KR100874329B1 - Radiation-sensitive composition and color filter for colored layer formation - Google Patents

Abstract

According to the present invention, a mixed solvent containing (A) colorant, (B) alkali-soluble resin, (C) polyfunctional monomer, (D) photopolymerization initiator, and (E) dipropylene glycol methyl ether acetate 3 to 8.5 wt% It can contain and provide the radiation sensitive composition for colored layer formation. This composition has high solubility of the dry matter generated in the slit nozzle portion and furthermore does not leave crater-like traces on the dry coating film.

Description

Radiation sensitive composition and color filter for colored layer formation {RADIATION SENSITIVE COMPOSITION FOR FORMING A COLORED LAYER, AND COLOR FILTER}

[Document 1] Japanese Unexamined Patent Publication No. 2-144502

[Document 2] Japanese Unexamined Patent Publication No. 3-53201

The present invention relates to a radiation-sensitive composition for forming a colored layer, a method for forming a color filter, a color filter, and a color liquid crystal display panel. In more detail, the radiation sensitive composition used for formation of the pixel and / or black matrix which are colored layers useful for manufacture of a color filter used for a transmissive or reflective color liquid crystal display device, a color image tube element, etc., and this radiation sensitive composition It is related with the formation method of the color filter to be used, the color filter provided with the colored layer formed from the said radiation sensitive composition, and the color liquid crystal display panel provided with this color filter.

Conventionally, when manufacturing a color filter using the radiation sensitive composition for colored layer formation, the coating film of the radiation sensitive composition for colored layer formation is normally formed on the board | substrate or the board | substrate in which the light shielding layer of the desired pattern was formed previously, After exposing the radiation through a photomask having a desired pattern shape, developing the solution, dissolving and removing the unexposed portion, and then heat treating using a clean oven or a hot plate to obtain pixels of each color (Japanese Patent Laid-Open) (Japanese Patent Application Laid-Open No. 2-144502 and Japanese Patent Laid-Open No. 3-53201) are known. When manufacturing a color filter by such a method, the radiation sensitive composition for colored layer formation is generally apply | coated on a board | substrate by the spin method, but according to the enlargement of a board | substrate, a coating method is a slit-and-spin method or spinless. A shift is made using a slit nozzle such as a system.

However, in the slit-and-spin method or the spinless method, coating is performed by using a slit nozzle, which causes problems of applicability and yield. That is, since contamination of the slit nozzle by the radiation sensitive composition for colored layer formation cannot be avoided, the slit nozzle cleaning process is required. In the washing step, the slit nozzle is usually washed with the main solvent of the radiation sensitive composition for forming the colored layer. However, when the solubility in the main solvent is low, the radiation sensitive composition for forming the colored layer remaining in the nozzle portion is formed as a protrusion. Remaining, when the radiation-sensitive composition for forming a colored layer is applied to the substrate, streaks are generated in the advancing direction of the nozzle, or the dried material of the radiation-sensitive composition for forming a colored layer falls and adheres to the substrate, resulting in defects. The problem of lowering the yield arises. Therefore, the resolubility to the solvent of the dried material of the radiation sensitive composition for colored layer formation becomes important.

On the other hand, the use of a high boiling point solvent in combination with the radiation-sensitive composition for forming a colored layer can suppress the occurrence of a dried product, but in this case, it is difficult to evaporate the solvent sufficiently, resulting in sticking and longer productivity due to a longer heating time. A problem arises that causes the deterioration of. In addition, depending on the selection and the addition amount of the high boiling point solvent species, in the heating step after applying the radiation-sensitive composition for forming the colored layer, minute bubbles contained in the composition at the time of evaporation of the solvent appear on the surface of the coating film and remain as it is after drying. The problem also remains that it remains as a crater defect (henceforth a "dolby hole").

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems and to provide a radiation-sensitive composition for forming a colored layer having high solvent redissolution of the dried product of the radiation-sensitive composition for forming a colored layer generated in the slit nozzle portion and not generating a dolby hole. There is.

Another object of the present invention is to provide a method for producing a color filter from the radiation-sensitive composition for forming a colored layer, the color filter, and a liquid crystal display device having the color filter.

Still other objects and advantages of the present invention will become apparent from the following description.

MEANS TO SOLVE THE PROBLEM As a result of earnestly examining in order to solve the said subject, as a result of using the solvent which uses dipropylene glycol methyl ether acetate as an essential component as a solvent used for the radiation sensitive composition for colored layer formation, the persimmon for colored layer formation Solvent redissolution of the dried product of the radioactive composition was remarkably improved, and it was found that the occurrence of the Dolby pore could be suppressed, and thus the present invention was completed.

Therefore, the above objects and advantages of the present invention, firstly

(A) Colorant, (B) Alkali-soluble resin, (C) Polyfunctional monomer, (D) Photoinitiator, and (E) Solvent containing 3 to 8.5 weight% of dipropylene glycol methyl ether acetates, and is for forming a colored layer It is achieved by a radiation sensitive composition characterized in that.

The term "colored layer" as used in the present invention means a layer containing a pixel and / or a black matrix used in the color filter.

The objects and advantages of the present invention, secondly

It is achieved by the formation method of the color filter characterized by including the process of following (1)-(4).

(1) Process of forming the coating film of the radiation sensitive composition for colored layer formation on a board | substrate.

(2) The process of exposing to at least one part of the said coating film.

(3) The process of developing the coating film after exposure.

(4) The process of heat-processing the coating film after image development.

According to the present invention, the above objects and advantages of the present invention,

It is achieved by the color filter provided with the colored layer formed from the said radiation sensitive composition for colored layer formation.

According to the present invention, the above objects and advantages of the present invention,

It is achieved by a color liquid crystal display panel having the color filter.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

Colored layer  Forming Radiation  Composition

-(A) colorant-

The colorant in the present invention is not particularly limited in color tone, is appropriately selected according to the use of the color filter obtained, and may be a pigment, a dye or a natural dye.

Since the color filter requires high purity, high permeability color development and heat resistance, a colorant having high color development and high thermal decomposition resistance is preferable as the colorant in the present invention. Preference is given to organic pigments and inorganic pigments, particularly preferably organic pigments and carbon black.

As the organic pigment, for example, a compound classified as Pigment by Color Index (CI; issued by The Society of Dyers and Colourists), and specifically, the following Color Index (CI) number is given. It can be mentioned.

C.I. Pigment Yellow 83, C.I. Pigment Yellow 128, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 151, C.I. Pigment Yellow 152, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 156, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168, C.I. Pigment Yellow 175, C.I. Pigment yellow 185;

C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment violet 32, C.I. Pigment Violet 36, C.I. Pigment violet 38;

C.I. Pigment Red 177, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 208, C.I. Pigment Red 209, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 220, C.I. Pigment Red 224, C.I. Pigment Red 226, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 245, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment red 265;

C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment blue 60;

C.I. Pigment Green 7, C.I. Pigment green 36;

C.I. Pigment Black 1, C.I. Pigment Black 7.

The said organic pigment can be used individually or in mixture of 2 or more types.

In addition, the said organic pigment can be refine | purified and used, for example by the sulfuric acid recrystallization method, the solvent washing method, or a combination thereof.

In addition, examples of the inorganic pigments include titanium oxide, barium sulfate, calcium carbonate, zincated, lead sulfate, yellow lead, zinc sulfur, iron group (red iron oxide (III)), cadmium, ultramarine blue, blue, chromium oxide, and cobalt. Rust, invar, titanium black, synthetic iron black, carbon black, etc. are mentioned.

These inorganic pigments can be used individually or in mixture of 2 or more types.

When using the radiation sensitive composition for colored layer formation in this invention in order to form a pixel, Preferably, 1 or more types of organic pigments are used as a coloring agent, When using for forming a black matrix, Preferably As the colorant two or more organic pigments, carbon black or combinations thereof are used.

As carbon black used for formation of a black matrix, for example, SAF, SAF-HS, ISAF, ISAF-LS, ISAF-HS, HAF, HAF-LS, HAF-HS, NAF, FEF, FEF-HS, SRF, Furnace blacks such as SRF-LM, SRF-LS, GPF, ECF, N-339 and N-351; Thermal blacks, such as FT and MT, include acetylene black and the like.

These carbon blacks can be used individually or in mixture of 2 or more types.

In the present invention, each of the pigments can be used by modifying the particle surface of the polymer according to the purpose. As a polymer which modifies the particle surface of a pigment, the polymer of Unexamined-Japanese-Patent No. 8-259876, etc., a commercially available pigment dispersion polymer, an oligomer, etc. are mentioned, for example.

In addition, the coloring agent in this invention can be used with a dispersing agent according to the objective.

As said dispersing agent, surfactant, such as a cationic type, an anionic type, nonionic type, amphoteric, silicone type, and fluorine type, is mentioned, for example.

As a specific example of the said surfactant, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene alkylphenyl ethers such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether; Polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; Sorbitan fatty acid esters; Fatty acid modified polyesters; Tertiary amine modified polyurethanes; In addition to polyethyleneimines, KP (manufactured by Shin-Etsu Chemical Co., Ltd.), polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), and Mega Pack (die) Nippon Ink Kagaku Kogyo Co., Ltd.), Floride (Sumitomo 3M Co., Ltd.), Asahi Guard, Supron (above, Asahi Glass Co., Ltd.), Disperbyk-101, 103, 107, 110, 111 , 115, 130, 160, 161, 162, 163, 164, 165, 166, 170, 180, 182, 2000, 2001 (above, manufactured by Big Chemi Japan Co., Ltd.), Sol Super S5000, S12000, S13240, S13940, S17000, S20000, S22000, S24000, S24000GR, S26000, S27000, S28000 (above, manufactured by Avisia Co., Ltd.), EFKA46, 47, 48, 745, 4540, 4550, 6750, EFKA LP4008, 4009, 4010, 4015 , 4050, 4055, 4560, 4800, EFKA Polymer 400, 401, 402, 403, 450, 451, 453 (above, manufactured by Efka Chemicals Co., Ltd.), and the like.

These surfactant can be used individually or in mixture of 2 or more types.

The amount of the surfactant to be used is preferably 50 parts by weight or less, more preferably 0 to 30 parts by weight with respect to 100 parts by weight of the colorant.

In this invention, the radiation sensitive resin composition for colored layer formation can be manufactured by a suitable method. In the case of using a pigment as a colorant, for example, the pigment is mixed and dispersed in a solvent in the presence of a dispersant, optionally with an alkali-soluble resin, for example, by grinding with a bead mill, a roll mill, and the like, and then dispersed in a pigment dispersion. It is preferable to make it and to manufacture by mixing this with (B)-(E) component mentioned later.

The amount of the dispersant used in preparing the pigment dispersion is preferably 100 parts by weight or less, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 70 parts by weight, particularly preferably 100 parts by weight of the pigment. 10 to 50 parts by weight. When the amount of the dispersant used exceeds 100 parts by weight, there is a fear that the developability and the like are damaged.

Moreover, as a solvent used when manufacturing a pigment dispersion liquid, the same thing as the solvent illustrated about the component (E) mentioned later is mentioned, for example, The solvent used for manufacture of a pigment dispersion liquid is added to the said pigment dispersion liquid. It may be same as a solvent, and may differ.

The amount of the solvent used when producing the pigment dispersion is preferably 500 to 1,000 parts by weight, more preferably 700 to 900 parts by weight based on 100 parts by weight of the pigment.

In addition, the alkali-soluble resin used when manufacturing a pigment dispersion liquid may be the same as that of (B) component, and may differ.

When manufacturing a pigment dispersion, when manufacturing using a bead mill, the pigment mixture liquid containing a pigment, a solvent, and a dispersing agent, for example using glass beads, titania beads, etc. about 0.5-10 mm in diameter, Preferably The treatment can be carried out while cooling with cooling water or the like.

In this case, the filling rate of the beads is preferably 50 to 80 vol% of the mill capacity. The injection amount of the pigment mixture liquid is preferably about 20 to 50 vol% of the mill capacity. Further, the treatment time is preferably 2 to 50 hours, more preferably 2 to 25 hours.

In addition, when manufacturing using a roll mill, it can carry out by processing, for example, using a triaxial roll mill, a biaxial roll mill, etc., cooling a pigment mixture liquid with cooling water etc. preferably.

In this case, it is preferable that a roll space | interval is 10 micrometers or less, and a shear force becomes like this. Preferably it is about 10 ⁸ dyn / sec. Further, the treatment time is preferably 2 to 50 hours, more preferably 2 to 25 hours.

-(B) alkali-soluble resin-

As alkali-soluble resin in this invention, it acts as a binder with respect to (A) coloring agent, and when manufacturing a color filter, the developing solution used at the image development processing process, Especially preferably, what has solubility with respect to alkaline developing solution is used. . As an example, the copolymer of the polymerizable unsaturated monomer which has acidic functional groups, such as a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid, and another copolymerizable unsaturated monomer (henceforth a "copolymerizable unsaturated monomer") is mentioned.

As a polymerizable unsaturated monomer which has a carboxyl group (henceforth a "carboxyl group-containing unsaturated monomer"), for example

Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid;

Unsaturated dicarboxylic acids or anhydrides thereof such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride and mesaconic acid;

Trivalent or higher unsaturated polyvalent carboxylic acid or anhydrides thereof;

Mono [(meth) acryloyloxyalkyl] of divalent or more polyvalent carboxylic acid, such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl] Ester;

The mono (meth) acrylate etc. of the polymer which has a carboxyl group and a hydroxyl group in both terminal, such as (omega)-carboxy polycaprolactone mono (meth) acrylate, are mentioned.

Among these carboxyl group-containing unsaturated monomers, (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl],? -Carboxypolycaprolactone mono (meth) acrylate, and the like are particularly preferable.

The said carboxyl group-containing unsaturated monomer can be used individually or in mixture of 2 or more types.

Moreover, as a polymerizable unsaturated monomer which has a phenolic hydroxyl group, o-hydroxy styrene, m-hydroxy styrene, p-hydroxy styrene, o-hydroxy-alpha-methylstyrene, m-hydroxy-alpha, for example -Methyl styrene, p-hydroxy- (alpha) -methylstyrene, No-hydroxyphenyl maleimide, Nm-hydroxyphenyl maleimide, Np-hydroxyphenyl maleimide, etc. are mentioned.

The polymerizable unsaturated monomer which has these phenolic hydroxyl groups can be used individually or in mixture of 2 or more types.

Moreover, isoprene sulfonic acid, p-styrene sulfonic acid, etc. are mentioned as a polymerizable unsaturated monomer which has a sulfonic acid group, for example.

The polymerizable unsaturated monomer which has these sulfonic acid groups can be used individually or in mixture of 2 or more types.

Subsequently, as a copolymerizable unsaturated monomer, for example

Macromonomer which has a mono (meth) acryloyl group at the terminal of polymer molecular chains, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, and polysiloxane (henceforth simply called "macromonomer"). box):

N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No- N-position substituted maleimide, such as N- (substituted) aryl maleimide, such as methoxyphenyl maleimide, Nm-methoxyphenyl maleimide, and Np-methoxyphenyl maleimide, and N-cyclohexyl maleimide;

Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl Aromatic vinyl compounds such as ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, and p-vinyl benzyl glycidyl ether;

Indenes such as indene and 1-methylindene;

Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate , 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (Meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (Meth) acrylate, methoxy propylene glycol (meth) acrylate, Toxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth Unsaturated carboxylic esters such as acrylate;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl (meth) acrylate, 3 Unsaturated carboxylic acid aminoalkyl esters such as -dimethylaminopropyl (meth) acrylate;

Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;

Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate;

Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether;

Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide;

Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, and N-2-hydroxyethyl (meth) acrylamide;

And aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene.

Among these copolymerizable unsaturated monomers, macromonomer, N-position substituted maleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, and the like are preferable. Moreover, in a macromonomer, a polystyrene macromonomer and a polymethyl (meth) acrylate macromonomer are especially preferable, and among N-position substituted maleimide, N-phenylmaleimide and N-cyclohexyl maleimide are especially preferable.

The said copolymerizable unsaturated monomer can be used individually or in mixture of 2 or more types.

As preferable alkali-soluble resin in this invention, the copolymer (henceforth simply a "carboxyl group-containing copolymer") of a carboxyl group-containing unsaturated monomer and a copolymerizable unsaturated monomer is mentioned.

Examples of the carboxyl group-containing copolymer include (a) a carboxyl group-containing unsaturated monomer, (b) a polystyrene macromonomer, a polymethyl (meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, and 2-hydroxyethyl (Meth) acrylates, benzyl (meth) acrylates and glycerol (meth) acrylates containing one or more selected from the group; (c) optionally styrene, α-methylstyrene, methyl (meth) acrylates And a copolymer of a monomer mixture further containing one or more selected from the group of allyl (meth) acrylate and phenyl (meth) acrylate (hereinafter referred to as "carboxyl group-containing copolymer (I)"), In particular, (a) (meth) acrylic acid is an essential component, and succinic acid mono [2- (meth) acryloyloxyethyl] and / or ω-carboxypolycaprolactone mono (meth) acrylate are optionally The carboxyl group-containing unsaturated monomer which contains further, (b) polystyrene macromonomer, polymethyl (meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexyl maleimide, 2-hydroxyethyl (meth) acrylate At least one selected from the group consisting of benzyl (meth) acrylate and glycerol (meth) acrylate, and (c) optionally styrene, α-methyl styrene, methyl (meth) acrylate, allyl (meth) Preferred is a copolymer (hereinafter referred to as "carboxyl group-containing copolymer (II)") of a monomer mixture further containing at least one member selected from the group of acrylates and phenyl (meth) acrylates.

As a specific example of the carboxyl group-containing copolymer (II),

(Meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,

(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / N-phenylmaleimide / α-methylstyrene / benzyl (meth) acrylate,

(Meth) acrylic acid / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / N-cyclohexylmaleimide / α-methylstyrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / allyl (meth) acrylate copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / allyl (meth) acrylate copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer,

(Meth) acrylic acid / styrene / 2-hydroxyethyl (meth) acrylate copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide / styrene / phenyl (meth) acrylate / polystyrene macromonomer copolymer,

(Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / N-phenylmaleimide / styrene / phenyl (meth) acrylate / polymethylmethacrylate macromonomer copolymer,

(Meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / omega-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer etc. are mentioned.

The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. If the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility in the alkali developer of the radiation-sensitive composition for forming a colored layer to be obtained tends to decrease, while when it exceeds 50% by weight, the solubility in the alkaline developer is exceeded. When it develops excessively and develops with alkaline developing solution, there exists a tendency which becomes easy to cause the fall of the colored layer from the board | substrate and the film | membrane roughness of the colored layer surface.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is preferably 3,000 to 300,000, more preferably Is from 3,000 to 100,000.

The polystyrene reduced number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is preferably 3,000 to 60,000, and more. Preferably it is 3,000-25,000.

Moreover, ratio (Mw / Mn) of Mw and Mn of alkali-soluble resin in this invention becomes like this. Preferably it is 1-5, More preferably, it is 1-4.

By using alkali-soluble resin which has such specific Mw or Mn, the radiation sensitive composition for colored layer formation excellent in developability is obtained, and the colored layer which has a sharp pattern edge part can be formed by this, and at the time of developing Residues, background contamination, film residues, etc., on the substrate and the light shielding layer of the unexposed portion become difficult to occur.

In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.

The usage-amount of alkali-soluble resin in this invention becomes like this. Preferably it is 10-1,000 weight part, More preferably, it is 20-500 weight part with respect to 100 weight part of (A) coloring agents. When the amount of the alkali-soluble resin used is less than 10 parts by weight, for example, alkali developability may decrease, or background contamination or film residue may occur on the substrate or the light shielding layer of the unexposed part, and when it exceeds 1,000 parts by weight, Since the colorant concentration decreases relatively, it may be difficult to achieve the target color density as a thin film.

-(C) polyfunctional monomer-

The polyfunctional monomer in the present invention is a monomer having two or more polymerizable unsaturated bonds in the molecule.

As a polyfunctional monomer, for example

Di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol;

Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol;

Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, and modified dicarboxylic acids thereof;

Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin and spiran resin;

Di (meth) acrylates of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone,

Tris [2- (meth) acryloyloxyethyl] phosphate etc. are mentioned.

Of these polyfunctional monomers, poly (meth) acrylates of trivalent or higher polyhydric alcohols and their dicarboxylic acid modified substances, specifically trimethylolpropane tri (meth) acrylate and pentaerythritol tri (meth) acrylate , Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like are preferable, and trimethylolpropane triacrylate and pentaerythritol triacryl are particularly preferred. The rate and dipentaerythritol hexaacrylate are preferable in terms of high colored layer strength, excellent smoothness of the surface of the colored layer, and low background contamination, film residue, etc. on the substrate and the light shielding layer of the unexposed portion.

These polyfunctional monomers can be used individually or in mixture of 2 or more types.

The usage-amount of the polyfunctional monomer in this invention becomes like this. Preferably it is 5-500 weight part, More preferably, it is 20-300 weight part with respect to 100 weight part of (B) alkali-soluble resin. When the amount of the polyfunctional monomer used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tends to decrease. On the other hand, when the amount of the polyfunctional monomer exceeds 500 parts by weight, for example, alkali developability is lowered, or on the substrate or the light shielding layer of the unexposed part. Background contamination, film residues, etc. tend to occur.

In this invention, the monofunctional monomer which has one polymerizable unsaturated bond in a molecule | numerator can also be used together with a polyfunctional monomer.

As said monofunctional monomer, the carboxyl group-containing unsaturated monomer, copolymerizable unsaturated monomer, and N-vinyl succinimide, N-vinylpyrrolidone, and N-vinyl phthal which were illustrated, for example with respect to said (B) alkali-soluble resin are mentioned, for example. Mead, N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrolidine, N-vinylimidazole, N-vinylimidazolidine, N-vinyl N- such as indole, N-vinyl indolin, N-vinyl benzimidazole, N-vinylcarbazole, N-vinyl piperidine, N-vinyl piperazine, N-vinylmorpholine, and N-vinylphenoxadine Vinyl derivatives; As a commercial item besides N- (meth) acryloyl morpholine, M-5300, M-5400, M-5600 (above, Toagosei Co., Ltd. product) etc. are mentioned.

These monofunctional monomers can be used individually or in mixture of 2 or more types. The use ratio of a monofunctional monomer becomes like this. Preferably it is 90 weight% or less, More preferably, it is 50 weight% or less with respect to the sum total of a polyfunctional monomer and a monofunctional monomer. When the use ratio of a monofunctional monomer exceeds 90 weight%, there exists a tendency for the intensity | strength and surface smoothness of a colored layer to fall.

-(D) photoinitiator-

The photopolymerization initiator in the present invention is an active species capable of initiating the polymerization of the above-mentioned (C) polyfunctional monomer and the monofunctional monomer used in some cases by exposure to visible light, ultraviolet ray, far ultraviolet ray, electron beam, X-ray and the like. It is a compound that can occur.

As such a photoinitiator, an acetophenone type compound, a biimidazole type compound, a triazine type compound, a benzoin type compound, a benzophenone type compound, the (alpha)-diketone type compound, a polynuclear quinone type compound, a xanthone type compound, a diazo type compound, for example Etc. can be mentioned.

In this invention, a photoinitiator can be used individually or in mixture of 2 or more types. As the photopolymerization initiator in the present invention, at least one selected from the group of acetophenone compounds, biimidazole compounds, and triazine compounds is preferably used.

The usage-amount of the photoinitiator in this invention becomes like this. Preferably it is 0.01-80 weight part, More preferably, it is 1-60 weight part with respect to 100 weight part of total (C) polyfunctional monomers or this and a monofunctional monomer. If the amount of the photopolymerization initiator is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged along a predetermined arrangement. There exists a tendency for it to fall easily from a board | substrate at the time of image development.

As a specific example of an acetophenone type compound among the preferable photoinitiators in this invention, 2-hydroxy-2- methyl-1- phenyl propane- 1-one, 2-methyl-1- [4- (methylthio) phenyl]- 2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,2- Dimethoxy-1,2-diphenylethan-1-one, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), and the like.

Among these acetophenone compounds, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholine Nophenyl) butan-1-one, 1,2-octanedione-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) and the like are preferable.

The acetophenone compounds may be used alone or in combination of two or more thereof.

In this invention, the usage-amount when using an acetophenone type compound as a photoinitiator, Preferably it is 0.01-80 weight part with respect to a total of 100 weight part of (C) polyfunctional monomer or this and a monofunctional monomer, More preferably Preferably 1 to 60 parts by weight, more preferably 1 to 30 parts by weight. If the amount of the acetophenone-based compound is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged along a predetermined arrangement. There exists a tendency for a layer to fall easily from a board | substrate at the time of image development.

Moreover, as a specific example of the said biimidazole type compound, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetrakis (4-ethoxycarbonylphenyl) -1,2' -Biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl) -1,2'-biimidazole, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl)- 4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4,4', 5,5'- Tetraphenyl-1,2'-biimidazole, 2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2, 2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6- Tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, etc. are mentioned.

Among these biimidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis ( 2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4,6-trichlorophenyl) -4, 4 ', 5,5'-tetraphenyl-1,2'-biimidazole and the like are preferred, in particular 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'- Tetraphenyl-1,2'-biimidazole is preferred.

The biimidazole-based compound is excellent in solubility in a solvent, does not produce foreign matters such as undissolved seafood, precipitates, etc., has high sensitivity, sufficiently proceeds the curing reaction by exposure of a small amount of energy, and has a high contrast. Since no curing reaction occurs in the unexposed portion, the coated film after exposure is clearly divided into an insoluble hardened portion with respect to the developer and an uncured portion with high solubility with the developer, whereby a colored layer pattern without undercut is defined. It is possible to form a high-precision color filter disposed along the arrangement of. The said biimidazole type compound can be used individually or in mixture of 2 or more types.

In this invention, the usage-amount when using a biimidazole type compound as a photoinitiator becomes like this. Preferably it is 0.01-40 weight part with respect to a total of 100 weight part of (C) polyfunctional monomer or this and a monofunctional monomer, More Preferably it is 1-30 weight part, More preferably, it is 1-20 weight part. If the amount of the non-imidazole compound is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged along a predetermined arrangement. There exists a tendency which becomes easy to cause the fall of the colored layer formed at the time from the board | substrate, and the roughness of the colored layer surface.

In this invention, when using a biimidazole type compound as a photoinitiator, using the following hydrogen donor together is preferable at the point which can improve a sensitivity further.

The "hydrogen donor" here means a compound which can donate a hydrogen atom with respect to the radical which generate | occur | produced from the biimidazole type compound by exposure.

As the hydrogen donor in the present invention, mercaptan compounds and amine compounds defined below are preferable.

The mercaptan compound is a compound having a benzene ring or a heterocycle as a mother nucleus, and having at least one mercapto group bonded directly to the mother nucleus, preferably 1 to 3, more preferably 1 to 2 (hereinafter, "mercap" Carbon-based hydrogen donor.

The amine compound is a compound having a benzene ring or a hetero ring as a mother nucleus, and having at least one, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as "amine type Hydrogen donor ”.

These hydrogen donors may also have a mercapto group and an amino group at the same time.

Hereinafter, these hydrogen donors will be described in more detail.

The mercaptan-based hydrogen donor may have one or more benzene rings or heterocycles, and may have both a benzene ring and a heterocycle, and in the case of having two or more of these rings, a condensed ring may be formed or not formed. It may not.

In addition, when the mercaptan-based hydrogen donor has two or more mercapto groups, as long as one or more free mercapto groups remain, one or more of the remaining mercapto groups may be substituted with an alkyl group, an aralkyl group, or an aryl group, and one or more mercapto groups. As long as the free mercapto group remains, it may have a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or a structural unit in which two sulfur atoms are bonded in the form of disulfide.

In addition, the mercaptan-based hydrogen donor may be substituted by a carboxyl group, a (substituted) alkoxycarbonyl group, a (substituted) phenoxycarbonyl group, a nitrile group, or the like in portions other than the mercapto group.

Specific examples of such mercaptan-based hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2 Mercapto-2,5-dimethylaminopyridine and the like.

Among these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and the like are preferable, and 2-mercaptobenzothiazole is particularly preferable.

The amine-based hydrogen donor may have one or more benzene rings or heterocycles in the molecule, and may have both a benzene ring and a heterocycle, and in the case of having two or more of these rings, a condensed ring may be formed and formed. You may not.

In addition, the amine-based hydrogen donor may be substituted with at least one amino group by an alkyl group or a substituted alkyl group, and may be substituted by a carboxyl group, a (substituted) alkoxycarbonyl group, a (substituted) phenoxycarbonyl group, a nitrile group, or the like in a portion other than the amino group. have.

Specific examples of such amine hydrogen donors include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, and 4-dimethylaminopropiophenone. , Ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile, and the like.

Among these amine-based hydrogen donors, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, and the like are preferable, and 4,4'-bis (diethylamino) is particularly preferred. Benzophenone is preferred.

The amine hydrogen donor also has a function as a sensitizer even in the case of photopolymerization initiators other than the biimidazole compound.

In the present invention, the hydrogen donors may be used alone or in combination of two or more thereof. In particular, the combination of one or more mercaptan-based hydrogen donors and one or more amine-based hydrogen donors is preferable in that the sensitivity is high, the colored layer formed is unlikely to drop off from the substrate at the time of development, and the strength of the colored layer is also high. .

Specific examples of preferred combinations of mercaptan-based hydrogen donors and amine-based hydrogen donors include 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone and 2-mercaptobenzothiazole / 4,4'-bis (Diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzophenone Etc. can be mentioned. More preferred combinations are 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzophenone, and the like. Particularly preferred combination is 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone.

The weight ratio of the mercaptan-based hydrogen donor to the amine-based hydrogen donor in the combination of the mercaptan-based hydrogen donor and the amine-based hydrogen donor is preferably 1: 1 to 1: 4, more preferably 1: 1 to 1: 3.

In the present invention, the amount used when the hydrogen donor is used in combination with the non-imidazole compound is preferably 0.01 to 40 parts by weight, more preferably 100 parts by weight of the total of the (C) polyfunctional monomer or monofunctional monomer. It is preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. When the amount of the hydrogen donor used is less than 0.01 part by weight, the effect of improving the sensitivity tends to decrease. On the other hand, when the amount of the hydrogen donor exceeds 40 parts by weight, the formed colored layer tends to fall off the substrate during development.

In addition, specific examples of the triazine-based compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [ 2- (5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4, 6-bis (trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4 Triazine type compounds which have halomethyl groups, such as a 6-bis (trichloromethyl) -s-triazine, are mentioned.

Among these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is particularly preferable.

The said triazine type compound can be used individually or in mixture of 2 or more types.

In this invention, the usage-amount when using a triazine type compound as a photoinitiator becomes like this. Preferably it is 0.01-40 weight part with respect to a total of 100 weight part of (C) polyfunctional monomer or this and monofunctional monomer, More preferably, Is 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. If the amount of the triazine-based compound is less than 0.01 part by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged along a predetermined arrangement. There exists a tendency for it to fall easily from a board | substrate at this time of image development.

-(E) solvent-

The solvent in the present invention is a mixed solvent and contains dipropylene glycol methyl ether acetate as an essential component.

The content ratio of dipropylene glycol methyl ether acetate in the solvent is 3 to 8.5% by weight, preferably 3 to 7.5% by weight, particularly preferably 3 to 7% by weight. If the content ratio of dipropylene glycol methyl ether acetate is less than 3% by weight, the inhibitory effect of dried products or dolby holes of the radiation-sensitive composition for forming a colored layer may decrease. There is a possibility that this decreases and an insoluble matter precipitates.

The solvent in the present invention is 91.5 to 97% by weight, preferably 92.5 to 97% by weight, particularly preferably 93 to 97% by weight of solvents other than dipropylene glycol methyl ether acetate (hereinafter referred to as "other solvents"). It contains.

The other solvent is appropriately selected as long as it disperses or dissolves the components (A) to (D) constituting the radiation-sensitive composition for forming a colored layer or the additive component described later, does not react with these components, and has appropriate volatility. Although it can use, it is preferable that a solvent below boiling point 150 degreeC, Preferably it is 130 degreeC or more and less than 150 degreeC (henceforth a "low boiling point solvent"). "Boiling point" as used in the present invention means a value at 1 atmosphere.

Specific examples of the low boiling point solvent include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, 2-heptanone, n-butyl acetate, i-butyl acetate, i-pentyl acetate, ethyl butyrate, and n-butyric acid. Propyl, butyric acid i-propyl, ethyl pyruvate and the like.

Among these low boiling point solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, 2-heptanone, i-pentyl acetate, ethyl pyruvate and the like are preferable, and in particular, propylene glycol monomethyl ether and propylene glycol mono Ethyl ether and propylene glycol methyl ether acetate are preferable.

The said low boiling point solvent can be used individually or in mixture of 2 or more types.

The content ratio of the low boiling point solvent in the mixed solvent (E) is preferably 30 to 70% by weight, more preferably 50 to 70% by weight, particularly preferably 50 to 65% by weight. If the content ratio of the low boiling point solvent is less than 30% by weight, there is a risk of causing sticking or a decrease in productivity due to a long heating time, and if it exceeds 70% by weight, the effect of inhibiting dry matter of the radiation-sensitive composition for forming a colored layer. May become insufficient.

In the present invention, the mixed solvent (E) is a solvent having a boiling point of 150 ° C. or more and less than 180 ° C., preferably 155 ° C. or more and less than 180 ° C., together with a low boiling point solvent as another solvent (hereinafter, referred to as “middle boiling point solvent”). It is preferable to further contain.

Specific examples of the middle boiling point solvent include ethylene glycol mono-n-butyl ether, ethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, and cyclohexanone And ethyl 3-ethoxypropionate, n-butyl butyrate, methyl acetoacetate, and the like.

Among these middle boiling point solvents, ethylene glycol mono-n-butyl ether, ethylene glycol ethyl ether acetate, propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, cyclohexanone, Ethyl 3-ethoxypropionate and the like are preferable, and propylene glycol ethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone and ethyl 3-ethoxypropionate are particularly preferable. Do.

The middle boiling point solvents may be used alone or in combination of two or more thereof.

The content ratio of the middle boiling point solvent in the solvent is preferably 20 to 60% by weight, more preferably 20 to 50% by weight, particularly preferably 25 to 45% by weight. If the content ratio of the middle boiling point solvent is less than 20% by weight, the dried material of the radiation-sensitive composition for forming the colored layer tends to be easily generated, while if it exceeds 60% by weight, the productivity due to the occurrence of sticking or the long heating time is increased. There is a risk of deterioration.

In the present invention, the mixed solvent (E) further contains a solvent having a boiling point of 180 ° C. or higher (except dipropylene glycol methyl ether acetate) (hereinafter referred to as a “high boiling point solvent”) together with each of the above solvents. You may.

Specific examples of the high boiling point solvents include benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, benzoate ethyl and oxalic acid di Ethyl, diethyl maleate, gamma -butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate, and the like.

The said high boiling point solvent can be used individually or in mixture of 2 or more types.

When the content ratio of each solvent in the solvent in this invention is shown more concretely, Preferably it is 3 to 8.5 weight% of dipropylene glycol methyl ether acetate, 40 to 70 weight% of a low boiling point solvent, and 20 to 60 weight of a medium boiling point solvent. %, High boiling point solvent is 20 weight% or less, More preferably, 3 to 7.5 weight% of dipropylene glycol methyl ether acetate, 50 to 70 weight% of low boiling point solvent, 20 to 50 weight% of middle boiling point solvent, and high boiling point The solvent is 20% by weight or less, particularly preferably 3 to 7% by weight of dipropylene glycol methyl ether acetate, 50 to 65% by weight of low boiling point solvent, 25 to 45% by weight of medium boiling point solvent and 20% of high boiling point solvent. It is% or less. By using such a mixed solvent, generation | occurrence | production of the dry matter, a dolby hole, etc. of the radiation sensitive composition for colored layer formation is suppressed remarkably, and it does not cause the fall of productivity by the generation of sticking and a long heating time, and an insoluble matter The radiation sensitive composition for forming a colored layer which does not precipitate is obtained.

Although the total usage-amount of the solvent in the radiation sensitive composition for colored layer formation of this invention is not specifically limited, Solid content concentration except the solvent of the said composition from the viewpoint of the coating property, stability, etc. of the composition obtained becomes like this. Preferably it is 5-50. It is preferred that the amount be by weight, particularly preferably 10 to 40% by weight.

Other additives

Although the radiation sensitive composition for colored layer formation of this invention makes said (A)-(E) component an essential component, it may contain another additive as needed.

As said other additive, For example, fillers, such as glass and an alumina; Polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate) s; Surfactants such as nonionic surfactants, cationic surfactants, and anionic surfactants; Vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tri (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropyl methyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropyl methyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyl trimethoxysilane, 3-chloropropylmethyl dimethoxysilane, 3-chloropropyl trimethoxysilane, 3-methacryloyloxypropyl trimethoxysilane, 3-mercaptopropyl trimethoxysilane, etc. Adhesion promoter; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butylphenol; Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; Agglomeration inhibitors, such as sodium polyacrylate, etc. are mentioned.

color  How to Form Filter

Next, the method of forming the color filter of this invention is demonstrated using the radiation sensitive composition for colored layer formation (henceforth simply "the composition for colored layer formation") of this invention.

The formation method of the color filter of this invention includes the process of following (1)-(4) at least.

(1) The process of forming the coating film of the composition for colored layer formation on a board | substrate.

(2) The process of exposing to at least one part of the said coating film.

(3) The process of developing the coating film after exposure.

(4) Process of heat-processing (henceforth "post baking") the coating film after image development.

Hereinafter, these processes are demonstrated in order.

(1) process

First, on the surface of a board | substrate, a light shielding layer is formed so that the part which forms a pixel may be divided as needed, and a coating composition for colored layer formation is apply | coated on this board | substrate, and it prebakes under reduced pressure ("vacuum baking" hereafter). Is evaporated to remove the solvent to form a coating film.

Examples of the substrate used in this step include glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyether sulfone, ring-opening polymers of cyclic olefins and hydrogenated products thereof. Can be.

In addition, these substrates may be subjected to appropriate pretreatment such as chemical treatment with a silane coupling agent or the like, plasma treatment, ion plating, sputtering, vapor phase reaction, vacuum deposition, or the like.

Although it does not specifically limit as a method of apply | coating the composition for colored layer formation to a board | substrate, The method of using slit nozzles, such as a slit and spin coating method and a spinless coating method (henceforth a "slit nozzle coating method"). This is preferable.

Solid content of the composition for colored layer formation used for a slit nozzle coating method becomes like this. Preferably it is 10-20 weight%, Especially preferably, it is 13-18 weight%.

The coating conditions in the slit nozzle coating method differ depending on the slit and spin coating method, the spinless coating method, the size of the coating substrate, and the like, but for example, the fifth generation glass substrate (1,100 mm × 1,250 mm) by the spinless coating method. ), The discharge amount of the colored layer-forming composition from the slit nozzle is preferably 500 to 2,000 microliters / second, more preferably 800 to 1,500 microliters / second. In addition, the coating speed is preferably 500 to 1,500 mm / sec, more preferably 700 to 1,200 mm / sec.

The conditions for the vacuum baking are preferably 0.1 to 1.0 torr, more preferably about 0.2 to 0.5 torr, the temperature is preferably 60 to 120 ° C, more preferably about 70 to 110 ° C, and baking time. Is preferably 1 to 5 minutes, more preferably about 2 to 4 minutes.

The thickness of the coating film formed in this step is preferably 0.1 to 10 µm, more preferably 0.2 to 8.0 µm, and particularly preferably 0.2 to 6.0 µm as the film thickness after solvent removal.

(2) process

Then, it exposes to at least one part of the formed coating film. When exposing to a part of coating film, it exposes normally through the photomask which has a suitable pattern.

As radiation used for exposure, visible light, an ultraviolet-ray, an ultraviolet ray, an electron beam, X-rays, etc. can be used, for example, but the radiation in the range whose wavelength is 190-450 nm is preferable.

The exposure dose of radiation is preferably about 10 to 10,000 J / m ² .

(3) process-

Then, it develops using a developing solution and removes and removes the unexposed part of a coating film.

As the developer, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo Alkali developing solution containing aqueous solutions, such as-[4.3.0] -5-nonene, is preferable.

An appropriate amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may be added to the alkaline developer. After alkali development, it washes with water preferably.

As the development treatment method, suitable methods such as a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid immersion) development method, and the like can be adopted.

As for image development conditions, about 5 to 300 second is preferable at normal temperature.

(4) process

Thereafter, the colored layer can be formed on the substrate by postbaking.

As for the conditions of postbaking, 20 to 40 minutes are preferable at 180-230 degreeC.

In the formation method of the color filter of this invention, the said (1)-(4) process is repeated using each colored layer formation composition in which the red, green, or blue pigment was disperse | distributed, and the red pixel pattern and green By forming the pixel pattern and the blue pixel pattern on the same substrate, a colored layer in which the pixel patterns of the three primary colors of red, green and blue are arranged in a predetermined arrangement can be formed on the substrate. However, in this invention, the formation order of the pixel pattern of each color is not specifically limited.

The film thickness of the pixel thus formed is preferably 0.5 to 5.0 m, more preferably 1.5 to 3.0 m.

Best Mode for Carrying Out the Invention

The radiation sensitive composition for colored layer formation of this invention contains (A) coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, (D) photoinitiator, and (E) mixed solvent, (E ) Although the mixed solvent contains 3 to 8.5% by weight of dipropylene glycol methyl ether acetate, particularly preferred compositions are as follows (a) to (tea).

(A) Coloring in which (B) component contains a carboxyl group-containing copolymer (II) and (D) component contains 1 or more types chosen from the group of acetophenone type compound, a biimidazole type compound, and a triazine type compound. Radiation-sensitive composition for layer formation.

(B) In the above (a), the component (B) contains a carboxyl group-containing copolymer (II), and the acetophenone compound in the component (D) is 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinopropaneone-1,2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 and 1,2-octanedione-1- [4- (phenyl Thio) phenyl] -2- (O-benzoyloxime), and the biimidazole-based compound in component (D) is 2,2'-bis (2-chlorophenyl) -4 , 4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,4', 5,5'-tetraphenyl-1 From the group of, 2'-biimidazole and 2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole It includes at least one selected, the triazine-based compound in (D) component is 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-tri The radiation sensitive composition for colored layer formation containing azine.

(C) The said (A) or (B) WHEREIN: The carboxyl group-containing copolymer (II) in (B) component is (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / Benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / N-cyclohexyl Maleimide / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / allyl (meth) acrylate copolymer , (Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / succinic acid mono [2- (meth Acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / allyl (meth) Acrylate copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / styrene / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl ( Meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / benzyl (meth) acrylate / glycerol mono (meth) acrylate air Copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / styrene / 2-hydroxyethyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (Meth) acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (Meth) acrylate / benzyl (meth) acrylate / poly Macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer and (meth) acrylic acid / N-phenylmaleimide The radiation sensitive composition for colored layer formation containing 1 or more types chosen from the group of the / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer.

(D) The one of (a) to (c), wherein (C) component is one selected from the group of trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. The radiation sensitive composition for colored layer formation containing the above.

(E) The radiation sensitive composition for colored layer formation in any one of said (A)-(D) whose (A) component contains an organic pigment and / or carbon black.

(F) The radiation sensitive composition for forming a colored layer according to any one of the above (a) to (e), wherein the component (E) contains 40 to 70 wt% of a low boiling point solvent.

(G) The radiation sensitive composition for forming a colored layer according to the above (bar), wherein the low boiling point solvent comprises at least one selected from the group consisting of propylene glycol monomethyl ether, propylene glycol monoethyl ether, and propylene glycol monomethyl ether acetate. .

(H) The radiation sensitive composition for forming a colored layer according to the above (bar) or (g), wherein the component (E) further contains 20 to 60% by weight of a middle boiling point solvent.

(D) In the above (a), the middle boiling point solvent is propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, cyclohexanone and 3-ethoxypropionic acid The radiation sensitive composition for colored layer formation containing 1 or more types chosen from the group of ethyl.

In addition, the preferred color filter of the present invention,

(K) formed of the radiation-sensitive composition for forming a colored layer of (a), (b), (c), (d), (e), (f), (d), or (d) It has a pixel and / or a black matrix.

Moreover, the preferable color liquid crystal display panel of this invention is

(Ta) The color filter of said (ka) is provided.

As described above, the radiation-sensitive composition for forming a colored layer of the present invention has high solvent re-solubility in dried products, can suppress generation of dolby holes, and is very preferably applied to the formation of a color filter using a slit nozzle coating method. can do.

<Example>

Hereinafter, an Example is given and this invention is demonstrated further more concretely. However, this invention is not limited to the following Example.

<Example 1>

(A) As a coloring agent, C.I. Pigment Red 254 / C.I. Pigment Red 177 = 80/20 (weight ratio) 15 parts by weight of the mixture, 4 parts by weight of Disperbyk-2001 as a dispersant (solid content), (B) methacrylic acid / N-phenylmaleimide / styrene / benzyl as alkali-soluble resin 6 parts by weight of the methacrylate copolymer (copolymerization weight ratio = 20/30/20/30, Mw = 9,500, Mn = 5,000) and 75 parts by weight of propylene glycol methyl ether acetate as a solvent were treated with a bead mill to give a pigment dispersion (R1). (100 parts by weight in total) was prepared.

Next, 100 parts by weight of the pigment dispersion (R1), (B) methacrylic acid / succinic acid mono (2-methacryloyloxyethyl) / N-phenylmaleimide / styrene / benzyl methacrylate copolymer ( Copolymer weight ratio = 25/10/30/20/15, Mw = 12,000, Mn = 6,500) 5 parts by weight, (C) 10 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 2 as a photopolymerization initiator 5 parts by weight of -methyl-1- [4- (methylthio) phenyl] -2-morpholinopropaneone-1, and (E) 12.5 parts by weight of dipropylene glycol methyl ether acetate as a mixed solvent ( 5 weight%), propylene glycol methyl ether acetate (75 weight parts of the total mixed solvent combined with the amount in (R1)), 75 weight part of 3-methoxybutyl acetate (30 weight% of the total mixed solvent), and cyclohexa 12.5 parts by weight of paddy (5% by weight of the total mixed solvent) was mixed to prepare a composition for forming a colored layer (R1-1). It was. The solvent in the colored layer formation composition (R1-1) contains the solvent in the pigment dispersion liquid (R1), and is the same also in each of the following colored layer formation compositions.

About the obtained composition for colored layer formation (R1-1), it evaluated in the following procedure. The evaluation results are shown in Table 1 below.

Solvent of dry matter Resoluble  evaluation

The composition for coloring layer formation (R1-1) was apply | coated to a glass substrate, and it air-dried for 30 minutes on 23 degreeC and the conditions of 50% of humidity. Then, the glass substrate with a dry coating film was immersed in propylene glycol monomethyl ether acetate for 10 minutes, and the following three steps were evaluated according to the re-dissolution state of a dry coating film.

○: All of the dry coating film dissolved during immersion

(Triangle | delta): A part of dry coating film remains after immersion for 10 minutes

X: The dry coating film does not melt | dissolve most or all after immersion for 10 minutes

Dolby  Evaluation of holes

After coating the composition for forming a colored layer (R1-1) with a spin coater on a soda glass substrate (300 mm x 400 mm) on which a SiO ₂ film was formed on the surface to prevent elution of sodium ions, the degree of vacuum was 0.3 at 23 ° C. Vacuum baking was performed until it reached torr, and the coating film of 2.5 micrometers in thickness was formed.

Then, the obtained board | substrate was observed with the optical microscope, the number of the dolby holes which generate | occur | produce in the arbitrary area | regions of 5 mm x 400 mm square of a coating film was counted, and the following three steps were evaluated.

○: less than 500

△: 500 or more, less than 1,000

×: 1,000 or more

<Example 2>

21.25 weight part of dipropylene glycol methyl ether acetate (8.5 weight% of all the mixed solvents), and 75 weight of propylene glycol methyl ether acetates of (E) mixed solvent added with respect to 100 weight part of pigment dispersion liquids (R1) in Example 1 A composition for forming a colored layer was obtained in the same manner as in Example 1 except for changing to a part (60% by weight of the total mixed solvent) and 78.75 parts by weight of ethyl 3-ethoxypropionate (31.5% by weight of the total mixed solvent). 2) was prepared and evaluated. The evaluation results are shown in Table 1.

<Example 3>

21.25 weight part of dipropylene glycol methyl ether acetate (8.5 weight% of all the mixed solvents), and 25 weight of propylene glycol methyl ether acetates of (E) mixed solvent added with respect to 100 weight part of pigment dispersion liquids (R1) in Example 1 A composition for forming a colored layer was formed in the same manner as in Example 1 except that the amount was changed to 40 parts by weight of the total mixed solvent and 128.75 parts by weight of diethylene glycol methylethyl ether (51.5% by weight of the total mixed solvent). 3) was prepared and evaluated. The evaluation results are shown in Table 1.

<Example 4>

In Example 1, 7.5 parts by weight of dipropylene glycol methyl ether acetate (3% by weight of the total mixed solvent) of 5 parts by weight of dipropylene glycol methyl ether acetate was added to 100 parts by weight of the pigment dispersion (R1). A composition for forming a colored layer was obtained in the same manner as in Example 1 except that the amount was changed to 50 parts by weight of the total mixed solvent and 117.5 parts by weight of the 3-methoxybutyl acetate (47% by weight of the total mixed solvent). 4) was prepared and evaluated. The evaluation results are shown in Table 1.

Comparative Example 1

In Example 1, 25 weight part of propylene glycol methyl ether acetates (40 weight% of all the mixed solvents), and 75 weight part of 3-methoxybutyl acetate were added the mixed solvent added with respect to 100 weight part of pigment dispersions (R1). Except having changed into 30 weight% of mixed solvent) and 75 weight part of cyclohexanone (30 weight% of all the mixed solvent), it carried out similarly to Example 1, and manufactured and evaluated the composition for coloring layer formation (R1-5). It was. The evaluation results are shown in Table 1.

Comparative Example 2

In Example 1, 50 weight part of propylene glycol methyl ether acetate (50 weight% of all the mixed solvent), 75 weight part of ethyl 3-ethoxypropionate (total amount) of the mixed solvent added with respect to 100 weight part of pigment dispersions (R1) Except having changed into 30 weight% of mixed solvent) and 50 weight part of diethylene glycol methylethyl ether (20 weight% of the total mixed solvent), it carried out similarly to Example 1, and carried out the composition for colored layer formation (R1-6). Was prepared and evaluated. The evaluation results are shown in Table 1.

Comparative Example 3

In Example 1, 37.5 parts by weight of dipropylene glycol methyl ether acetate (15% by weight of the total mixed solvent) was added to 100 parts by weight of the pigment dispersion (R1), and 25 parts by weight of propylene glycol methyl ether acetate (total A colored layer-forming composition (R1-7) was prepared in the same manner as in Example 1 except for changing to 40 wt% of the mixed solvent) and 112.5 parts by weight of diethylene glycol methylethyl ether (45 wt% of the total mixed solvent). Was prepared and evaluated. The evaluation results are shown in Table 1.

Example 5

(A) As a coloring agent, C.I. Pigment Green 36 / C.I. Pigment Yellow 138 / C.I. Pigment Yellow 150 = 50/40/10 (weight ratio) 15 parts by weight of the mixture, 4 parts by weight of Disperbyk-2001 as a dispersant (solid content), (B) methacrylic acid / ω-carboxydicaprolactone mono as the alkali-soluble resin 5 parts by weight of acrylate / N-phenylmaleimide / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymerization weight ratio = 15/10/20/10/35/10, Mw = 6,000, Mn = 3,000) , And 76 parts by weight of propylene glycol methyl ether acetate as a solvent were treated with a beads mill to prepare a pigment dispersion (G1) (100 parts by weight in total).

Next, 100 parts by weight of the pigment dispersion (G1) and (B) methacrylic acid / N-phenylmaleimide / styrene / benzyl methacrylate / glycerol monomethacrylate copolymer (copolymerization weight ratio = 15/25 / 15/35/10, Mw = 13,500, Mn = 6,000) 5 parts by weight, (C) 10 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer, (D) 2-benzyl-2-dimethylamino as the photopolymerization initiator 5 parts by weight of -1- (4-morpholinophenyl) butanone-1, and (E) 12.5 parts by weight of dipropylene glycol methyl ether acetate as a mixed solvent (5.0% by weight of the total mixed solvent), and propylene glycol methyl ether 50 parts by weight of acetate (50.0% by weight of the total mixed solvent in combination with the amount in (G1)), 87.5 parts by weight of 3-methoxybutyl acetate (35.0% by weight of the total mixed solvent) and 25 parts by weight of cyclohexanone (of the total mixed solvent 10.0 wt%) was mixed to form a composition for forming a colored layer (G1-1). It was.

Next, it evaluated by the same procedure as Example 1 except having used the obtained composition for colored layer formation (G1-1). The results are shown in Table 2 below.

<Example 6>

21.25 weight part of dipropylene glycol methyl ether acetate (about 8.5 weight% of all the mixed solvent), and the propylene glycol methyl ether acetate 75 of (E) mixed solvent added with respect to 100 weight part of pigment dispersion liquids (G1) in Example 5 A composition for forming a colored layer in the same manner as in Example 5 except for changing to parts by weight (about 60.0% by weight of the total mixed solvent) and 78.75 parts by weight of ethyl 3-ethoxypropionate (about 31.5% by weight of the total mixed solvent). After manufacturing (G1-2), it evaluated by the same procedure as Example 1. The evaluation results are shown in Table 2.

<Example 7>

21.25 parts of dipropylene glycol methyl ether acetate (about 8.5% by weight of the total mixed solvent) of (E) mixed solvent added to 100 parts by weight of the pigment dispersion (G1) in Example 5, propylene glycol methyl ether acetate 25 A composition for forming a colored layer in the same manner as in Example 5 except for changing to parts by weight (about 40.2% by weight of the total mixed solvent) and 128.75 parts by weight (about 51.3% by weight of the total mixed solvent) of 3-methoxybutyl acetate. After manufacturing (G1-3), it evaluated by the same procedure as Example 1. The evaluation results are shown in Table 2.

<Example 8>

7.5 weight part of dipropylene glycol methyl ether acetate (about 3.0 weight% of all the mixed solvents), and the propylene glycol methyl ether acetate 50 of (E) mixed solvent added with respect to 100 weight part of pigment dispersion liquids (G1) in Example 5 A composition for forming a colored layer was prepared in the same manner as in Example 5, except that the weight part (about 50.2 weight% of the total mixed solvent) and 117.5 weight part (46.8 weight% of the total mixed solvent) of 3-methoxybutyl acetate were changed. G1-4) was manufactured and evaluated in the same procedure as in Example 1. The evaluation results are shown in Table 2.

<Comparative Example 4>

In Example 5, 75 parts by weight of propylene glycol methyl ether acetate (60% by weight of the total mixed solvent) was added to 100 parts by weight of the pigment dispersion (G1), and 50 parts by weight of ethyl 3-ethoxypropionate (total A colored layer-forming composition (G1-5) was prepared in the same manner as in Example 5 except for changing to 20% by weight of the mixed solvent) and 50 parts by weight of diethylene glycol methylethyl ether (20% by weight of the total mixed solvent). After manufacture, it evaluated by the same procedure as Example 1. The evaluation results are shown in Table 2.

Comparative Example 5

In Example 5, 75 weight part of propylene glycol methyl ether acetates (30 weight% of all the mixed solvents), 125 weight part of ethyl 3-ethoxypropionate (total amount) with respect to 100 weight part of pigment dispersions (G1) A colored layer-forming composition (G1-6) was prepared in the same manner as in Example 5 except for changing to 50% by weight of the mixed solvent) and 50 parts by weight of 3-methoxybutyl acetate (20% by weight of the total mixed solvent). After manufacture, it evaluated by the same procedure as Example 1. The evaluation results are shown in Table 2.

Comparative Example 6

In Example 5, 37.5 parts by weight of dipropylene glycol methyl ether acetate (15% by weight of the total mixed solvent) was added to 100 parts by weight of the pigment dispersion (G1), and 24 parts by weight of propylene glycol methyl ether acetate (total A colored layer-forming composition (G1-7) was prepared in the same manner as in Example 5 except for changing to 40 wt% of the mixed solvent) and 112.5 parts by weight of 3-methoxybutyl acetate (45 wt% of the total mixed solvent). After manufacture, it evaluated by the same procedure as Example 1. The evaluation results are shown in Table 2.

Example 9

(A) As a coloring agent, C.I. Pigment Blue 15 / C.I. Pigment Violet 23 = 90/10 (weight ratio) 15 parts by weight of the mixture, 5 parts by weight of Disperbyk-2001 as a dispersant (solid content), (B) acrylic acid / N-phenylmaleimide / styrene / phenylmethacryl as alkali-soluble resin 4 parts by weight of rate / 2-hydroxyethyl methacrylate / polymethylmethacrylate macromonomer copolymer (copolymerization weight ratio = 15/20/10/35/10/10, Mw = 23,000, Mn = 11,000), and a solvent 76 parts by weight of propylene glycol methyl ether acetate was treated with a bead mill to prepare a pigment dispersion (B1) (100 parts by weight in total).

Next, 100 parts by weight of the pigment dispersion (B1) and (B) methacrylic acid / N-phenylmaleimide / α-methylstyrene / benzyl methacrylate (copolymerization weight ratio = 20/25/25/30, Mw) as alkali-soluble resin. = 43,000, Mn = 21,000) 10 parts by weight, (C) 20 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer, (D) 2-methyl-1- [4- (methylthio) phenyl] as a photopolymerization initiator 5 parts by weight of -2-morpholinopropanone-1, and (E) 16 parts by weight of dipropylene glycol methylethyl acetate as a mixed solvent (about 4.9% by weight of the total mixed solvent), 104 parts by weight of propylene glycol methyl ether acetate (About 55.2% by weight of the total mixed solvent in combination with the amount in (B1)), 32 parts by weight of diethylene glycol methylethyl ether (about 9.8% by weight of the total mixed solvent) and 98 parts by weight of 3-methoxybutyl acetate (total mixed solvent Of about 30.1 wt%) was mixed to prepare a composition for forming a colored layer (B1-1).

It evaluated by the same procedure as Example 1 except having used the obtained composition for colored layer formation (B1-1). The evaluation results are shown in Table 3 below.

<Example 10>

27.75 parts of dipropylene glycol methyl ether acetate (about 8.5% by weight of the total mixed solvent) of (E) mixed solvent added to 100 parts by weight of the pigment dispersion (B1) in Example 9, propylene glycol methyl ether acetate 104 A composition for forming a colored layer in the same manner as in Example 9 except for changing to parts by weight (about 55.2% by weight of the total mixed solvent) and 118.25 parts by weight of ethyl 3-ethoxypropionate (about 36.3% by weight of the total mixed solvent). After manufacturing (B1-2), it evaluated by the same procedure as Example 1. The evaluation results are shown in Table 3.

<Example 11>

In Example 9, 27.75 parts by weight of dipropylene glycol methyl ether acetate (about 8.5% by weight of the total mixed solvent) of (E) mixed solvent added to 100 parts by weight of the pigment dispersion (B1), propylene glycol methyl ether acetate 56 Parts by weight (about 40.5% by weight of the total mixed solvent), 81 parts by weight of 3-methoxybutyl acetate (about 24.8% by weight of the total mixed solvent) and 85.25 parts by weight of cyclohexanone (about 26.2% by weight of the total mixed solvent) Except having changed, after producing the colored layer formation composition (B1-3) similarly to Example 9, it evaluated by the same procedure as Example 1. The evaluation results are shown in Table 3.

<Example 12>

In Example 9, 9.8 parts by weight of dipropylene glycol methyl ether acetate (about 3.0% by weight of the total mixed solvent) of (E) mixed solvent added to 100 parts by weight of the pigment dispersion (B1), propylene glycol methyl ether acetate 54.4 Parts by weight (about 40.0% by weight of the total mixed solvent), 163 parts by weight of diethylene glycol methylethyl ether (about 50.0% by weight of the total mixed solvent) and 22.8 parts by weight of 3-methoxybutyl acetate (about 7.0 weight of the total mixed solvent) Except having changed into%), it carried out similarly to Example 9, and manufactured the composition for colored layer formation (B1-4), and evaluated by the same procedure as Example 1. The evaluation results are shown in Table 3.

Comparative Example 7

In Example 9, 56 parts by weight of propylene glycol methyl ether acetate (40.5% by weight of the total mixed solvent) and 194 parts by weight of ethyl 3-ethoxypropionate (total amount) were added to 100 parts by weight of the pigment dispersion (B1). Except having changed into 59.5 weight% of mixed solvents, the coloring layer formation composition (B1-5) was produced like Example 9, and was evaluated in the same procedure as Example 1. The evaluation results are shown in Table 3.

<Comparative Example 8>

In Example 9, 88 parts by weight of propylene glycol methyl ether acetate (50.3% by weight of the total mixed solvent) and 97 parts by weight of 3-methoxybutyl acetate were added to the mixed solvent added with respect to 100 parts by weight of the pigment dispersion (B1). A colored layer-forming composition (B1-6) was prepared in the same manner as in Example 9 except that the solvent was changed to 29.8 wt% of the mixed solvent) and 65 parts by weight of cyclohexanone (19.9 wt% of the total mixed solvent). , The same procedure as in Example 1 was performed. The evaluation results are shown in Table 3.

Comparative Example 9

In Example 9, 49 parts by weight of dipropylene glycol methyl ether acetate (about 15.0% by weight of the total mixed solvent) was added to 100 parts by weight of the pigment dispersion (B1), and 55 parts by weight of propylene glycol methyl ether acetate ( About 40.2% by weight of the total mixed solvent), 81 parts by weight of 3-methoxybutyl acetate (about 24.8% by weight of the total mixed solvent) and 65 parts by weight of cyclohexanone (about 20.0% by weight of the total mixed solvent) Except having produced the colored layer formation composition (B1-7) similarly to Example 9, it evaluated in the same procedure as Example 1. The evaluation results are shown in Table 3.

According to the present invention, a mixed solvent containing (A) colorant, (B) alkali-soluble resin, (C) polyfunctional monomer, (D) photopolymerization initiator, and (E) dipropylene glycol methyl ether acetate 3 to 8.5 wt% It can contain and provide the radiation sensitive composition for colored layer formation.

Claims (7)

(A) a colorant, (B) (b1) a polymerizable unsaturated monomer having an acidic functional group, (b2) a macromonomer having a mono (meth) acryloyl group at the terminal of the polymer molecular chain, an N-position substituted maleimide, an aromatic vinyl compound, indene, 1 type selected from the group consisting of unsaturated carboxylic acid esters, unsaturated carboxylic acid aminoalkyl esters, unsaturated carboxylic acid glycidyl esters, carboxylic acid vinyl esters, unsaturated ethers, vinyl cyanide compounds, unsaturated amides and aliphatic conjugated dienes Alkali-soluble resin which is a copolymer with the above unsaturated monomer, (C) a monomer having two or more polymerizable unsaturated bonds in the molecule, (D) photoinitiator, and (E) (e1) dipropylene glycol methyl ether acetate selected from the group consisting of 3 to 8.5% by weight, (e2) a solvent having a boiling point of less than 150 ° C, a solvent having a boiling point of 150 ° C or more and less than 180 ° C, and a solvent having a boiling point of 180 ° C or more. Mixed solvent containing 91.5-97 weight% of 1 or more types of solvents other than said (e1) It is for forming a colored layer and solid content concentration except the (E) mixed solvent is 5 to 50 weight%, The radiation sensitive composition characterized by the above-mentioned. The radiation sensitive composition of Claim 1 in which the mixed solvent (E) contains 30 to 70 weight% of a solvent below boiling point 150 degreeC. The radiation sensitive composition of Claim 2 in which (E) mixed solvent contains 20 to 60 weight% of a boiling point of 150 degreeC or more and less than 180 degreeC. (1) Process of forming the coating film of the radiation sensitive composition of any one of Claims 1-3 on a board | substrate, (2) exposing to at least part of the coating film; (3) developing the coating film after exposure; (4) Process of heat-processing the coating film after image development A method of forming a color filter, comprising each step of. The formation method of the color filter of Claim 4 which performs coating film formation of a radiation sensitive composition using a slit nozzle in the process of (1). The color filter provided with the colored layer formed from the radiation sensitive composition of any one of Claims 1-3. The color liquid crystal display panel provided with the color filter of Claim 6.