigment (c), materials having excellent various resistances are referred to as a color index (C.
I. ) Indicate by number.

Yellow pigment: C.I. I. 24, 83, 86, 93, 94, 1
08, 109, 110, 117, 125, 137, 13
8, 147, 153, 154, 166, 168 Orange pigment: C.I. I. 36, 43, 51, 55, 5
9, 61 Red pigment: C.I. I. 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 Violet pigment: C.I. I. 19, 23, 29, 30,
37, 40, 50 Blue pigment: C.I. I. 15, 15: 1, 15: 3, 15:
4, 15: 6, 22, 60, 64 Green pigment: C.I. I. 7, 36 Brown pigment: C.I. I. 23, 25, 26 Black pigment: C.I. I. 7 Photopolymerization Initiator (d) The photopolymerization initiator (d) is decomposed by irradiation with actinic rays, and is polymerized by the polymerizable unsaturated group of the acrylic resin (a) and the ethylenically unsaturated compound (b). It has a function of initiating a (crosslinking) reaction, and in the composition of the present invention, a mixture of a thioxanthone compound and an acetophenone compound and / or a phosphorus-containing initiator is used. In the composition of the present invention, these do not have a large effect of initiating the polymerization reaction, but the thioxanthone compound and the acetophenone compound and / or the phosphorus-containing initiator are mixed to start the polymerization reaction. The work to be done becomes synergistically large.

Typical examples of the above thioxanthone compounds include 2,4-diethylthioxanthone, thioxanthone and 2-isopropylthioxanthone.

Typical examples of the acetophenone compound include 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl). Examples thereof include butanone, acetophenone, α-isohydroxyisobutylphenone, α, α′-dichloro-4-phenoxyacetophenone, 1-hydroxy-1-cycle hexylacetophenone, and 2,2-dimethoxy-2-phenylacetophenone.

As a typical example of the phosphorus-containing initiator, 2,
4,6-trimethylbenzoyldiphenylphosphine oxide, bis (acyl) phosphine oxide and the like can be mentioned.

The mixing ratio of the thioxanthone compound and the acetophenone compound and / or the phosphorus-containing initiator is not particularly limited, but the former / the latter weight ratio is
It is preferably in the range of 1/99 to 99/1, and more preferably 5/95 to 95/5. Pigment dispersant (e) The pigment dispersant is used to effectively and uniformly disperse the color pigment as the component (c), and includes an anionic, cationic or nonionic surfactant and a coloring agent. Examples thereof include organic dye derivatives into which a substituent effective for dispersing the pigment is introduced. Commercially available products of the above-mentioned surfactant include, for example, Disperbyk-182 manufactured by BYK Chemie.
, Disperbyk-184 and the like.

The composition of the present invention comprises the above (a), (b),
The components (c), (d) and (e) are essential components, and the compounding amount of each component is not particularly limited, but it is usually suitable that it is within the following range.

That is, the blending ratio of the resin (a) and the ethylenically unsaturated compound (b) is usually such that the weight ratio of (a) / (b) is 97/3 to 40/60, and further 95/5. ~ 5
It is preferably within the range of 0/50.

The content of the color pigment (c) is usually 20 with respect to the total of 100 parts by weight of the components (a) and (b).
˜120 parts by weight, more preferably 40 to 100 parts by weight is suitable from the viewpoint of the coloring property and transparency of the formed colored coating film.

The amount of the photopolymerization initiator (d) to be added is usually 100 parts by weight of the total of the components (a) and (b).
It is suitable that the amount is in the range of 0.1 to 25 parts by weight, and more preferably 0.2 to 10 parts by weight from the viewpoint of the photosensitivity of the coating film and the storage stability of the composition.

The amount of the pigment dispersant (e) is usually 1 with respect to 100 parts by weight of the total of the components (a) and (b).
It is suitable to be in the range of -40 parts by weight, more preferably 2-20 parts by weight from the viewpoint of fluidity and viscosity of the photosensitive coloring composition.

The composition of the present invention comprises the essential components (a) to
In addition to the component (e) and water, a sensitizer, a coating surface adjusting agent, an organic solvent and the like may be contained if necessary.

The sensitizer is added as necessary to accelerate the photopolymerization reaction by the polymerization initiator,
For example, triethylamine, triethanolamine, 2
-Dimethylaminoethanol, isoamyl 4-dimethylaminobenzoate, Michler's ketone, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate and the like can be mentioned.

Examples of the coating surface modifier include acrylic oligomers, silicone modifiers and amide modifiers.

The organic solvent is used for the purpose of adjusting the fluidity of the dispersion medium at the time of dispersing the pigment and adjusting the fluidity of the resulting water-based photosensitive coloring composition. As this organic solvent, a solvent miscible with water is preferable, and examples thereof include ketones (acetone etc.), esters (ethyl acetate etc.), ethers (tetrahydrofuran, dioxane, dimethoxyethane etc.), cellosolves (methyl cellosolve, ethyl). Cellosolve, butyl cellosolve, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, etc.), alcohols (ethyl alcohol, isopropyl alcohol, etc.) and the like.

The composition of the present invention can be prepared by a conventionally known method. For example, a pigment dispersant, water and / or an organic solvent, and, if necessary, neutralization as a resin (a),
When a water-dispersed resin is used, the color pigment (c) is dispersed in a mixture of the resins before water-dispersion to prepare a color pigment paste, and this and the remaining components are uniformly mixed. Good.

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 film obtained from the above-mentioned photosensitive coloring composition for color filters on a transparent substrate.

As a method for forming the photosensitive coating on the transparent substrate, (a) the water-based photosensitive coloring composition is formed on the transparent substrate,
Dip method, spray method, spin coating method, silk screen method, roll coating method or curtain flow coating method and drying method, (b) cover coat layer if necessary on a substrate that has been previously subjected to easy peeling treatment When a water-based photosensitive coloring composition is formed on the substrate or the cover coat layer and dried, and then there is a photosensitive coating layer and a cover coat layer on the substrate which has been subjected to easy peeling treatment, Examples thereof include a method of forming a photosensitive coating and, if necessary, a cover coat layer on the transparent substrate by transferring onto the transparent substrate including the 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 (b), the substrate before the easy peeling treatment may be a substrate having a smooth surface and capable of being subjected to the easy peeling treatment, such as glass or 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), a photosensitive film obtained from the water-based photosensitive coloring composition is formed on the transparent substrate by the method (a) or (b). The film thickness of the photosensitive film is not particularly limited, but is usually 0.5 to
It is preferably within the range of 5 μm.

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

In the above method (b), when the cover coat layer is formed on the substrate which has been previously subjected to the easy peeling treatment, the cover coat layer is non-photosensitive and is substantially non-tacky 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
It is preferably in the range of -80 ° C, particularly 40-70 ° 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 is 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.

A cover coat layer can be formed by applying a solution such as an aqueous solution of these film-forming resins 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 (b), the water-based photosensitive coloring composition is applied onto the substrate or the cover coat layer obtained as described above and dried to form a photosensitive coating layer,
The photosensitive coating layer formed on the substrate that has been subjected to the easy peeling treatment and the cover coating layer, if necessary, are transferred onto the transparent substrate to form the photosensitive coating layer and the cover coating layer on the transparent substrate. Form. In this case, the transfer operation can be more easily and surely performed by providing an adhesive layer on the transparent substrate that receives the photosensitive coating layer and the cover coat layer if necessary by transfer. The productivity in filter manufacturing can be greatly improved.

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, if necessary, and when the cover coat layer is not formed in the step (1), This is a process performed as necessary.

In order to form a cover coat layer on the photosensitive film in the step (2), a solution such as an aqueous solution of a film-forming resin used as the cover coat in the method (b) of the step (1) is made photosensitive. It may be applied on the film and dried. The thickness of the cover coat layer is usually 0.5 to 5 μm,
Further, it is preferably within the range of 1 to 3 μm. In the method of the present invention, the step (3) is a step of exposing the photosensitive coating to actinic rays in a pattern to cure the exposed portion of the photosensitive coating. The exposure can be performed by a known method, such as a method of irradiating an active ray through a photomask, a direct drawing method by laser scanning, or the like.

Examples of the actinic ray that can be used for irradiation include ultraviolet rays, visible rays, and laser rays (for example, visible light lasers and ultraviolet lasers).
Usually 0.1 to 1,000 mj / cm ² , preferably 1 to 500
The range of mj / cm ² is suitable. Further, as the irradiation source of the above-mentioned actinic rays, those conventionally used for light irradiation of the photocurable resin composition can be similarly used, for example, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, an argon laser. , And excimer laser.

In the method of the present invention, in the step (4), the photosensitive coating film which has been exposed and cured in a pattern form in the above step (3) is subjected to a developing treatment to remove the photosensitive coating film in the unexposed area to form a color pattern. It is a process of forming.

In the above-mentioned development processing, since the unexposed portion of the photosensitive film is anionic, an aqueous solution of a basic substance such as sodium hydroxide, sodium carbonate, potassium hydroxide, tetramethylammonium hydroxide and ammonia is usually used as the developer. To be done. When a cover coat layer is present on the photosensitive film, it is preferable to dissolve and remove the cover coat layer during the development process.

In the method of the present invention, the step (5) is a step of heating the color pattern formed in the above step (4) to further cure it, 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 method of the present invention, after the above step (4) or step (5),
A color filter is manufactured by repeating steps (1) to (5) a required number of times using a photosensitive coloring composition of different colors on a transparent substrate having a color pattern formed thereon to form a multicolored color pattern. be able to. 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.

[0075]

The present invention will be described more specifically with reference to the following examples. In the examples, "parts" and "%" all indicate "parts by weight" and "% by weight" unless otherwise specified.

Aqueous tree containing polymerizable unsaturated group and acid group
Synthetic Production Example 1 of Fat Emulsion 1 In a 2L four-necked flask, 1 part of sodium dodecylbenzene sulfonate was dissolved in 600 parts of water, and the mixture was stirred well and foamed. In it, 75 parts of styrene and 3 parts of butyl acrylate were added.
00 parts, methyl methacrylate 75 parts, acrylic acid 50
Part and a monomer mixed solution of 1 part of dodecyl mercaptan were added and emulsified to obtain an emulsion. 7 this emulsion
The mixture was heated to 0 ° C., and 100 parts of a 3% aqueous solution of ammonium persulfate was added dropwise from a dropping funnel under a nitrogen stream over 2 hours to carry out emulsion polymerization. After that, the temperature was raised to 90 ° C. and kept for 4 hours to crush the remaining polymerization initiator. After that, 50 parts of glycidyl methacrylate dissolved with 0.1 part of ditertiary butyl methylphenol and 5 parts of tetramethylammonium chloride were added and held at the same temperature for about 3 hours, the epoxy group completely disappeared, and the desired resin emulsion was obtained. Got The amount of carboxyl groups in the resin of the obtained emulsion was 0.82 equivalent / kg resin, and the amount of polymerizable unsaturated groups was 0.46 equivalent / kg resin. About 70% of the epoxy groups of glycidyl methacrylate
Had reacted with the carboxyl group. The obtained emulsion has a solid content of 44% and a particle size of about 0.2 μm.
Met.

Production Example 2 In a 2 L four-necked flask, 1 part of sodium dodecylbenzene sulfonate was dissolved in 600 parts of water, then 50 parts of acrylamide was added, and the mixture was stirred well and bubbled.
A monomer mixed solution of 5 parts, 300 parts of butyl acrylate, 25 parts of methyl methacrylate, 50 parts of acrylic acid and 1 part of dodecyl mercaptan was added and emulsified to obtain an emulsion. This emulsion was heated to 70 ° C., and a 3% aqueous solution of ammonium persulfate 100% was added from a dropping funnel under a nitrogen stream.
Part was added dropwise over 2 hours to carry out emulsion polymerization.
After that, the temperature was raised to 90 ° C. and kept for 4 hours to crush the remaining polymerization initiator. Then 50 parts of glycidyl methacrylate and 0.1 parts of tetramethylammonium chloride in which 0.1 part of ditert-butylmethylphenol was dissolved.
When parts were added and the mixture was kept at the same temperature for about 3 hours, the epoxy groups completely disappeared, and the intended resin emulsion was obtained. The amount of carboxyl groups in the resin of the obtained emulsion was 0.82 equivalent / kg resin, and the amount of polymerizable unsaturated groups was 0.46 equivalent / kg resin. About 70% of the epoxy groups of glycidyl methacrylate were reacted with carboxyl groups. The solid content of the obtained emulsion is 44.
%, And the particle size was about 0.2 μm.

Production Example 3 A mixture of 60 parts of styrene, 10 parts of methyl acrylate, 30 parts of acrylic acid and 3 parts of azobisisobutyronitrile was held in a nitrogen gas atmosphere at 110 ° C. in 90 parts of propylene glycol monomethyl ether. To 3
It was dropped over time. 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 233). ) A solution was obtained. Next, 35 parts of glycidyl methacrylate, 0.13 part of hydroquinone and 0.6 part of tetraethylammonium bromide were added to this solution and reacted at 110 ° C. for 5 hours while blowing air, and the epoxy group disappeared and solid content was about 57%. An acrylic resin solution having a polymerizable unsaturated group of was obtained. The obtained resin has a carboxyl group amount of 1.25 equivalent / kg resin,
Polymerizable unsaturated group amount is 1.83 equivalent / kg resin, Tg
The point was 45 ° C.

After 10 parts of triethylamine was added to the resulting acrylic resin solution to sufficiently neutralize it, deionized water was added to adjust the solid content concentration to 30%, and the mixture was stirred to obtain a resin emulsion. .

Example 1 The total amount of the coloring pigment and the pigment dispersant shown in Table 1 below was mixed with 340 parts of deionized water and dispersed by a sand mill to obtain a pigment paste. Next, the remaining components shown in Table 1 below were blended and uniformly dispersed in the mixture to obtain red, green, blue and black photosensitive coloring compositions. The total of the resin (a) and the ethylenically unsaturated compound (b) in each composition has a polymerizable unsaturated group concentration of 3.36 equivalents / kg and a carboxyl group concentration of 0.57 equivalents / kg. The average particle size of the pigment in each color composition is as follows: red composition: 80 nm, green composition:
The composition was 50 nm, the blue composition was 90 nm, and the black composition was 60 nm. In all compositions, 95% or more of the pigments had a particle size of 120 nm or less.

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, a 12% aqueous solution of polyvinyl alcohol (polymerization degree: 1,700, Tg: 65 ° C, oxygen permeability: 2 × 10 ^-14 cc · cm / cm ² · sec · cmHg) is spin-coated. Was uniformly applied to give a dry film thickness of 2 μm and dried at 80 ° C. for 10 minutes to form a red photosensitive coating layer and a cover coating layer on a glass plate. Then, using a high pressure mercury lamp for this photosensitive film, the exposure amount was 200 mj / c.
The pattern was exposed through a photomask under three-stage irradiation conditions of m ² , 400 mj / cm ² and 800 mj / cm ² . Then, it was sprayed with a 0.25% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 30 seconds, developed, washed with water, drained and dried, and then baked at 140 ° C. for 60 minutes 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 in the same manner as above on the glass plate on which the red color pattern is formed, and exposure, development, washing and draining are carried out. After drying and baking, a green color pattern was obtained on the glass plate in addition to red.

Then, the same steps as described above are repeated by using the blue and black photosensitive coloring compositions to form red, green, blue and black color patterns on the glass plate, thereby forming a multicolor suitable for color filters. Got the color pattern of.

Line / space (L / L) of each color pattern
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).

Examples 2 to 9 and Comparative Examples 1 to 12 Implementation was carried out except that the photopolymerizable resin emulsion obtained in Production Example 1, Production Example 2 or Production Example 3 and other components were blended as shown in Table 1 below. In the same manner as in Example 1, red, green, blue and black photosensitive coloring compositions were obtained. The total of the resin (a) and the ethylenically unsaturated compound (b) in the compositions of Examples and Comparative Examples has the following polymerizable unsaturated group concentration and carboxyl group concentration. In each of the compositions of Examples 2 and 3 and Comparative Examples 1 to 6, the concentration of the polymerizable unsaturated group was 3.
It is 36 equivalents / kg and the carboxyl group concentration is 0.57 equivalents / kg. In each of the compositions of Examples 4 to 6 and Comparative Examples 7 to 9, the concentration of the polymerizable unsaturated group was 4.98 equivalent / kg, and the concentration of the carboxyl group was 0.49 equivalent / kg. Also, Examples 7 to 9
In each composition of Comparative Examples 10 to 12, the concentration of the polymerizable unsaturated group was 3.08 equivalent / kg, and the concentration of the carboxyl was 1.0.
It is 6 equivalents / kg. Further, in all the compositions, 95% by weight or more of the pigment had a particle size of 120 nm or less.

In each example, a multicolor color pattern was obtained in the same manner as in Example 1 except that each of the above photosensitive coloring compositions was used.

Example 10 On a polyethylene terephthalate film having a film thickness of 75 μm, the 12% aqueous solution of polyvinyl alcohol used for the cover coat in Example 1 was applied uniformly by a roll coating method so as to have a dry film thickness of 2 μm. 10 at ℃
After drying for a minute, a cover coat transfer film was obtained. The red photosensitive coloring composition obtained in Example 1 was applied on 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 obtain a transfer type red color. A photosensitive coating layer was 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.

[0089] was further exposed in a pattern through a photomask with irradiation conditions of the photosensitive film using a high pressure mercury lamp in an exposure amount 200mj / cm ^2, 3 stages of 400 mj / cm ² and 800 mJ / cm ^2. Then, it is sprayed with a 0.25% tetramethylammonium hydroxide aqueous solution at 25 ° C. for 30 seconds to develop, wash with water, dry with water, and then dry at 140 ° C.
After baking at 60 ° C. for 60 minutes, a red color pattern was obtained.

Next, the transfer type green photosensitive coating layer was formed on the cover coat transfer film using the green photosensitive coloring composition obtained in Example 1 instead of the above red photosensitive coloring composition. . 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 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 developability of each pattern in forming color patterns in Examples 1 to 9 and Comparative Examples 1 to 12 was evaluated according to the following criteria. The test results are shown in Table 1 below.

◯: A good image pattern without defects is obtained. Δ: Partial peeling of the image pattern is seen. ×: Image pattern is dissolved and no pattern is obtained. The developability of the pattern at this time was as good as that of Example 1, and a good image pattern without defects was obtained.

The photosensitive coloring compositions of the examples are all aqueous emulsions, and are excellent in environmental protection and resource saving as compared with organic solvent type ones.
Each of the photosensitive coloring compositions of 6 has an organic solvent amount of less than 5% by weight in the composition, and is particularly excellent in the above points.

Further, (Note) in Table 1 below has the following meanings.

(* 1) Disperbyk-182: manufactured by Big Chemie, a surfactant which is a polymer copolymer solution having a nonvolatile content of 43%, and an amine value of 14 mgKOH / g.

(* 2) Disperbyk-184: manufactured by Big Chemie, a surfactant which is a polymer copolymer solution having a nonvolatile content of 52%, and an amine value of 14 mgKOH / g.

[0098]

[Table 1]

[0099]

[Table 2]

[0100]

[Table 3]

[0101]

[Table 4]

[0102]

[Table 5]

[0103]

[Table 6]

[0104]

[Table 7]

[0105]

EFFECTS OF THE INVENTION The composition of the present invention is a water-based photosensitive coloring composition for a color filter containing a color pigment, which is used in combination with a photopolymerizable water-dispersible resin and a specific photopolymerization initiator. By this, high sensitivity, excellent curability,
It is possible to obtain a colored photoresist for a color filter which is also excellent in developer resistance.

The cured colored coating obtained by exposing the coating of the composition of the present invention to a multi-color color filter has a good resistance to development even if it is repeatedly contacted with the developing solution in the developing step. Therefore, it is suitable as a photosensitive coloring composition for color filters.

Further, since the composition of the present invention is water-based, it is preferable in terms of environmental protection and resource saving.

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location G03F 7/40 501 G03F 7/40 501 (72) Inventor Kenji Seko 4-17-1 Higashihachiman, Hiratsuka-shi, Kanagawa In Kansai Paint Co., Ltd. (72) Inventor Nakatani ▲ Sakae ▼ Product 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd.

Claims (6)

[Claims] 1. A photopolymerizable water-dispersible resin having (a) a polymerizable unsaturated group and an acid group, (b) an ethylenically unsaturated compound, (c) a colored pigment, and (d) a thioxanthone compound. A water-based photosensitive coloring composition comprising a photopolymerization initiator composed of a mixture with an acetophenone compound and / or a phosphorus-containing initiator and (e) a pigment dispersant. 2. The water-dispersible resin (a) is an aqueous resin emulsion obtained by adding a compound having a polymerizable unsaturated group and an epoxy group in one molecule to an aqueous emulsion having an acid group. 1. The photosensitive coloring composition according to 1. 3. An aqueous resin emulsion in which the water-dispersible resin (a) is obtained by adding a compound having a polymerizable unsaturated group and a glycidyl group in one molecule to an aqueous emulsion having an acid group and an amide group. The photosensitive coloring composition according to claim 1. 4. The photopolymerization initiator (d) is 2-methyl-2.
-Morpholino (4-thiomethylphenyl) propane-1
The photosensitive coloring composition according to any one of claims 1 to 3, which is a mixture of -one and 2,4-diethylthioxanthone. 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 exposing the photosensitive coating to actinic rays in a pattern to cure the exposed portion of the photosensitive coating, and (4) a developing treatment to remove the photosensitive coating in the non-exposed portion to form a color pattern. And a step of heating (5) if necessary, a method of manufacturing a color filter. 6. A step of forming a color pattern,
And (5) after the step of heating as necessary, the steps (1) to (5) are repeated a necessary number of times on the transparent substrate on which the color pattern is formed, using the photosensitive coloring composition of different colors. The method for producing a color filter according to claim 5, wherein a color pattern of colors is formed.