JPH09114095A - Photosensitive colored composition and production of color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colored photoresist for a color filter having high sensitivity, excellent in curability and excellent also in developer resistance even when a coloring pigment is contained by using photopolymerizable acrylic resin as a resin component and a specified photopolymn. initiator. SOLUTION: This compsn. contains photopolymerizable acrylic resin having polymerizable unsatd. groups, an ethylenically unsatd. compd., a photopolymn. initiator made of a mixture of a thioxanthone compd. with an acetophenone compd. and/or a P-contg. initiator and an org. solvent. The polymerizable unsatd. groups are groups which can be polymerized by irradiation with active light in the presence of a polymn. initiator and they are, e.g. (meth)acryloyl groups or cinnamoyl groups. Since the photopolymn. initiator is made of the mixture, the polymn. reaction initiating action is synergistically increased.

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 having a wide development width used in a display device such as a liquid crystal and a method for producing a color filter using the 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.

Therefore, the inventors of the present invention have earnestly studied to obtain a colored photoresist having high sensitivity, excellent curability and excellent developer resistance even in a colored photoresist containing a large amount of pigment, and as a result, photopolymerization was conducted. It has been found that the above object can be achieved by using a possible acrylic resin as a resin component and using a specific photopolymerization initiator.

[0005]

That is, the present invention provides:
(A) Photopolymerizable acrylic resin having a polymerizable unsaturated group, (b) ethylenically unsaturated compound, (c) color pigment,
(D) A photo-polymerization initiator comprising a mixture of a thioxanthone compound and an acetophenone compound and / or a phosphorus-containing initiator, and (e) an organic solvent, which is a photosensitive coloring composition for a color filter. Is provided.

[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.

A photopolymerizable actuator having a polymerizable unsaturated group
Lil resin (a) The resin (a) is a photocurable resin containing a polymerizable unsaturated group that can be polymerized (crosslinked) by irradiation with actinic rays, and is polymerized by irradiation with light to give an alkaline aqueous solution or an acid aqueous solution. On the other hand, the portion which is substantially insoluble or hardly soluble and which is not exposed is soluble in the developing solution. For example, when the resin has many anionic groups, it is soluble in the alkaline developer, and when it has many cationic groups, it is soluble in the acid developer, and the ionic groups are contained in the resin. When it is not present, it is soluble in organic solvents.

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 in the resin (a) can be varied over a wide range depending on the type and molecular weight of the resin, but it is generally 0.2 to 7.0.
Suitably it is included in an amount of mol / kg resin, preferably 0.7 to 4.5 mol / kg resin.

The resin (a) is generally 1,000 to
100,000, preferably 5,000 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) Photocurable acrylic resin containing (meth) acryloyl group: The photocurable resin can be produced, for example, by adding a glycidyl group-containing unsaturated compound to a high acid value acrylic resin. The high acid value acrylic resin used at that time is, for example, α, β-ethylenically unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and esters of (meth) acrylic acid, For example, 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. The number average molecular weight and glass transition temperature (Tg) of the high acid value acrylic resin are the same as those of the photocurable resin obtained by adding a glycidyl group-containing (meth) acrylic acid ester compound to the high acid value acrylic resin. It is appropriately adjusted so as to have a number average molecular weight and Tg.

On the other hand, the glycidyl group-containing (meth) acrylic acid ester compound added to the above high acid value acrylic resin is specifically glycidyl acrylate,
Examples thereof include glycidyl methacrylate.

The addition reaction between the above-mentioned high acid value acrylic resin and the glycidyl group-containing (meth) acrylic acid ester compound is carried out according to a method known per se, for example, using a catalyst such as tetraethylammonium bromide in the range of 80 to 12
It can be easily carried out by reacting at 0 ° C. for 1 to 5 hours.

The photo-curable acrylic resin containing a (meth) acryloyl group can also be produced by adding a reaction product of a hydroxyl group-containing polymerizable unsaturated compound and a diisocyanate compound to the hydroxyl group-containing acrylic resin. You can

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,
A non-yellowing type is preferable, and examples thereof include isophorone diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and lysine diisocyanate.

The above hydroxyl group-containing acrylic resin is
The α, β-ethylenically unsaturated acid and a hydroxyl group-containing polymerizable unsaturated compound such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are used as essential components, and a hydroxyl group is added if necessary. It can be obtained by copolymerizing an ester of (meth) acrylic acid that does not have it and other polymerizable unsaturated monomer.

(B) Photocurable acrylic resin containing a cinnamoyl group as a polymerizable unsaturated group: This resin is, for example,
It can be produced by reacting a hydroxyl group-containing acrylic resin with a substituted or unsubstituted halide of cinnamic acid in the presence of a base, for example, in a pyridine solution. The hydroxyl group-containing acrylic resin used at that time may be the same as the hydroxyl group-containing acrylic resin described in the above item (a).

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. Included, and more specifically,
Cinnamic acid chloride, p-nitrocinnamic acid chloride,
Examples thereof include p-methoxycinnamic acid chloride and p-ethoxycinnamic acid chloride.

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

[0023]

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Or by adding the reaction product of the (meth) allyl alcohol and the diisocyanate compound described in (a) above to the hydroxyl group-containing acrylic resin described in (a) above. can do.

The above-mentioned addition reaction between the high acid value acrylic resin and allyl glycidyl ether is carried out in the same manner as the reaction between the high acid value acrylic resin and the glycidyl group-containing (meth) acrylic acid ester described in the above item (a). It can be carried out.

In the composition of the present invention, the photocurable acrylic resin (a) contains an anionic resin having an acid group such as a carboxyl group, a cationic resin having an amino group and a cationic group, and an ionic group. It may be any resin that does not have it.

When the amount of the ionic groups in the resin (a) is in the range of 0.2 to 3.5 mol / kg resin, it can be developed with an alkali developing solution or an acid developing solution at the time of development and remains after the development. The performance of the colored coating film can be improved.

Examples of such a cationic resin include a resin 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. A resin containing a tertiary amino group; an epoxy resin is reacted with a polymerizable unsaturated monocarboxylic acid or a hydroxyl group-containing unsaturated compound, And the like; excess of epoxy groups a tertiary amino compounds, thioethers, phosphines such as onium onium salt group-containing resin obtained by chloride in the presence of a carboxylic acid.

As the resin having no ionic group,
For example, in the above (a), (b), and (c), when introducing a polymerizable unsaturated group into a high acid value acrylic resin, it is reacted with substantially all of the acid groups in the acrylic resin to eliminate the acid group. Can be obtained.

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

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, 9
3, 94, 108, 109, 110, 117, 125,
137, 138, 147, 153, 154, 166, 1
68 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. Organic solvent (e) The organic solvent is used for the purpose of adjusting the fluidity of the dispersion medium at the time of dispersing the pigment, adjusting the fluidity and viscosity of the resulting photosensitive coloring composition, and the like. Examples of the organic solvent include 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 hydrocarbons (chloroform, trichlorethylene, dichloromethane, etc.), alcohols (ethyl alcohol, benzyl alcohol, etc.), and others (dimethylformamide) , Dimethyl sulfone oxime, etc.) 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 mixing ratio of the acrylic resin (a) and the ethylenically unsaturated compound (b) is usually (a) /
The weight ratio of (b) is 97/3 to 40/60, and further 95
It is preferably in the range of / 5 to 50/50.

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).
It is suitable from the viewpoint of the coloring property, transparency, etc. of the formed colored film that the amount is in the range of from 120 to 120 parts by weight, more preferably from 40 to 90 parts by weight.

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 organic solvent (e) compounded is usually 10 with respect to 100 parts by weight of the total of the components (a) and (b).
It is preferable that the amount is in the range of ˜3,000 parts by weight, and further in the range of 20 to 2,000 parts by weight, from the viewpoint of fluidity and viscosity of the photosensitive coloring composition. In addition to the essential components (a) to (e), the composition of the present invention may contain a pigment dispersant, a sensitizer, a coating surface adjusting agent, etc., if necessary.

The above-mentioned pigment dispersant is used to effectively and uniformly disperse the color pigment as the component (c), and it is used as an anionic, cationic or nonionic surfactant or a color pigment. Examples thereof include organic dye derivatives into which a substituent effective for dispersion is introduced. Examples of commercially available products of the above-mentioned surfactant include BYK1610, BYK161 manufactured by BYK Chemie, and Kusumoto Kasei Co.
Disparlon P24000 and the like can be mentioned.

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 composition of the present invention can be prepared by a conventionally known method, for example, a mixture of a part of the acrylic resin (a), an organic solvent and, if necessary, a pigment dispersant, a colored pigment (c). ) Is dispersed to create a color pigment paste,
It suffices to uniformly mix this and the rest of the components.

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 the method for forming the photosensitive coating on the transparent substrate, (a) the photosensitive coloring composition is formed on the transparent substrate by dipping, spraying, spin coating, silk screen, roll coating or curtain. A method of applying by a flow coating method and drying, (b) a cover coat layer is formed on a substrate that has been subjected to easy peeling treatment in advance, if necessary, and a photosensitive coloring composition is formed on the substrate or on the cover coat layer. After coating and drying, if there is a photosensitive coating layer or cover coat layer on the substrate that has been subjected to easy peeling treatment, transfer it to the transparent substrate including the cover coat layer to make it photosensitive on the transparent substrate. Examples thereof include a method of forming a coating film and, if necessary, 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 (b), 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 step (1), a photosensitive coating film obtained from the 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 5
It is preferably in the range of μm.

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

In the method (b), when 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 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
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 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 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 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, which is easily peeled off. The photosensitive coating layer formed on the treated substrate and, if necessary, the cover coat layer are transferred onto the transparent substrate to form the photosensitive coating layer and, if necessary, the cover coat layer on the transparent substrate. 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 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 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 as the cover coat in the method (b) of the step (1) is 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 film which has been patterned and exposed in the step (3) is subjected to a developing treatment to remove the photosensitive film in the unexposed area to form a color pattern. It is a process of forming.

The development treatment can be carried out by rinsing 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. Part of the photosensitive film is ionic,
It can be carried out by washing off with an organic solvent regardless of whether it is nonionic.

In the above development processing, the alkaline aqueous solution is usually caustic soda, sodium carbonate, caustic
An aqueous solution of a basic substance such as tetramethylammonium hydroxide or ammonia is used, an aqueous solution of an acid such as acetic acid, formic acid, or lactic acid is usually used as the acid aqueous solution, and an organic solvent is, for example, a polar solvent such as methanol or ethanol. A solvent can be mentioned.

When a cover coat layer is provided on the photosensitive film, it is preferable that the cover coat layer is also dissolved and removed during the developing treatment.

In the method of the present invention, the step (5) is a step of heating the color pattern formed in the step (4) to further cure it, and is carried out as 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.

[0076]

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.

Synthesis of Photopolymerizable Acrylic Resin Synthesis Example 1 Methyl methacrylate 40 parts by weight, butyl acrylate 40 parts by weight, acrylic acid 20 parts by weight and azobisisobutyronitrile 2 parts by weight under a nitrogen gas atmosphere. Was added dropwise to 90 parts by weight of propylene glycol monomethyl ether (hydrophilic solvent) maintained at 110 ° C. for 3 hours. After the dropwise addition, the mixture was aged for 1 hour, and a mixed solution comprising 1 part by weight of azobisdimethylvaleronitrile and 10 parts by weight of propylene glycol monomethyl ether was added to 1 part.
The solution was dropped over a period of time and aged for 5 hours to obtain a high acid value acrylic resin (acid value 155) solution. Next, 24 parts by weight of glycidyl methacrylate, 0.12 parts by weight of hydroquinone and 0.6 parts by weight of tetraethylammonium bromide were added to this solution, and while blowing air at 110 ° C.
Photopolymerizable acrylic resin by reacting for 5 hours (resin acid value about 50, polymerizable unsaturated group concentration 1.35 mol / kg, Tg
A solution having a point of 20 ° C. and a number average molecular weight of about 20,000) was obtained.
The resin solution had a solid content of about 54%.

Synthesis Example 2 60 parts by weight of styrene, 10 parts by weight of methyl acrylate,
A mixed solution of 30 parts by weight of acrylic acid and 3 parts by weight of azobisisobutyronitrile was added to 1
It was added dropwise to 90 parts by weight of cellosolve kept at 20 ° C. over 3 hours. After the dropping, the mixture was aged for 1 hour, a mixed solution of 1 part by weight of azobisdimethylvaleronitrile and 10 parts by weight of cellosolve was added dropwise over 1 hour, and the mixture was further aged for 5 hours to obtain a high acid value acrylic resin (acid value 233). A solution was obtained.
Next, 35 parts by weight of glycidyl methacrylate, 0.13 parts by weight of hydroquinone and 0.6 parts by weight of tetraethylammonium bromide were added to this solution, and the mixture was reacted at 110 ° C. for 5 hours while blowing in air to allow photopolymerization of an acrylic resin (resin). Acid value about 70, concentration of polymerizable unsaturated group 1.
83 mol / kg, Tg point of 45 ° C, number average molecular weight of about 15,0
00) solution was obtained. This resin solution has a solid content of about 5
7%.

Example 1 Red, green, blue and black photosensitive coloring compositions in which the photopolymerizable acrylic resin solution obtained in Synthesis Example 1 and other components were uniformly dispersed in the composition shown in Table 1 below. I got a thing.
The color pigment was mixed with a part of the photopolymerizable acrylic resin solution, a part of the pigment dispersant and a part of the organic solvent, and dispersed by a sand mill to be blended as a pigment paste. The total of the acrylic resin and the ethylenically unsaturated compound in each composition was such that the concentration of the polymerizable unsaturated group was 4.0 mol / kg and the concentration of the carboxyl group was 0.
It has 63 mol / kg. The average particle size of the pigment in each composition is as follows: red pigment: 60 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.

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 on the glass plate on which the red color pattern has been formed in the same manner as above, and exposed, developed, washed with water and drained. 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 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 a color filter. Got the color pattern of.

The line / space (L / space) 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).

Examples 2 to 6 and Comparative Examples 1 to 6 As Example 1 except that the photopolymerizable acrylic resin solution obtained in Synthesis Example 1 or Synthesis Example 2 and other components had the formulations shown in Table 1 below. Similarly, red, green, blue and black photosensitive coloring compositions were obtained. The total of the acrylic resin and the ethylenically unsaturated compound in each composition of Example 4 has a polymerizable unsaturated group concentration of 4.3 mol / kg and a carboxyl group concentration of 0.88 mol / 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 7 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.

[0088] 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 green photosensitive coloring composition obtained in Example 1 was used in place of the above red photosensitive coloring composition 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.

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 developability of each pattern in forming color patterns in Examples 1 to 7 and Comparative Examples 1 to 6 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 observed. ×: Image pattern is not dissolved and no pattern is obtained. (Note) in Table 1 below. Have the following meanings.

(* 1) BYK160: a surfactant which is a polymer copolymer manufactured by BYK Chemie.

(* 2) BYK161: a surfactant which is a polymer copolymer manufactured by BYK Chemie.

[0095]

[Table 1]

[0096]

[Table 2]

[0097]

[Table 3]

[0098]

[Table 4]

[0099]

The composition of the present invention is a photosensitive coloring composition for a color filter containing a coloring pigment, and by using a photopolymerizable acrylic resin in combination with a specific photopolymerization initiator, It was possible to obtain a colored photoresist for a color filter having high sensitivity, excellent curability, and excellent resistance to a developing solution.

The cured colored coating obtained by exposing the coating of the composition of the present invention to a multi-colored 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.

Front page continued (72) Inventor Koichi Tamura 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd. (72) Inventor Riki Norimatsu 4-1-1, East Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd. In-house (72) Inventor Nakatani ▲ Sakae ▼ Product 4-17-1, Higashi-Hachiman, Hiratsuka-shi, Kanagawa Kansai Paint Co., Ltd.

Claims (5)

[Claims] 1. A photopolymerizable acrylic resin having (a) a polymerizable unsaturated group, (b) an ethylenically unsaturated compound,
(C) a color pigment, (d) a photopolymerization initiator comprising a mixture of a thioxanthone compound and an acetophenone compound and / or a phosphorus-containing initiator, and (e) an organic solvent. Photosensitive coloring composition for use. 2. The photosensitive coloring composition according to claim 1, wherein the acrylic resin (a) is an anionic resin obtained by adding a glycidyl group-containing (meth) acrylic acid ester to a high acid value acrylic resin. 3. The photopolymerization initiator (d) is 2-methyl-2.
-Morpholino (4-thiomethylphenyl) propane-
The photosensitive coloring composition according to claim 1 or 2, which is a mixture of 1-one and 2,4-diethylthioxanthone. 4. A step of (1) forming a photosensitive coating from the photosensitive coloring composition according to claim 1 on a transparent substrate, (2) forming a cover coat layer on the photosensitive coating, if necessary. 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. 5. 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 manufacturing a color filter according to claim 4, wherein a color pattern of colors is formed.