JP4656036B2 - Radiation-sensitive composition for forming colored layer and color filter - Google Patents

Description

  The present invention relates to a radiation-sensitive composition for forming a colored layer, a method for forming a colored layer, a color filter, and a color liquid crystal display element, and more specifically, a transmissive or reflective color liquid crystal display device, a color image pickup tube element, and the like. A radiation-sensitive composition used for forming a colored layer useful for the production of a color filter used in the present invention, a method for forming a colored layer using the radiation-sensitive composition, and a colored layer formed from the radiation-sensitive composition The present invention relates to a color filter provided, and a color liquid crystal display element including the color filter.

  Conventionally, when producing a color filter using a radiation-sensitive composition for forming a colored layer, the radiation-sensitive composition for forming a colored layer is usually formed on a substrate or a substrate on which a light-shielding layer having a desired pattern has been previously formed. After forming a coating film and irradiating with radiation through a photomask having a desired pattern shape (hereinafter referred to as “exposure”), development is performed to dissolve and remove unexposed portions, and then a clean oven or hot plate is used. A method for obtaining pixels of each color by using and post-baking (see, for example, Patent Document 1 and Patent Document 2) is known. When manufacturing a color filter by such a method, the radiation-sensitive composition for forming a colored layer is generally applied onto a substrate by a spin method, but as the substrate becomes larger, the application method is slit and spin. The system and the spinless system are shifting.

JP-A-2-144502 JP-A-3-53201

  However, in the slit-and-spin method and the spinless method, since application is performed using a slit nozzle, there are problems in applicability and yield due to this. That is, since the stain of the slit nozzle due to the radiation-sensitive composition for forming the colored layer is unavoidable, a cleaning process for the slit nozzle is necessary. In this washing step, it is usual to wash the slit nozzle with the main solvent of the colored layer forming radiation-sensitive composition, but if the solubility in the main solvent is low, the radiation sensitivity for forming the colored layer remaining in the nozzle portion The composition remains as a projection, and when the radiation-sensitive composition for forming a colored layer is applied to the substrate, a problem such as generation of streaks in the traveling direction of the nozzle, or the radiation-sensitive composition for forming a colored layer The dry matter falls and adheres to the substrate, resulting in a defect that reduces the yield. Therefore, the re-solubility (solvent re-solubility) in the solvent of the dried product of the colored layer forming radiation-sensitive composition becomes important.

  On the other hand, by using a high-boiling solvent in combination with the radiation-sensitive composition for forming the colored layer, it is possible to suppress the generation of dry matter, but it becomes difficult to sufficiently evaporate, and the occurrence of sticking and vacuum baking This leads to a decrease in productivity due to an increase in length. In addition, depending on the selection and addition amount of the high-boiling solvent, in the vacuum baking process 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 may appear on the coating film surface. There is a problem that it appears and remains as a crater-like defect (hereinafter referred to as “bump hole”) after drying.

  The problem of the present invention is to solve the above-mentioned problems, and the solvent resolubility of the dried material of the radiation-sensitive composition for forming a colored layer generated in the slit nozzle portion is high, and the occurrence of bumps can be suppressed. The object is to provide a radiation-sensitive composition for forming a colored layer with high sensitivity.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have used a solvent having cyclohexyl acetate as an essential component as a solvent to be used for the radiation-sensitive composition for forming a colored layer. It is found that the solvent re-solubility of the dried product is remarkably improved and the formation of bumps can be remarkably suppressed, and by using a specific oxime type compound as a radiation-sensitive radical generator, the sensitivity is high, It has been found that even if the exposure amount is low, the pixel pattern is not chipped or undercut, and the present invention has been achieved.

The present invention, first,
A radiation-sensitive resin composition containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a radiation-sensitive radical generator, and (E) a solvent, (D) The radiation-sensitive radical generator contains a compound represented by the following formula (1) and / or a compound represented by the following formula (2) as an essential component, and (E) the solvent contains cyclohexyl acetate in an amount of 5 to 5. A radiation-sensitive composition for forming a colored layer, comprising 40% by weight.

[In Formula (1) and Formula (2), each R ¹ independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group, and each R ² and each R ³ are independently of each other a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an optionally substituted phenyl group, or a monovalent alicyclic group having 7 to 20 carbon atoms. Wherein R ⁴ is independently of each other a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms or a monovalent nitrogen-containing complex having 4 to 20 carbon atoms. A cyclic group or a monovalent sulfur-containing heterocyclic group having 4 to 20 carbon atoms, wherein each R ⁵ is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms. Group, a C1-C12 alkoxyl group or a C3-C8 cycloalkyloxy group, Each n is an integer of 1 to 5 independently of each other, each m is an integer of 0 to 5 independently of each other, (n + m) ≦ 5, and p is an integer of 0 to 6. ]
The “colored layer” in the present invention means a layer composed of pixels and / or a black matrix used for a color filter.

The present invention secondly,
A method for forming a colored layer, comprising at least the following steps (1) to (4):
(1) The process of forming the coating film of the said radiation sensitive composition for colored layer formation on a board | substrate.
(2) A step of exposing at least a part of the coating film.
(3) The process of developing the coating film after exposure.
(4) The process of heat-processing the coating film after image development.

Third, the present invention
A color filter provided with a colored layer formed using the radiation-sensitive composition for forming the colored layer.

The present invention fourthly,
A color liquid crystal display device comprising the color filter;

The present invention is described in detail below.
Radiation-sensitive composition for forming colored layer- (A) Colorant-
The colorant in the present invention is not particularly limited in color tone, and is appropriately selected according to the use of the obtained color filter, and may be any of a pigment, a dye, or a natural pigment.
Since the color filter is required to have high purity and highly transparent color development and heat resistance, the colorant in the present invention is preferably a colorant having high color developability and high heat decomposition resistance. Inorganic pigments, particularly preferably organic pigments and / or carbon black are used.
Examples of the organic pigment include a color index (CI; The Society of Dyers).
and Colorists (published by and Colorists)), specifically, compounds having a color index (CI) number as shown below.

CI Pigment Yellow 83, CI Pigment Yellow 128, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, CI Pigment Yellow 151, CI Pigment Yellow 152, CI Pigment Yellow 153, CI Pigment Yellow 154, CI Pigment Yellow 155, CI Pigment Yellow 156, CI Pigment Yellow 166, CI Pigment Yellow 168, CI Pigment Yellow 175, CI Pigment Yellow 185;
CI Pigment Violet 19, CI Pigment Violet 23, CI Pigment Violet 29, CI Pigment Violet 32, CI Pigment Violet 36, CI Pigment Violet 38;

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

CI Pigment Blue 15, CI Pigment Blue 15: 3, CI Pigment Blue 15: 4, CI Pigment Blue 15: 6, CI Pigment Blue 60;
CI Pigment Green 7, CI Pigment Green 36;
CI Pigment Black 1, CI Pigment Black 7.
The organic pigments can be used alone or in admixture of two or more.
The organic pigment can be used after being purified by, for example, a sulfuric acid recrystallization method, a solvent washing method, or a combination thereof.

Examples of the inorganic pigment include titanium oxide, barium sulfate, calcium carbonate, zinc white, lead sulfate, yellow lead, zinc yellow, red bean curd (red iron oxide (III)), cadmium red, ultramarine blue, bitumen, and chromium oxide. Examples include green, cobalt green, amber, titanium black, synthetic iron black, and carbon black.
These inorganic pigments can be used alone or in admixture of two or more.

  When the radiation-sensitive composition for forming a colored layer in the present invention is used to form a pixel, preferably, one or more organic pigments are used as a colorant, and are used to form a black matrix. If used, preferably two or more organic pigments and / or carbon black are used as colorants.

Examples of carbon black used for forming a black matrix include SAF, SAF-HS, ISAF, ISAF-LS, ISAF-HS, HAF, HAF-LS, HAF-HS, NAF, FEF, FEF-HS, and SRF. SRF-LM, SRF-LS, GPF, ECF, N-339, N-351 and other furnace blacks; FT, MT and other thermal blacks; acetylene black and the like.
These carbon blacks can be used alone or in admixture of two or more.

  In the present invention, each of the pigments can be used by modifying the particle surface with a polymer, if desired. Examples of the polymer that modifies the pigment particle surface include the polymers described in Patent Document 3 and the like, and various commercially available polymers or oligomers for dispersing pigments.

JP-A-8-259876

Further, the colorant in the present invention can be used together with a dispersant as desired.
Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants.
Specific examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n- Polyoxyethylene alkylphenyl ethers such as 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, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), F-top (manufactured by Tochem Products) Megafuck (Dainippon Ink Chemical Co., Ltd.), Florard (Sumitomo 3M Co., Ltd.), Asahi Guard, Surflon (manufactured by Asahi Glass Co., Ltd.), Disperbyk-101, 103, 107, 110 111, 115, 130, 160, 160, 161, 162, 163, 164, 165, 166, 170, 180, 182, 2000, 2001 (above, Big Chemie Manufactured by Japan Co., Ltd.), Solsperse S5000, S12000, S13240, S13940, S17000, S20000, S22000, S24000, S24000GR, S26000, S27000, S28000 (above, manufactured by Avicia Co., Ltd.) ), EFKA46, 47, 48, 745, 4540 4550, 6750, EFKA LP4008, 4009, 4010, 4015, 4050, 4055, 4560, 4800, EFKA Polymer400, 401, 402, 403, 450, 451, 453 (manufactured by Fuka Chemicals Co., Ltd.).
These surfactants can be used alone or in admixture of two or more.
The usage-amount of surfactant is 50 parts weight or less normally with respect to 100 weight part of coloring agents, Preferably it is 0-30 weight part.

  In the present invention, the radiation-sensitive resin composition can be prepared by an appropriate method. However, when a pigment is used as a colorant, the pigment is used in a solvent in the presence of a dispersant, as will be described later. B) Along with an alkali-soluble resin, for example, a bead mill, a roll mill or the like is mixed and dispersed while being pulverized to obtain a pigment dispersion, which is prepared by mixing with components (B) to (E) described later. It is preferable.

The amount of the dispersant used in preparing the pigment dispersion is usually 100 parts by weight or less, preferably 0.5 to 100 parts by weight, more preferably 1 to 70 parts by weight, particularly 100 parts by weight of pigment. Preferably it is 10-50 weight part. In this case, if the amount of the dispersant used exceeds 100 parts by weight, developability and the like may be impaired.
Moreover, as a solvent used when preparing a pigment dispersion liquid, the thing similar to the (E) solvent mentioned later can be mentioned, for example, The solvent used for preparation of a pigment dispersion liquid is the last coloring. The solvent may be the same as or different from the solvent added to the pigment dispersion in the step of preparing the radiation-sensitive composition for layer formation.
The amount of the solvent used in preparing the pigment dispersion is usually 500 to 1,000 parts by weight, preferably 700 to 900 parts by weight with respect to 100 parts by weight of the pigment.

When preparing a pigment dispersion using a bead mill, for example, glass beads or titania beads having a diameter of about 0.5 to 10 mm are used, and a pigment mixture composed of a pigment, a solvent and a dispersant is used. Preferably, it can be carried out by mixing and dispersing while cooling with cooling water or the like.
In this case, the filling rate of the beads is usually 50 to 80% of the mill capacity, and the injection amount of the pigment mixture is usually about 20 to 50% of the mill capacity. The treatment time is usually 2 to 50 hours, preferably 2 to 25 hours.
Moreover, when preparing using a roll mill, it can carry out by processing, for example, using a 3 roll mill, a 2 roll mill, etc., preferably cooling a pigment liquid mixture with cooling water etc.
In this case, the roll interval is preferably 10 μm or less, and the shearing force is usually about 10 8 dyn / sec. The treatment time is usually 2 to 50 hours, preferably 2 to 25 hours.

-(B) Alkali-soluble resin-
As the alkali-soluble resin in the present invention, (A) acts as a binder for the colorant, and when producing a color filter, it is preferably used for the developer used in the development processing step, particularly preferably for the alkali developer. Although it is not particularly limited as long as it has solubility, for example, a polymerizable unsaturated monomer having an acidic functional group such as a carboxyl group, a phenolic hydroxyl group, and a sulfonic acid and other copolymerizable monomers. Examples thereof include copolymers with saturated monomers (hereinafter referred to as “copolymerizable unsaturated monomers”).

Examples of the polymerizable unsaturated monomer having a carboxyl group (hereinafter referred to as “carboxyl group-containing unsaturated monomer”) include:
Unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid;
Unsaturated dicarboxylic acids such as maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconic acid, citraconic anhydride, mesaconic acid or the like;
A trivalent or higher unsaturated polycarboxylic acid or anhydride thereof;
Mono [(meth) acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids such as succinic acid mono [2- (meth) acryloyloxyethyl] and phthalic acid mono [2- (meth) acryloyloxyethyl];
Examples thereof include mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate.

Among these carboxyl group-containing unsaturated monomers, (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], ω-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.

Examples of the polymerizable unsaturated monomer having a phenolic hydroxyl group include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methyl. Examples thereof include styrene, p-hydroxy-α-methylstyrene, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide and the like.
These polymerizable unsaturated monomers having a phenolic hydroxyl group can be used alone or in admixture of two or more.
Examples of the polymerizable unsaturated monomer having a sulfonic acid group include isoprene sulfonic acid and p-styrene sulfonic acid.
These polymerizable unsaturated monomers having a sulfonic acid group can be used alone or in admixture of two or more.

Next, as the copolymerizable unsaturated monomer, for example,
A macromonomer having a mono (meth) acryloyl group at the end of a polymer molecular chain such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane or the like (hereinafter simply referred to as “macromonomer”). Class:
N-phenylmaleimide, N-o-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxy N- (substituted) arylmaleimide such as phenylmaleimide and N-substituted maleimides such as N-cyclohexylmaleimide;
Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl ether, m -Aromatic vinyl compounds such as vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, 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 Rate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl Unsaturated carboxylic esters such as (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate;

2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl acrylate, 3-aminopropyl (meth) acrylate, 3-dimethylaminopropyl ( Unsaturated carboxylic acid aminoalkyl esters such as (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, 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, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
Examples thereof include aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene.

Of these copolymerizable unsaturated monomers, macromonomers, N-substituted maleimides, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate and the like are preferable. Among the macromonomers, polystyrene macromonomers and polymethyl (meth) acrylate macromonomers are particularly preferable, and among the N-substituted maleimides, N-phenylmaleimide and N-cyclohexylmaleimide are particularly preferable.
The said copolymerizable unsaturated monomer can be used individually or in mixture of 2 or more types.

As a preferable alkali-soluble resin in the present invention, for example, a copolymer of a carboxyl group-containing unsaturated monomer and a copolymerizable unsaturated monomer (hereinafter simply referred to as “carboxyl group-containing copolymer”). Can be mentioned.
As the carboxyl group-containing copolymer, (a) a carboxyl group-containing unsaturated monomer, (b) a polystyrene macromonomer, a polymethyl (meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxy And at least one selected from the group consisting of ethyl (meth) acrylate, benzyl (meth) acrylate, and glycerol (meth) acrylate, and (c) optionally styrene, α-methylstyrene, methyl (meth) acrylate, allyl ( A copolymer of a monomer mixture further containing at least one selected from the group of (meth) acrylate and phenyl (meth) acrylate (hereinafter referred to as “carboxyl group-containing copolymer (I)”) is particularly preferable. , (A) (meth) acrylic acid is an essential component Optionally, a carboxyl group-containing unsaturated monomer further containing succinic acid mono [2- (meth) acryloyloxyethyl] and / or ω-carboxypolycaprolactone mono (meth) acrylate, and (b) polystyrene macro Monomer, polymethyl (meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol (meth) acrylate And (c) a monomer mixture further containing at least one selected from the group of styrene, α-methylstyrene, methyl (meth) acrylate, allyl (meth) acrylate and phenyl (meth) acrylate. Copolymer (hereinafter, referred to as "carboxyl group-containing copolymer (II)".) Are preferred.

As specific examples of the carboxyl group-containing copolymer (II),
(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 / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(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 / 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 / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polymethylmethacrylate macromonomer copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / benzyl (meth) acrylate / glycerol mono (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 / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer and the like.

  The copolymerization ratio of the carboxyl group-containing unsaturated monomer in the carboxyl group-containing copolymer is usually 5 to 50% by weight, preferably 10 to 40% by weight. In this case, if the copolymerization ratio of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility of the resulting radiation-sensitive composition in an alkaline developer tends to decrease, whereas if it exceeds 50% by weight. In addition, the solubility in an alkali developer becomes excessive, and when developing with an alkali developer, the colored layer tends to drop off from the substrate and the surface of the colored layer tends to be rough.

The polystyrene-converted 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, and more preferably Preferably it is 3,000-100,000.
The polystyrene-equivalent 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. More preferably, it is 3,000 to 25,000.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the alkali-soluble resin in the present invention is usually 1 to 5, preferably 1 to 4.
By using such an alkali-soluble resin having a specific Mw or Mn, a radiation-sensitive composition for forming a colored layer having excellent developability can be obtained, thereby forming a colored layer having sharp pattern edges. In addition, residues, background stains, film residues, and the like are less likely to occur on the unexposed substrate and the light shielding layer during development.
In this invention, alkali-soluble resin can be used individually or in mixture of 2 or more types.

  The usage-amount of the alkali-soluble resin in this invention is 10-1,000 weight part normally with respect to 100 weight part of (A) coloring agents, Preferably it is 20-500 weight part. In this case, when the amount of the alkali-soluble resin used is less than 10 parts by weight, for example, the alkali developability of the resulting radiation-sensitive composition is reduced, or background stains or film residues are left on the unexposed substrate or the light shielding layer. On the other hand, when the amount exceeds 1,000 parts by weight, the colorant concentration is relatively lowered, and 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.
As the multifunctional 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, etc. and their dicarboxylic acid-modified products;
Oligo (meth) acrylates such as polyester, epoxy resin, urethane resin, alkyd resin, silicone resin, spirane resin;
Di (meth) acrylates of hydroxylated polymers at both ends such as both ends hydroxypoly-1,3-butadiene, both ends hydroxypolyisoprene, both ends hydroxypolycaprolactone,
And tris [2- (meth) acryloyloxyethyl] phosphate.

Among these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid modified products, specifically, trimethylolpropane tri (meth) acrylate, pentaerythritol tris. (Meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like are preferable, and trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol are particularly preferable. Hexaacrylate is preferred because it has high strength of the colored layer, excellent smoothness of the surface of the colored layer, and hardly causes scumming or film residue on the unexposed substrate and the light shielding layer.
In this invention, a polyfunctional monomer can be used individually or in mixture of 2 or more types.

  The usage-amount of the polyfunctional monomer in this invention is 5-500 weight part normally with respect to 100 weight part of (B) alkali-soluble resin, Preferably it is 20-300 weight part. In this case, if the amount of the polyfunctional monomer used is less than 5 parts by weight, the strength and surface smoothness of the colored layer tend to be reduced. On the other hand, if it exceeds 500 parts by weight, for example, the resulting radiation-sensitive composition There is a tendency that the alkali developability of the product is lowered, and background stains, film residue, etc. are likely to occur on the substrate in the unexposed area or on the light shielding layer.

In the present invention, a part of the polyfunctional monomer can be replaced with a monofunctional monomer having one polymerizable unsaturated bond.
Examples of the monofunctional monomer include the carboxyl group-containing unsaturated monomer, copolymerizable unsaturated monomer, N-vinyl succinimide, and N-vinyl exemplified for the (B) alkali-soluble resin. Pyrrolidone, N-vinylphthalimide, N-vinyl-2-piperidone, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrolidine, N-vinylimidazole, N-vinylimidazolidine, N-vinylindole, N N-vinyl derivatives such as vinylindoline, N-vinylbenzimidazole, N-vinylcarbazole, N-vinylpiperidine, N-vinylpiperazine, N-vinylmorpholine, N-vinylphenoxazine; N- (meth) In addition to acryloylmorpholine, as commercial products, the trade names are M-5300 and M-5400. M-5600 (manufactured by Toagosei Co., Ltd.), and the like can be given.
These monofunctional monomers can be used alone or in admixture of two or more. The proportion of the monofunctional monomer used is usually 90% by weight or less, preferably 50% by weight or less, based on the total of the polyfunctional monomer and the monofunctional monomer. In this case, if the use ratio of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the colored layer tend to be lowered.

-(D) Radiation sensitive radical generator-
The radiation-sensitive radical generator (hereinafter referred to as “(D) radical generator”) in the present invention is referred to as a compound represented by the above formula (1) (hereinafter referred to as “oxime type radical generator (1)”). ) And / or a compound represented by the above formula (2) (hereinafter referred to as “oxime type radical generator (2)”) as an essential component, such as visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc. It is a component that generates radicals capable of initiating polymerization of the (C) polyfunctional monomer and optionally used monofunctional monomer by exposure to radiation.

In Formula (1) and Formula (2), examples of the alkyl group having 1 to 20 carbon atoms of R ¹ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, sec- Examples include butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. be able to.
Further, the cycloalkyl group having a carbon number of R ¹ 3 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group.

In Formula (1) and Formula (2), R ¹ is preferably, for example, a methyl group, an ethyl group, or the like.

In formula (1) and formula (2), examples of the alkyl group having 1 to 20 carbon atoms of R ² and R ³ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, and an n-butyl group. , Sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group Etc.
Further, the cycloalkyl group having 3 to 8 carbon atoms R ² and R ^3, examples thereof include a cyclopentyl group, a cyclohexyl group.

Examples of the substituent for the phenyl group of R ² and R ³ include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, sec-butyl group, t-butyl group, and n-pentyl. Group, an alkyl group having 1 to 6 carbon atoms such as n-hexyl group; a cycloalkyl group having 3 to 6 carbon atoms such as cyclopentyl group and cyclohexyl group: methoxy group, ethoxy group, n-propoxy group, i-propoxy group, an alkoxyl group having 1 to 6 carbon atoms such as an n-butoxy group and a t-butoxy group; a cycloalkyloxy group having 3 to 6 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group: a phenyl group; a fluorine atom, a chlorine atom, etc. A halogen atom etc. can be mentioned.

Examples of the monovalent alicyclic group having 7 to 20 carbon atoms of R ² and R ³ (excluding the cycloalkyl group) include, for example, a group having a 1-alkylcycloalkane skeleton and a bicycloalkane skeleton. A group having a tricycloalkane skeleton, a group having a spiroalkane skeleton, a group having a terpene skeleton, a group having an adamantane skeleton, and the like.

In Formula (1) and Formula (2), R ² and R ³ are preferably a hydrogen atom, a methyl group, an ethyl group, or the like.

In formula (1) and formula (2), R ^{4 is} a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms and a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms. Examples of the group or monovalent sulfur-containing heterocyclic group having 4 to 20 carbon atoms include thiolanyl group, azepinyl group, dihydroazepinyl group, dioxolanyl group, triazinyl group, oxathianyl group, thiazolyl group, oxadiazinyl group, Xidodanyl group, dihyanaphthalenyl group, furanyl group, thiophenyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, pyrazolyl group, furazanyl group, pyranyl group, pyridinyl group, pyridazinyl group, pyrimidyl group, Pyrazinyl group, pyrrolinyl group, morpholinyl group, piperazinyl group, quinuclidinyl group, indolyl group, iso Ndryl, benzofuranyl, benzothiophenyl, indolizinyl, chromenyl, quinolinyl, isoquinolinyl, purinyl, quinazolinyl, cinnolinyl, phthalazinyl, pteridinyl, carbazolyl, acridinyl, phenanthridinyl, Examples thereof include a thioxanthenyl group, a phenazinyl group, a phenothiazinyl group, a phenoxathinyl group, a phenoxazinyl group, a thianthenyl group, a tetrahydrofuranyl group, and a tetrahydropyranyl group.

In Formula (1) and Formula (2), R ⁴ is preferably a tetrahydrofuranyl group, a tetrahydropyranyl group, or the like.

In Formula (1) and Formula (2), examples of the alkyl group having 1 to 12 carbon atoms of R ⁵ include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, sec- Examples include butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, etc. be able to.
Further, the cycloalkyl group having a carbon number of R ⁵ 3 to 8, and examples thereof include a cyclopentyl group, a cyclohexyl group.

As the alkoxyl group having 1 to 12 carbon atoms of R ^5, for example, a methoxy group, an ethoxy group, n- propoxy group, i- propoxy, n- butoxy, t-butoxy group, n- pentyloxy group, Examples include n-hexyloxy group, n-heptyloxy group, n-octyloxy group, n-nonyloxy group, n-decyloxy group, n-undecyloxy group, n-dodecyloxy group and the like.
Moreover, as a C3-C8 cycloalkyloxy group of R < ⁵ >, a cyclopentyloxy group, a cyclohexyloxy group, etc. can be mentioned, for example.

In Formula (1) and Formula (2), R ⁵ is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a methoxy group, an ethoxy group, or the like.

  In the formulas (1) and (2), n is preferably 1, m is preferably 0, 1 or 2, particularly preferably 1, and p is preferably 0, 1 or 2, particularly 1. Is preferred.

As a specific example of the oxime type radical generator (1),
Ethanone-1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),

Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),

Ethanone-1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),

Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylbenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime), ethanone-1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) benzoyl ] -9. H. -Carbazol-3-yl] -1- (O-acetyloxime)
Etc.
These oxime type radical generators (1) can be used alone or in admixture of two or more.

Moreover, as a specific example of the oxime type radical generator (2),
Ethanone-1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),

Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone 1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),

Ethanone-1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-2-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-2-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-2-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-3-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-3-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-3-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),

Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranyloxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),
Ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-benzoylacetyloxime),
Ethanone-1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl] -1- (O-acetyloxime)
Etc.
These oxime type radical generators (2) can be used alone or in admixture of two or more.

  The radical generator (D) in the present invention preferably contains at least the oxime radical generator (2), and in particular, ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxy). Benzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), and ethanone-1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl] -9. H. Those containing at least one selected from the group of -carbazol-3-yl] -1- (O-acetyloxime) are preferred.

In the present invention, as the radical generator (D), other radical generators can be used in combination with the oxime radical generator (1) and the oxime radical generator (2).
Examples of the other radical generator include an oxime radical generator (1) and an oxime radical generator other than the oxime radical generator (2) (hereinafter referred to as “other oxime radical generator”). be able to.
Specific examples of the other oxime type radical generator include 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione-1- [4- (Phenylthio) phenyl] -2- (O-benzoyloxime), 1,2-butanedione-1- [4- (phenylthio) phenyl] -2- (O-acetyloxime), 1,2-octadion-1- [ 4- (methylthio) phenyl] -2- (O-benzoyloxime), 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O- (4-methylbenzoyloxime)) and the like be able to.
Of these, 1,2-octadion-1- [4- (phenylthio) phenyl] -2- (O-benzoyloxime) is particularly preferable.

  As other radical generators other than the oxime type radical generator, for example, at least one main skeleton represented by the following formula (3-1), formula (3-2) or formula (3-3) is used. Examples thereof include biimidazole compounds, benzoin compounds, acetophenone compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds, phosphine compounds, and triazine compounds.

  Examples of the biimidazole compound include 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 2,2′-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 and the like can be mentioned.

-Hydrogen donor-
Moreover, in this invention, when using a biimidazole type compound together as (D) radical generator, using in combination with the hydrogen donor mentioned below is preferable at the point which can improve a sensitivity further.
The “hydrogen donor” as used herein means a compound that can donate a hydrogen atom to a radical generated from a biimidazole compound by exposure.
As such a hydrogen donor, a mercaptan compound defined below, an amine compound defined below, and the like are preferable.
The mercaptan-based compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having one or more, preferably 1 to 3, more preferably 1 to 2, mercapto groups directly bonded to the mother nucleus (hereinafter referred to as “mercaptan”). It is referred to as “system hydrogen donor”).
The amine compound is a compound having a benzene ring or a heterocyclic ring as a mother nucleus and having 1 or more, preferably 1 to 3, more preferably 1 to 2 amino groups directly bonded to the mother nucleus (hereinafter referred to as “the amine compound”). "Amine-based hydrogen donor").
These hydrogen donors can also have a mercapto group and an amino group at the same time.

Hereinafter, the hydrogen donor will be described more specifically.
The mercaptan-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When two or more of these rings are present, It may or may not be formed.
In addition, when the mercaptan hydrogen donor has two or more mercapto groups, at least one of the remaining mercapto groups is substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. Furthermore, as long as at least one free mercapto group remains, a structural unit in which two sulfur atoms are bonded via a divalent organic group such as an alkylene group, or two sulfur atoms are It can have structural units linked in the form of disulfides.
Furthermore, the mercaptan-based hydrogen donor may be substituted with a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted or unsubstituted phenoxycarbonyl group, a nitrile group, or the like at a place other than the mercapto group.

Specific examples of such mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole, 2-mercapto- 2,5-dimethylaminopyridine and the like can be mentioned.
Of these mercaptan-based hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzoxazole are preferable, and 2-mercaptobenzothiazole is particularly preferable.

Next, the amine-based hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. When these two or more rings are present, A condensed ring may or may not be formed.
In the amine-based hydrogen donor, at least one of the amino groups may be substituted with an alkyl group or a substituted alkyl group, and a carboxyl group, a substituted or unsubstituted alkoxycarbonyl group, a substituted group may be substituted at a position other than the amino group. Alternatively, it may be substituted with an unsubstituted phenoxycarbonyl group, nitrile group or the like.

Specific examples of such amine-based hydrogen donors include 4,4′-bis (dimethylamino) benzophenone, 4,4′-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, Examples include ethyl 4-dimethylaminobenzoate, i-amyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Among these amine-based hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable. In addition, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone can act as a photoradical initiator alone even in the absence of a biimidazole compound. .

In the present invention, the hydrogen donor can be used alone or in admixture of two or more. However, one or more mercaptan hydrogen donors and one or more amine hydrogen donors are used in combination. It is preferable that the formed colored layer does not easily fall off the substrate during development, and the strength and sensitivity of the colored layer are high.
Specific examples of a preferred combination of a mercaptan hydrogen donor and an amine hydrogen donor include 2-mercaptobenzothiazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4′-. Bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (dimethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and the like are further preferable combinations. Are 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone and 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzothia A Lumpur / 4,4'-bis (diethylamino) benzophenone.
The weight ratio of mercaptan hydrogen donor to amine hydrogen donor in the combination of mercaptan hydrogen donor and amine hydrogen donor is usually 1: 1 to 1: 4, preferably 1: 1 to 1: 3.

Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and methyl 2-benzoylbenzoate.
Examples of the acetophenone compound include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl Examples include phenyl ketone and 2,2-dimethoxy-1,2-diphenylethane-1-one. Kill.

Examples of the benzophenone compound include 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone.
Examples of the α-diketone compound include diacetyl, dibenzoyl, methylbenzoylformate, and the like.
Examples of the polynuclear quinone compound include anthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, 1,4-naphthoquinone, and the like.
Examples of the xanthone compound include xanthone, thioxanthone, and 2-chlorothioxanthone.
Examples of the phosphine compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide and 2,4,6-trimethylbenzoyldiphenylphosphine oxide.

  Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- (Furan-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (5-methylfuran-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- Kishisuchiriru) -4,6-bis (trichloromethyl) -s-triazine, 2-(4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine,

Compound represented by the following formula (4)

等のハロメチル基を有する化合物等を挙げることができる。
前記他のラジカル発生剤は、単独でまたは２種以上を混合して使用することができる。 And a compound represented by the following formula (5):

Examples thereof include compounds having a halomethyl group.
The other radical generators can be used alone or in admixture of two or more.

  In the present invention, the use ratio of the other radical generator is preferably 50% by weight or less, more preferably 1 to 30% by weight, based on the total amount of the (D) radical generator. In this case, if the use ratio of the other radical generator exceeds 50% by weight, the intended effect of the present invention may be impaired.

In the present invention, the amount of the (D) radical generator used is usually 0.1% relative to a total of 100 parts by weight of the (C) polyfunctional monomer and the monofunctional monomer optionally used. The amount is from 01 to 200 parts by weight, preferably from 1 to 120 parts by weight, particularly preferably from 1 to 100 parts by weight. In this case, if the amount of the radical generator (D) used is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it is difficult to obtain a pattern array in which pixel patterns or black matrix patterns are arranged according to a predetermined arrangement. On the other hand, if the amount exceeds 200 parts by weight, the formed colored layer tends to fall off from the substrate during development, and background stains, film residue, etc. are likely to occur on the unexposed portion of the substrate or on the light shielding layer. Become.
Furthermore, in the present invention, one or more of a sensitizer, a curing accelerator or a polymer photocrosslinking / sensitizer can be used in combination with the radical generator (D) as necessary.

-(E) Solvent-
The solvent in the present invention contains cyclohexyl acetate as an essential component.
The content ratio of cyclohexyl acetate in the solvent is 5 to 40% by weight, preferably 15 to 35% by weight, and particularly preferably 20 to 30% by weight. In this case, if the content of cyclohexyl acetate is too small, the effect of suppressing the generation of dry matter and bumps in the radiation-sensitive composition may be reduced. On the other hand, if the content is too large, the dissolving power as a solvent is reduced. There is a risk that insoluble matter is likely to precipitate.

The solvent in the present invention contains a solvent other than cyclohexyl acetate (hereinafter referred to as “other solvent”) in an amount of 60 to 95% by weight, preferably 65 to 85% by weight, particularly preferably 70 to 80% by weight. .
As other solvents, the components (A) to (D) and additive components constituting the radiation-sensitive composition for forming the colored layer are dispersed or dissolved, and do not react with these components and have appropriate volatility. As long as it has, it can be appropriately selected and used, but it preferably contains a solvent having a boiling point of less than 150 ° C., preferably 130 ° C. or more and less than 150 ° C. (hereinafter referred to as “low boiling solvent”). The “boiling point” 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-peptanone, n-butyl acetate, i-butyl acetate, i-pentyl acetate, ethyl butyrate, n-butyrate -Propyl, i-propyl butyrate, ethyl pyruvate and the like.

Of these low-boiling solvents, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether acetate, 2-peptanone, i-pentyl acetate, ethyl pyruvate, and the like are preferable. Particularly, propylene glycol monomethyl ether, propylene glycol Monoethyl ether and propylene glycol monomethyl ether acetate are preferred.
The low boiling point solvents can be used alone or in admixture of two or more.

  The content of the low boiling point solvent in the solvent is preferably 10 to 60% by weight, more preferably 20 to 50% by weight, and particularly preferably 20 to 45% by weight. In this case, if the content of the low-boiling solvent is too small, there is a risk of causing a reduction in productivity due to the occurrence of sticking or a long vacuum baking time, while if too high, the content of the dried radiation-sensitive composition is reduced. There is a possibility that the effect of suppressing the occurrence is insufficient.

In the present invention, the other solvent is a solvent having a boiling point of 150 ° C. or higher and lower than 180 ° C., preferably 155 ° C. or higher and lower than 180 ° C. (excluding cyclohexyl acetate) (hereinafter referred to as “medium boiling solvent”). It is desirable to include.
Specific examples of the medium boiling point solvent include ethylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, and 3-ethoxy. Examples include ethyl propionate, n-butyl butyrate, and methyl acetoacetate.

Among these medium boiling solvents, ethylene glycol mono-n-butyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3-ethoxypropion Ethyl acid is preferred, and propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, and ethyl 3-ethoxypropionate are particularly preferred.
The medium boiling solvents can be used alone or in admixture of two or more.

  The content of the medium boiling point solvent in the solvent is preferably 30 to 70% by weight, more preferably 30 to 60% by weight, and particularly preferably 30 to 50% by weight. In this case, if the content of the medium-boiling solvent is too small, the effect of suppressing the generation of the dried product of the radiation-sensitive composition may be insufficient. On the other hand, if it is too large, the occurrence of sticking and the vacuum baking time will be long. This may lead to a decrease in productivity.

Furthermore, in the present invention, a solvent having a boiling point exceeding 180 ° C. (hereinafter referred to as “high boiling point solvent”) can be used in combination with each of the solvents.
Specific examples of the high boiling point solvent include benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, Mention may be made of diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate and the like.
The high boiling point solvents can be used alone or in admixture of two or more.

  More specifically, the content ratio of each solvent in the solvent in the present invention is preferably 5 to 40% by weight of cyclohexyl acetate, 10 to 60% by weight of low boiling point solvent, and 30 to 70% by weight of medium boiling point solvent. The high-boiling solvent is 20% by weight or less, more preferably 15 to 35% by weight of cyclohexyl acetate, 20 to 50% by weight of low-boiling solvent, 30 to 60% by weight of medium-boiling solvent, and 20 to 20% of high-boiling solvent. The cyclohexyl acetate is 20 to 30% by weight, the low boiling point solvent is 20 to 45% by weight, the medium boiling point solvent is 30 to 50% by weight, and the high boiling point solvent is 20% by weight or less. By using such a mixed solvent, the generation of dry matter and bumps in the radiation-sensitive composition is remarkably suppressed, and there is no decrease in productivity due to the occurrence of sticking or a long vacuum baking time. In addition, a good radiation-sensitive composition for forming a colored layer can be obtained in which the dried product of the radiation-sensitive composition is excellent in solvent re-solubility and insoluble matter does not precipitate.

  The total amount of the solvent used in the radiation-sensitive composition for forming a colored layer of the present invention is not particularly limited, but from the viewpoints of applicability and stability of the resulting composition, the solvent of the composition is used. The total concentration of the removed components is preferably 5 to 50% by weight, particularly preferably 10 to 40% by weight.

-Other additives-
Although the radiation sensitive composition for colored layer formation of this invention contains the said (A)-(E) component, it can also contain another additive as needed.
Examples of the other additives include fillers such as glass and alumina; polymer compounds such as polyvinyl alcohol and poly (fluoroalkyl acrylate); nonionic surfactants, cationic surfactants, anionic surfactants Surfactant such as an agent; vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) ) -3-Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Methoxysilane, 3-chloropropylmethyldimeth Adhesion promoters such as silane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane; 2,2-thiobis (4-methyl-6-tert-butylphenol), 2 Antioxidants such as 1,6-di-t-butylphenol; UV absorbers such as 2- (3-tert-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenones; polyacryl An aggregation inhibitor such as sodium acid can be used.

Method for Forming Colored Layer Next, a method for forming a colored layer using the radiation-sensitive composition for forming a colored layer of the present invention (hereinafter also simply referred to as “colored layer forming composition”) will be described.
The colored layer forming method of the present invention includes at least the following steps (1) to (4).
(1) The process of forming the coating film of the composition for colored layer formation on a board | substrate.
(2) A step of exposing at least a part of the coating film.
(3) The process of developing the coating film after exposure.
(4) The process of heat-processing the coating film after image development.

Hereinafter, these steps will be sequentially described.
-Step (1)-
First, on the surface of the substrate, if necessary, a light-shielding layer is formed so as to partition a pixel forming portion, and after applying a colored layer forming composition on the substrate, vacuum baking is performed under reduced pressure. To remove the solvent by evaporation to form a coating film.
Examples of the substrate used in this step include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, polyethersulfone, cyclic olefin ring-opening polymer, and hydrogenated products thereof. be able to.
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, gas phase reaction method, vacuum deposition, etc., if desired.

A method for applying the colored layer forming composition to the substrate is not particularly limited, but a method using a slit nozzle such as a slit-and-spin coating method or a spinless coating method (hereinafter referred to as “slit nozzle coating method”). ") Is preferred.
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 coated substrate, etc., but for example, the coating is applied to the fifth generation glass substrate (1100 mm × 1250 mm) by the spinless coating method. In this case, the discharge amount of the colored layer forming composition from the slit nozzle is usually 500 to 2,000 microliters / second, preferably 800 to 1,500 microliters / second, and the coating speed is Usually, it is 500 to 1,500 mm / second, preferably 700 to 1,200 mm / second.
The solid content concentration of the colored layer forming composition used for the slit nozzle coating method is usually 10 to 20% by weight, preferably 13 to 18% by weight.
The vacuum baking conditions are such that the degree of vacuum is usually about 0.1 to 1.0 torr, preferably about 0.2 to 0.5 torr, and the temperature is usually about 60 to 120 ° C., preferably about 70 to 110 ° C. The baking time is usually about 1 to 5 minutes, preferably about 2 to 4 minutes.
The thickness of the coating film to be formed is usually 0.1 to 10 μm, preferably 0.2 to 8.0 μm, particularly preferably 0.2 to 6.0 μm as the film thickness after removal of the solvent.

-Step (2)-
Thereafter, at least a part of the formed coating film is exposed. When exposing a part of the coating film, it is usually exposed through a photomask having an appropriate pattern.
As the radiation used for the exposure, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, and radiation having a wavelength in the range of 190 to 450 nm is preferable.
Exposure of radiation is usually, 10~10,000J / m ² approximately.

-Step (3)-
Then, it develops using a developing solution and melt | dissolves and removes the unexposed part of a coating film.
Examples of the developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo. -An alkaline developer composed of an aqueous solution such as [4.3.0] -5-nonene is preferable.
For example, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant or the like can be added to the alkaline developer. In addition, it is usually washed with water after alkali development.
As a development processing method, a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be employed.
The development conditions are preferably about 5 to 300 seconds at room temperature.

-Step (4)-
Then, a colored layer can be formed on the substrate by heat treatment (hereinafter referred to as “post-bake”).
The post-baking conditions are preferably 180 to 230 ° C. and about 20 to 40 minutes.

In the method for forming a colored layer of the present invention, the steps (1) to (4) are repeated using each colored layer forming composition in which a red, green or blue pigment is dispersed. By forming the green pixel pattern and the blue pixel pattern on the same substrate, it is possible to obtain a substrate on which the three primary color pixel patterns of red, green, and blue are arranged in a predetermined arrangement. However, in the present invention, the order of forming the pixel patterns of the respective colors is not particularly limited.
Further, by sequentially performing the steps (1) to (4) using a colored layer forming composition in which a black pigment is dispersed, a substrate on which a black matrix pattern is arranged in a predetermined arrangement can be obtained. .
The thickness of the colored layer thus formed is usually 0.5 to 5.0 μm, preferably 1.5 to 3.0 μm.

Color filter The color filter of the present invention comprises a colored layer formed as described above. Color liquid crystal display element The color liquid crystal display element of the present invention comprises the color filter of the present invention.
Further, as one form of the color liquid crystal display element of the present invention, a pixel and / or a black matrix is formed as described above on the thin film transistor substrate array using the radiation-sensitive composition for forming a colored layer of the present invention. By doing so, a color liquid crystal display element having particularly excellent characteristics can be produced.

Preferred Embodiments of the Invention The radiation-sensitive composition for forming a colored layer of the present invention comprises (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a radical generator, and (E) a solvent is contained as an essential component, (D) the radical generator is an oxime radical generator (1) and / or an oxime radical generator (2) as an essential component, and (E) the solvent is cyclohexyl acetate. Although it contains 5 to 40 weight%, when a particularly preferable composition is illustrated concretely, it is as follows (a)-(ke).

(A) A radiation-sensitive composition for forming a colored layer, wherein the component (B) contains a carboxyl group-containing copolymer (II), and the component (D) contains at least an oxime type radical generator (2).
(A) The component (B) contains the carboxyl group-containing copolymer (II), and the component (D) is ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9. . H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), and ethanone-1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxy Benzoyl] -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) The radiation sensitive composition for colored layer formation of said (a) containing at least 1 sort (s) chosen from the group.

(C) The carboxyl group-containing copolymer (II) in the component (B) is a (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 (meta ) Acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) Acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate Tomacromonomer 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, (meta ) 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 / N-phenylmaleimide / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer, (meth) acrylic acid / N-phenylmaleimide / styrene / 2- Hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / N-phenylmaleimide / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polymethyl Methacrylate macromonomer copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / benzyl (meth) acrylate / glycerol mono (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 and (meth) acrylic acid / ω-carboxypolycaprolactone mono (meta ) Acrylate / N-phenylmaleimi The radiation-sensitive composition for forming a colored layer according to (a) or (b), comprising at least one selected from the group consisting of copolymer / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer.

(D) The colored layer of (A), (I) or (U), wherein the component (C) contains at least one selected from the group of trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. Radiation sensitive composition for forming.
(E) The radiation-sensitive composition for forming a colored layer according to (a), (b), (c) or (d), wherein the component (A) contains an organic pigment and / or carbon black.

(F) The radiation-sensitive composition for forming a colored layer according to (a), (b), (c), (e) or (e), wherein the component (E) contains 10 to 60% by weight of a low-boiling solvent. .
(G) The radiation sensitive composition for forming a colored layer according to (f), wherein the low boiling point solvent contains 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 (f) or (g), wherein the component (E) further contains 30 to 70% by weight of a medium-boiling solvent.
(G) The medium (boiling point) containing at least one selected from the group consisting of propylene glycol monoethyl ether acetate, 3-methoxybutyl acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone and ethyl 3-ethoxypropionate. ) For forming a colored layer.

Further, the preferred color filter of the present invention is
(K) The radiation-sensitive composition for forming a colored layer according to (a), (b), (c), (d), (e), (f), (g), (g) or (g). A pixel and / or a black matrix formed using the same.

The preferred color liquid crystal display element of the present invention is
(Sa) The color filter of (co) is provided,
Further preferred color liquid crystal display elements of the present invention are:
(F) The color filter of (v) is provided on the thin film transistor substrate array.

  The radiation-sensitive composition for forming a colored layer of the present invention has a high solvent re-dissolvability in the dried product of the radiation-sensitive composition for forming a colored layer generated in the slit nozzle portion, and significantly suppresses the occurrence of bump holes. In particular, it can be applied to the formation of a colored layer using a slit nozzle coating method because it has high sensitivity and does not cause chipping or undercutting in the pixel pattern even at low exposure. it can.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
Example 1
(A) CI Pigment Red 254 / CI Pigment Red 177 = 80/20 (weight ratio) mixture 15 parts by weight as a colorant, Disperbyk-2001 4 parts by weight (in terms of solid content) as a dispersant, (B) Alkali-soluble resin Methacrylic acid / N-phenylmaleimide / styrene / benzyl methacrylate copolymer (copolymerization weight ratio = 20/30/20/30, Mw = 9,500, Mn = 5,000) 6 parts by weight, (E) solvent As a result, 75 parts by weight of propylene glycol monomethyl ether acetate was treated with a bead mill to prepare a pigment dispersion (R1).

  Next, 100 parts by weight of pigment dispersion (R1), (B) methacrylic acid / succinic acid mono (2-methacryloyloxyethyl) / N-phenylmaleimide / styrene / benzyl methacrylate copolymer (copolymerization weight ratio) as alkali-soluble resin = 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) radical Ethanone-1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) 1 part by weight, (E) 25 parts by weight (10% by weight) of cyclohexyl acetate as solvent, 25 parts by weight (40% by weight) of propylene glycol monomethyl ether acetate, A colored layer forming composition (R1-1) was prepared by mixing 75 parts by weight (30% by weight) of 3-methoxybutyl acetate and 50 parts by weight (20% by weight) of cyclohexanone. However, the content ratio (% by weight) of each solvent is a value including the solvent in the pigment dispersion (the same applies hereinafter).

The obtained colored layer forming composition (R1-1) was evaluated according to the following procedure. The evaluation results are shown in Table 1.
Evaluation of solvent re-solubility of dried product Glass coated with a dry coating film after coating the colored layer forming composition (R1-1) on a glass substrate and air-drying at 23 ° C. and 50% humidity for 30 minutes. The substrate was immersed in propylene glycol monomethyl ether acetate for 10 minutes. At this time, it evaluated in the following three steps by the redissolved state of the dry coating film.
○: All the dried coating film dissolves during immersion.
Δ: A part of the dried coating film remains after immersion for 10 minutes.
X: The dried coating film hardly or not dissolves after immersion for 10 minutes.

After applying a colored layer forming composition (R1-1) to a soda glass substrate (300 mm × 400 mm) on which a SiO ₂ film for preventing sodium ions from eluting is formed on the evaluation surface of the bump hole using a spin coater Then, vacuum baking was performed until the degree of vacuum reached 0.3 torr to form a coating film having a thickness of 2.5 μm.
Then, the obtained board | substrate was observed with the optical microscope, the number of bump holes which generate | occur | produce in the 5 mm x 400 mm square prescribed area | region of a coating film was counted, and the following three steps evaluated.
○: bump holes less than 500,
Δ: 500 or more bump holes and less than 1,000 holes,
X: 1,000 or more bump holes.

Evaluation of sensitivity The liquid composition (R1-1) was applied to a soda glass substrate on which a SiO ₂ film for preventing elution of sodium ions was formed on the surface using a spin coater, and then on a hot plate at 90 ° C. Pre-baking was performed for 2 minutes to form a coating film having a film thickness of 1.7 μm.
Next, after cooling the substrate to room temperature, the coating film was exposed to ultraviolet rays containing wavelengths of 365 nm, 405 nm, and 436 nm through a photomask (slit width 30 μm) using a high-pressure mercury lamp. The exposure amount at this time was 400 J / m ² . Thereafter, the substrate was immersed in a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried. Thereafter, post-baking was performed in a clean oven at 220 ° C. for 30 minutes to form a pixel array in which red stripe pixel patterns were arranged on the substrate. At this time, the pixel array on the substrate is observed with an optical microscope, the chip edge of the pixel pattern is observed, and the cross section of the pixel pattern is observed with a scanning electron microscope (SEM). The following three levels were evaluated.
<Pixel pattern edge missing (in Table 1, expressed as “edge missing”)>
○: No chipping is observed,
Δ: Some chipping is observed,
X: Many cracks are recognized.
<Undercut of the cross section of the pixel pattern (indicated as “undercut” in Table 1)>
○: Undercut is not recognized,
Δ: A little undercut is recognized,
X: Many undercuts are recognized.

Example 2
In Example 1, (E) the solvent added to 100 parts by weight of the pigment dispersion (R1) was mixed with 50 parts by weight (20% by weight) of cyclohexyl acetate and 125 parts by weight (50% by weight) of ethyl 3-ethoxypropionate. A colored layer-forming composition (R1-2) was prepared and evaluated in the same manner as in Example 1 except that the change was made. The (E) solvent in the colored layer forming composition (R1-2) also contains 75 parts by weight (30% by weight) of propylene glycol monomethyl ether acetate. The evaluation results are shown in Table 1.

Example 3
In Example 1, the solvent (E) added to 100 parts by weight of the pigment dispersion (R1) was 50 parts by weight (20% by weight) of cyclohexyl acetate, 50 parts by weight (50% by weight) of propylene glycol monomethyl ether acetate, A colored layer forming composition (R1-3) was prepared in the same manner as in Example 1 except that 25 parts by weight (10% by weight) of diethylene glycol methyl ethyl ether and 50 parts by weight (20% by weight) of 3-methoxybutyl acetate were used. ) Was prepared and evaluated. The evaluation results are shown in Table 1.

Example 4
In Example 1, the solvent (E) added to 100 parts by weight of the pigment dispersion (R1) was 37 parts by weight (20% by weight) of cyclohexyl acetate and 17 parts by weight of propylene glycol monomethyl ether acetate (about 49.7 parts by weight). %), Diethylene glycol methyl ethyl ether 19 parts by weight (about 10.3% by weight) and 3-methoxybutyl acetate 37 parts by weight (20% by weight). A composition (R1-4) was prepared and evaluated. The evaluation results are shown in Table 1.

Comparative Example 1
In Example 1, except that the solvent added to 100 parts by weight of the pigment dispersion (R1) was changed to 25 parts by weight of propylene glycol monomethyl ether acetate, 75 parts by weight of 3-methoxybutyl acetate and 75 parts by weight of cyclohexanone, In the same manner as in Example 1, a colored layer forming composition (R1-5) was prepared and evaluated. The evaluation results are shown in Table 1.

Comparative Example 2
In Example 1, the solvent added to 100 parts by weight of the pigment dispersion (R1) was changed to 50 parts by weight of propylene glycol monomethyl ether acetate, 75 parts by weight of ethyl 3-ethoxypropionate and 50 parts by weight of diethylene glycol methyl ethyl ether. A colored layer forming composition (R1-6) was prepared and evaluated in the same manner as in Example 1 except that. The evaluation results are shown in Table 1.

Comparative Example 3
In Example 1, the solvent added to 100 parts by weight of the pigment dispersion (R1) was changed to 25 parts by weight of propylene glycol monomethyl ether acetate, 75 parts by weight of 3-methoxybutyl acetate, and 75 parts by weight of cyclohexanone. D) Colored layer forming composition in the same manner as in Example 1 except that the radical generator was changed to 5 parts by weight of 2-methyl- (4-methylthiophenyl) -2-morpholino-1-propan-1-one. A product (R1-7) was prepared and evaluated. The evaluation results are shown in Table 1.

  Here, although the radiation sensitive resin composition using a red pigment was evaluated, similar results were obtained in the case of a radiation sensitive resin composition using a blue, green, yellow or black pigment.

Claims (7)

A radiation-sensitive resin composition containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, (D) a radiation-sensitive radical generator, and (E) a solvent, (D) The radiation-sensitive radical generator contains a compound represented by the following formula (1) and / or a compound represented by the following formula (2) as essential components, and (E) the solvent contains cyclohexyl acetate in an amount of 5 to 5. A radiation-sensitive composition for forming a colored layer, comprising 40% by weight.

[In Formula (1) and Formula (2), each R ¹ independently represents an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, or a phenyl group, and each R ² and each R ³ are independently of each other a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 8 carbon atoms, an optionally substituted phenyl group, or a monovalent alicyclic group having 7 to 20 carbon atoms. Wherein R ⁴ is independently of each other a monovalent oxygen-containing heterocyclic group having 4 to 20 carbon atoms or a monovalent nitrogen-containing complex having 4 to 20 carbon atoms. A cyclic group or a monovalent sulfur-containing heterocyclic group having 4 to 20 carbon atoms, wherein each R ⁵ is independently a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms. Group, a C1-C12 alkoxyl group or a C3-C8 cycloalkyloxy group, Each n is an integer of 1 to 5 independently of each other, each m is an integer of 0 to 5 independently of each other, (n + m) ≦ 5, and p is an integer of 0 to 6. ]   (E) The radiation-sensitive composition for forming a colored layer according to claim 1, wherein the solvent contains 10 to 60% by weight of a solvent having a boiling point of less than 150 ° C.   The radiation sensitive material for forming a colored layer according to claim 2, wherein the solvent further comprises 30 to 70% by weight of a solvent having a boiling point of 150 ° C or higher and lower than 180 ° C (excluding cyclohexyl acetate). Sex composition. A method for forming a colored layer, comprising at least the following steps (1) to (4):
(1) The process of forming the coating film of the radiation sensitive composition for colored layer formation in any one of Claims 1-3 on a board | substrate.
(2) A step of exposing at least a part of the coating film.
(3) The process of developing the coating film after exposure.
(4) The process of heat-processing the coating film after image development.   The method for forming a colored layer according to claim 4, wherein in the step (1), the radiation-sensitive composition for forming a colored layer is applied onto a substrate using a slit nozzle.   The color filter provided with the colored layer formed using the radiation sensitive composition for colored layer formation in any one of Claims 1-3.   A color liquid crystal display device comprising the color filter according to claim 6.