JP2008191519A - Radiation-sensitive composition for forming colored layer, color filter and color liquid crystal display element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a radiation-sensitive composition for forming colored layer, which is excellent in adhesion to a substrate, and cleaning property with an organic solvent, and from which pixels having a high-definition excellent pattern profile can be formed. <P>SOLUTION: The radiation-sensitive composition for forming colored layer contains (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer and (D) a photopolymerization initiator, wherein the alkali-soluble resin (B) contains a copolymer comprising a polymerizable unsaturated compound having a skeleton represented by formula (I) and a substituted maleimide as constituents. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a color liquid crystal display element. More specifically, the present invention relates to a color filter used for a transmissive or reflective color liquid crystal display device, a color imaging tube element, and the like. The present invention relates to a radiation-sensitive composition used for forming a useful colored layer, a color filter including a colored layer formed using the radiation-sensitive composition, and a color liquid crystal display element including the color filter.

Conventionally, in producing a color filter using a colored radiation-sensitive composition, after applying the colored radiation-sensitive composition on a substrate or a substrate on which a light-shielding layer having a desired pattern has been formed and drying, A method of obtaining pixels of each color by irradiating a dry coating film with a desired pattern shape (hereinafter referred to as “exposure”) and developing it is known (see, for example, Patent Document 1 and Patent Document 2). ing.
In recent years, in the technical field of color filters, the required performance for colored radiation-sensitive compositions and formed pixels and black matrices has become increasingly stringent. For pixels and black matrices, for example, the line width is 5 μm or less. In order to be able to cope with high definition, it is strongly required to have excellent adhesion to the substrate, and from the standpoint of yield during production of color filters, it is highly washable with organic solvents, and dry foreign matter is removed during color filter production. Although there is a strong demand not to occur, conventional colored radiation-sensitive compositions have not been able to sufficiently satisfy these requirements.

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

  It is an object of the present invention to form a new colored layer that has excellent adhesion to a substrate and is excellent in cleaning with an organic solvent, and can form a pixel and a black matrix having a high definition and an excellent pattern shape with a high product yield. The object is to provide a radiation-sensitive composition.

The present invention, first,
In the radiation-sensitive composition for forming a colored layer containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, (B) alkali-soluble A radiation sensitive material for forming a colored layer, wherein the resin contains a polymerizable unsaturated compound having a skeleton represented by the following formula (I) and a copolymer having an N-substituted maleimide as essential constituent components A composition.
In the present invention, the colored layer means “pixel and / or black matrix”.

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

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

Hereinafter, the present invention will be described in detail.
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-definition color development and heat resistance, the colorant in the present invention is preferably a colorant having high color developability and high heat resistance, in particular, a colorant having high heat decomposition resistance. Organic pigments or inorganic pigments are used, and organic pigments and carbon black are particularly preferably used.
Examples of the organic pigment include compounds classified as Pigment in the Color Index (CI; issued by The Society of Dyers and Colorists), specifically, the following Color Index (C .. I.) Numbers can be mentioned.

C. I. Pigment yellow 1, C.I. I. Pigment yellow 3, C.I. I. Pigment yellow 12, C.I. I. Pigment yellow 13, C.I. I. Pigment yellow 14, C.I. I. Pigment yellow 15, C.I. I. Pigment yellow 16, C.I. I. Pigment yellow 17, C.I. I. Pigment yellow 20, C.I. I. Pigment yellow 24, C.I. I. Pigment yellow 31, C.I. I. Pigment yellow 55, C.I. I. Pigment yellow 60, C.I. I. Pigment yellow 61, C.I. I. Pigment yellow 65, C.I. I. Pigment yellow 71, C.I. I. Pigment yellow 73, C.I. I. Pigment yellow 74, C.I. I. Pigment yellow 81, C.I. I. Pigment yellow 83, C.I. I. Pigment yellow 93, C.I. I. Pigment yellow 95, C.I. I. Pigment yellow 97, C.I. I. Pigment yellow 98, C.I. I. Pigment yellow 100, C.I. I. Pigment yellow 101, C.I. I. Pigment yellow 104, C.I. I. Pigment yellow 106, C.I. I. Pigment yellow 108, C.I. I. Pigment yellow 109, C.I. I. Pigment yellow 110, C.I. I. Pigment yellow 113, C.I. I. Pigment yellow 114, C.I. I. Pigment yellow 116, C.I. I. Pigment yellow 117, C.I. I. Pigment yellow 119, C.I. I. Pigment yellow 120, C.I. I. Pigment yellow 126, C.I. I. Pigment yellow 127, C.I. I. Pigment yellow 128, C.I. I. Pigment yellow 129, C.I. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150, C.I. I. Pigment yellow 151, C.I. I. Pigment yellow 152, C.I. I. Pigment yellow 153, C.I. I. Pigment yellow 154, C.I. I. Pigment yellow 155, C.I. I. Pigment yellow 156, C.I. I. Pigment yellow 166, C.I. I. Pigment yellow 168, C.I. I. Pigment yellow 175, C.I. I. Pigment yellow 180, C.I. I. Pigment yellow 185;

C. I. Pigment orange 1, C.I. I. Pigment orange 5, C.I. I. Pigment orange 13, C.I. I. Pigment orange 14, C.I. I. Pigment orange 16, C.I. I. Pigment orange 17, C.I. I. Pigment orange 24, C.I. I. Pigment orange 34, C.I. I. Pigment orange 36, C.I. I. Pigment orange 38, C.I. I. Pigment orange 40, C.I. I. Pigment orange 43, C.I. I. Pigment orange 46, C.I. I. Pigment orange 49, C.I. I. Pigment orange 51, C.I. I. Pigment orange 61, C.I. I. Pigment orange 63, C.I. I. Pigment orange 64, C.I. I. Pigment orange 71, C.I. I. Pigment orange 73;
C. I. Pigment violet 1, C.I. I. Pigment violet 19, C.I. I. Pigment violet 23, C.I. I. Pigment violet 29, C.I. I. Pigment violet 32, C.I. I. Pigment violet 36, C.I. I. Pigment violet 38;

C. I. Pigment red 1, C.I. I. Pigment red 2, C.I. I. Pigment red 3, C.I. I. Pigment red 4, C.I. I. Pigment red 5, C.I. I. Pigment red 6, C.I. I. Pigment red 7, C.I. I. Pigment red 8, C.I. I. Pigment red 9, C.I. I. Pigment red 10, C.I. I. Pigment red 11, C.I. I. Pigment red 12, C.I. I. Pigment red 14, C.I. I. Pigment red 15, C.I. I. Pigment red 16, C.I. I. Pigment red 17, C.I. I. Pigment red 18, C.I. I. Pigment red 19, C.I. I. Pigment red 21, C.I. I. Pigment red 22, C.I. I. Pigment red 23, C.I. I. Pigment red 30, C.I. I. Pigment red 31, C.I. I. Pigment red 32, C.I. I. Pigment red 37, C.I. I. Pigment red 38, C.I. I. Pigment red 40, C.I. I. Pigment red 41, C.I. I. Pigment red 42, C.I. I. Pigment red 48: 1, C.I. I. Pigment red 48: 2, C.I. I. Pigment red 48: 3, C.I. I. Pigment red 48: 4, C.I. I. Pigment red 49: 1, C.I. I. Pigment red 49: 2, C.I. I. Pigment red 50: 1, C.I. I. Pigment red 52: 1, C.I. I. Pigment red 53: 1, C.I. I. Pigment red 57, C.I. I. Pigment red 57: 1, C.I. I. Pigment red 57: 2, C.I. I. Pigment red 58: 2, C.I. I. Pigment red 58: 4, C.I. I. Pigment red 60: 1, C.I. I. Pigment red 63: 1, C.I. I. Pigment red 63: 2, C.I. I. Pigment red 64: 1, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 83, C.I. I. Pigment red 88, C.I. I. Pigment red 90: 1, C.I. I. Pigment red 97,

C. I. Pigment red 101, C.I. I. Pigment red 102, C.I. I. Pigment red 104, C.I. I. Pigment red 105, C.I. I. Pigment red 106, C.I. I. Pigment red 108, C.I. I. Pigment red 112, C.I. I. Pigment red 113, C.I. I. Pigment red 114, C.I. I. Pigment red 122, C.I. I. Pigment red 123, C.I. I. Pigment red 144, C.I. I. Pigment red 146, C.I. I. Pigment red 149, C.I. I. Pigment red 150, C.I. I. Pigment red 151, C.I. I. Pigment red 166, C.I. I. Pigment red 168, C.I. I. Pigment red 170, C.I. I. Pigment red 171, C.I. I. Pigment red 172, C.I. I. Pigment red 174, C.I. I. Pigment red 175, C.I. I. Pigment red 176, C.I. I. Pigment red 177, C.I. I. Pigment red 178, C.I. I. Pigment red 179, C.I. I. Pigment red 180, C.I. I. Pigment red 185, C.I. I. Pigment red 187, C.I. I. Pigment red 188, C.I. I. Pigment red 190, C.I. I. Pigment red 193, C.I. I. Pigment red 194, C.I. I. Pigment red 202, C.I. I. Pigment red 206, C.I. I. Pigment red 207, C.I. I. Pigment red 208, C.I. I. Pigment red 209, C.I. I. Pigment red 215, C.I. I. Pigment red 216, C.I. I. Pigment red 220, C.I. I. Pigment red 224, C.I. I. Pigment red 226, C.I. I. Pigment red 242, C.I. I. Pigment red 243, C.I. I. Pigment red 245, C.I. I. Pigment red 254, C.I. I. Pigment red 255, C.I. I. Pigment red 264, C.I. I. Pigment red 265;

C. I. Pigment blue 15, C.I. I. Pigment blue 15: 3, C.I. I. Pigment blue 15: 4, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 60;
C. I. Pigment green 7, C.I. I. Pigment green 36;
C. I. Pigment brown 23, C.I. I. Pigment brown 25;
C. I. Pigment black 1, C.I. I. Pigment Black 7.
These organic pigments 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 (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.

  In the present invention, the organic pigment and the inorganic pigment can be used alone or in admixture of two or more, and the organic pigment and the inorganic pigment can be used in combination. Preferably, one or more organic pigments are used, and two or more organic pigments and / or carbon black are preferably used in forming the black matrix.

  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

Moreover, in this invention, a coloring agent can be used with a dispersing agent depending on necessity. Examples of the dispersant include cationic, anionic, nonionic, amphoteric, silicone, and fluorine surfactants.
Examples of the surfactant include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, and polyoxyethylene oleyl ether; polyoxyethylene n-octylphenyl ether, polyoxyethylene n-nonyl Polyoxyethylene alkyl phenyl ethers such as phenyl 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; Polyethyleneimines In addition, the following trade names are KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Polyflow (manufactured by Kyoeisha Chemical Co., Ltd.), and F-Top (manufactured by Tochem Products). MegaFuck (Dainippon Ink & Chemicals), Florard (Sumitomo 3M), Asahi Guard, Surflon (Asahi Glass), BYK, Disperbyk (Bicchemy Japan) Product), Solsperse (manufactured by Seneca Corporation), and the like.
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 composition can be prepared by an appropriate method, for example, by mixing the components (A) to (D) with a solvent and an additive as described below depending on the case. However, when a pigment is used as a colorant, the pigment is mixed in a solvent in the presence of a dispersant, optionally together with a part of the component (B), for example, using a bead mill, a roll mill or the like. It is preferable to prepare a pigment dispersion by dispersing and adding the components (B) to (D) and, if necessary, additional solvents and additives, and mixing them.

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 the pigment. The amount is preferably 10 to 50 parts by weight. 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 solvent illustrated about the liquid composition of the radiation sensitive resin composition mentioned later can be mentioned, for example.
The amount of the solvent used in preparing the pigment dispersion is usually 200 to 1,200 parts by weight, preferably 300 to 1,000 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-
The alkali-soluble resin in the present invention includes a polymerizable unsaturated compound having a skeleton represented by the formula (I) (hereinafter referred to as “unsaturated compound (I)”) and an N-substituted maleimide as essential components. And an alkali used in the development processing step when forming a colored layer (A) acting as a binder for the colorant and the copolymer (hereinafter referred to as “copolymer (B1)”). This component is soluble in the developer.

  In the copolymer (B1), examples of the unsaturated compound (I) include (meth) acryloyl group-containing dehydroabietic acid esters represented by the following formula (I-1) (hereinafter referred to as “dehydroabietic acid ester ( I-1) ").

〔式（Ｉ−１）において、Ｒは水素原子またはメチル基を示し、Ｘは２価の有機基を示す。〕

[In Formula (I-1), R represents a hydrogen atom or a methyl group, and X represents a divalent organic group. ]

In the formula (I-1), examples of the divalent organic group represented by X include:
Methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,2-propylene group, 1,3-propylene group, 1,4-butylene group, 1,2-cyclopentylene group, 1,3 -(Cyclo) alkylene groups such as cyclopentylene group, 1,2-cyclohexylene group, 1,3-cyclohexylene group, 1,4-cyclohexylene group, and substituted derivatives thereof;

1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 4,4′-biphenylene group, —Ar—CH ₂ —Ar— (wherein Ar is a 1,4-phenylene group) . hereinafter the _{same), -. Ar-CH 2} C (CH 3) 2 CH 2 -Ar -, - Ar-CO-Ar-,
-Ar-O-Ar -, - Ar-SO 2 -Ar -, - or an arylene group Ar-NH ₂ -Ar-, etc., can be mentioned substituted derivatives thereof and the like.

  Examples of the substituent in the substituted derivative of the (cyclo) alkylene group and the substituted derivative of the arylene group include a hydroxyl group and an alkoxyl group (for example, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, t-butoxy group etc.), alkyl group (eg methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group etc.), alkylcarbonyloxy group (eg methylcarbonyloxy) Group, ethylcarbonyloxy group, n-propylcarbonyloxy group, i-propylcarbonyloxy group, n-butylcarbonyloxy group, t-butylcarbonyloxy group, etc.), carboxyl group, alkoxycarbonyl group (for example, methoxycarbonyl group, Ethoxycarbonyl group, n-propoxycarbonyl group i-propoxycarbonyl group, n-butoxycarbonyl group, t-butoxycarbonyl group, etc.), amino group, dialkylamino group (for example, dimethylamino group, diethylamino group, di-n-propylamino group, di-i-propylamino group) Group, di-n-butylamino group, di-t-butylamino group, etc.), halogen atoms (for example, fluorine atom, chlorine atom, bromine atom, etc.) and the like.

  Particularly preferred dehydroabietic acid ester (I-1) in the present invention includes, for example, a compound represented by the following formula (I-2) (hereinafter referred to as “dehydroabietic acid ester (I-2)”). be able to.

〔式（Ｉ−２）において、Ｒは水素原子またはメチル基を示す。〕
共重合体（Ｂ１）において、不飽和化合物（Ｉ）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。

[In formula (I-2), R represents a hydrogen atom or a methyl group. ]
In the copolymer (B1), the unsaturated compound (I) can be used alone or in admixture of two or more.

In the copolymer (B1), examples of the N-substituted maleimide include maleimide in which the N-position is substituted with a (cyclo) alkyl group, an aryl group, an aralkyl group, or a substituted derivative thereof.
Specific examples of the N-substituted maleimide include N-phenylmaleimide, N-o-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, N-o-methylphenylmaleimide, N- In addition to N- (substituted) arylmaleimide such as m-methylphenylmaleimide, Np-methylphenylmaleimide, N-o-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide, Np-methoxyphenylmaleimide, N -Cyclohexylmaleimide, N-benzylmaleimide and the like can be mentioned.
Of these N-substituted maleimides, maleimides in which the N-position is substituted with an aryl group or a substituted aryl group are preferred, and N-phenylmaleimide is particularly preferred.
In the copolymer (B1), N-substituted maleimides can be used alone or in admixture of two or more.

The copolymer (B1) can usually contain components other than the unsaturated compound (I) and the N-substituted maleimide (hereinafter referred to as “other components”).
As other components, for example, a polymerizable unsaturated compound having at least one or at least one acidic functional group such as a carboxyl group or a phenolic hydroxyl group in the molecule (hereinafter referred to as “acidic unsaturated compound”) or the like. And other polymerizable unsaturated compounds (hereinafter referred to as “other unsaturated compounds”).

As an acidic unsaturated compound, for example,
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 carboxy group and a hydroxyl group at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylate.
Succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are trade names of light ester HOA-MS and light ester HOA-MPE (above, manufactured by Kyoeisha Chemical Co., Ltd.), respectively. Is commercially available.

Moreover, as an acidic unsaturated compound other than the above, for example,
o-vinylphenol, m-vinylphenol, p-vinylphenol, 2-methyl-4-vinylphenol, 3-methyl-4-vinylphenol, o-isopropenylphenol, m-isopropenylphenol, p-isopropenylphenol Unsaturated phenols such as
2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl-1-naphthol, etc. Of unsaturated naphthols.

Of these acidic unsaturated compounds, (meth) acrylic acid, p-vinylphenol and the like are preferable, and (meth) acrylic acid is particularly preferable.
In the copolymer (B1), the acidic unsaturated compounds can be used alone or in admixture of two or more.

Moreover, as another unsaturated compound, for example,
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 (meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethyl Unsaturated carboxylic acid aminoalkyl esters such as aminopropyl (meth) acrylate;
Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate;
Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, vinylidene cyanide;
Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide, N-2-hydroxyethyl (meth) acrylamide;
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;
Aliphatic conjugated dienes such as 1,3-butadiene, isoprene, chloroprene;
Examples thereof include macromonomers 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, and polysiloxane.
In the copolymer (B1), other unsaturated compounds can be used alone or in admixture of two or more.

In the present invention, as a preferable copolymer (B1), more specifically, for example,
(I) Unsaturated compound (I) having dehydroabietic acid ester (I-1) as an essential component, (ii) N-substituted maleimide having N-phenylmaleimide as an essential component, (iii) (meth) acrylic acid Unsaturated compounds containing as an essential component, and (iv) styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol Mention may be made of copolymers of other unsaturated compounds selected from the group of mono (meth) acrylates, polystyrene macromonomers and polymethyl (meth) acrylate macromonomers,

As a particularly preferred copolymer (B1), for example,
(I) Unsaturated compound (I) having dehydroabietic acid ester (I-2) as an essential component, (ii) N-substituted maleimide having N-phenylmaleimide as an essential component, (iii) (meth) acrylic acid Unsaturated compounds containing styrene as an essential component, and (iv) styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol Mention may be made of copolymers of other unsaturated compounds selected from the group of mono (meth) acrylates, polystyrene macromonomers and polymethyl (meth) acrylate macromonomers.

In the copolymer (B1), the copolymerization ratio of the unsaturated compound (I) is preferably 1 to 70% by weight, particularly preferably 1 to 40% by weight, and the copolymerization ratio of the N-substituted maleimide is It is preferably 1 to 70% by weight, particularly preferably 1 to 40% by weight, and the copolymerization ratio of the acidic unsaturated compound is preferably 1 to 40% by weight, particularly preferably 5 to 30% by weight. The copolymerization ratio of the unsaturated compound is preferably 10 to 90% by weight, particularly preferably 20 to 70% by weight.
In the present invention, by setting the copolymerization ratio of each unsaturated compound in the copolymer (B1) within the above range, the radiation sensitivity for forming the colored layer is excellent in sensitivity, adhesion to the substrate, and washing with an organic solvent. Sex composition can be obtained.

In the present invention, other alkali-soluble resins can be used in combination with the copolymer (B1).
The other alkali-soluble resin is not particularly limited as long as it functions as a binder for (A) the colorant and is soluble in the alkali developer used in the development processing step when forming the colored layer. For example, an alkali-soluble resin having a carboxyl group (hereinafter referred to as “another carboxyl group-containing alkali-soluble resin”) is preferable.

  Preferred other carboxyl group-containing alkali-soluble resins include, for example, (i) a copolymer of an acidic unsaturated compound and (ii) another unsaturated compound, and more preferably (i) ( Carboxy group-containing unsaturated compound containing meth) acrylic acid as an essential component, and (ii) styrene, methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, phenyl It is a copolymer with another unsaturated compound selected from the group of (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl (meth) acrylate macromonomer.

In the present invention, Mw of the copolymer (B1) and other alkali-soluble resins is preferably 1,000 to 10,000, particularly preferably 5,000 to 10,000.
Moreover, Mw / Mn of the copolymer (B1) and other alkali-soluble resins is preferably 1.0 to 2.0, particularly preferably 1.0 to 1.5, respectively.
In the present invention, the copolymer (B1) having the specific Mw and / or Mw / Mn is used, or the copolymer (B1) and another copolymer having the specific Mw and / or Mw / Mn are used. By using in combination with an alkali-soluble resin, a radiation-sensitive composition having excellent developability can be obtained, whereby a pixel having a sharp pattern edge and a black matrix can be formed, and an unexposed area during development Residues, background stains, film residues and the like hardly occur on the substrate and the light shielding layer.

  For example, the copolymer (B1) is obtained by converting each unsaturated compound as a component into 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2 , 2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) and the like, and pyrazole-1-dithiocarboxylic acid cyano (dimethyl) methyl ester, pyrazole-1-dithiocarboxylic acid benzyl ester, Tetraethylthiuram disulfide, bis (pyrazol-1-ylthiocarbonyl) disulfide, bis (3-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (4-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis ( 5-methyl-pyrazol-1-ylthiocarbonyl) disulfide, bis 3,4,5-trimethyl-pyrazol-1-ylthiocarbonyl) disulfide, bis (pyrrol-1-ylthiocarbonyl) disulfide, bis (thiobenzoyl) disulfide, bis (n-octylsulfanylthiocarbonyl) disulfide, bis ( n-dodecylsulfanylthiocarbonyl) disulfide) in the presence of a molecular weight controlling agent that acts as an iniferter, in an inert solvent, the reaction temperature is usually 0 to 150 ° C., preferably 50 to 120 ° C., and living radical polymerization is performed. Can be manufactured.

In this invention, a copolymer (B1) can be used individually or in mixture of 2 or more types, and other alkali-soluble resin is also the same.
In this invention, the total usage-amount of alkali-soluble resin 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, if the total use amount of the alkali-soluble resin is less than 10 parts by weight, for example, the alkali developability may be lowered, or there is a possibility that background stains or film residue may occur on the unexposed part of the substrate or on the light shielding layer. On the other hand, when the amount exceeds 1,000 parts by weight, the colorant concentration relatively decreases, and it may be difficult to achieve the target color density as a thin film.
Moreover, the usage-amount of the copolymer (B1) in alkali-soluble resin becomes like this. Preferably it is 10-100 weight%, Most preferably, it is 30-100 weight%. In this case, if the proportion of the copolymer (B1) used is less than 10% by weight, the intended effect of the present invention may be impaired.

-(C) polyfunctional monomer-
The polyfunctional monomer in this invention consists of a monomer which has a 2 or more polymerizable unsaturated bond.
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 and the like, 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 polyhydric alcohols having three or more valences and their dicarboxylic acid-modified products, specifically, trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, Pentaerythritol triacrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, etc. are preferred, particularly tri Methylolpropane triacrylate, pentaerythritol triacrylate, dipentaerythritol hexaacrylate Rate, the strength of the colored layer is high, excellent surface smoothness of the colored layer, and the substrate on and stain on the light-shielding layer in the unexposed portion, are unlikely to generate film residue and the like.
The said polyfunctional monomer can be used individually or in mixture of 2 or more types.

  In this invention, the usage-amount of a polyfunctional monomer 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, alkali developability is reduced. There is a tendency that background contamination, film residue, etc. are likely to occur on the unexposed substrate or 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 (B) compounds similar to those exemplified for the N-position-substituted maleimide, acidic unsaturated compound or other unsaturated compound in the alkali-soluble resin, or N- (meth). In addition to acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, examples of commercially available products include M-5600 (trade name, manufactured by Toagosei Co., Ltd.).
The 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, when the use ratio of the monofunctional monomer exceeds 90% by weight, the strength and surface smoothness of the resulting colored layer may be insufficient.

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

-(D) Photopolymerization initiator-
The photopolymerization initiator in the present invention is the above-mentioned (C) polyfunctional monomer and a monofunctional monomer used in some cases upon exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, electron beam, and X-ray. It is a compound that generates active species capable of initiating polymerization of the body.
Examples of such photopolymerization initiators include acetophenone compounds, biimidazole compounds, triazine compounds, O-acyloxime compounds, onium salt compounds, benzoin compounds, benzophenone compounds, α-diketone compounds. , Polynuclear quinone compounds, xanthone compounds, diazo compounds, imide sulfonate compounds, and the like. These compounds are components that generate active radicals or active acids or both active radicals and active acids upon exposure.

  In the present invention, the photopolymerization initiator can be used alone or in admixture of two or more. As the photopolymerization initiator in the present invention, an acetophenone compound, a biimidazole compound, a triazine compound, At least one selected from the group of O-acyloxime compounds and onium salt compounds is preferred.

  In this invention, the general usage-amount of a photoinitiator is 0.01-120 weight normally with respect to a total of 100 weight part of (C) polyfunctional monomer and a monofunctional monomer. Parts, preferably 1 to 100 parts by weight. In this case, when the amount of the photopolymerization initiator used is less than 0.01 part by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 120 parts by weight, the formed colored layer tends to be detached from the substrate during development.

Among preferred photopolymerization initiators in the present invention, specific examples of acetophenone compounds include 2-hydroxy-2-methyl-1-phenylpropan-1-one and 2-methyl-1- [4- (methylthio) phenyl. ] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy- Examples include 1,2-diphenylethane-1-one and 1,2-octanedione.
Among these acetophenone compounds, in particular, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpho Linophenyl) butan-1-one, 1,2-octanedione and the like are preferred.
The acetophenone compounds can be used alone or in admixture of two or more.

  In the present invention, when the acetophenone compound is used as the photopolymerization initiator, the amount used is usually 0 with respect to 100 parts by weight of the total of the (C) polyfunctional monomer and the monofunctional monomer. 0.01 to 80 parts by weight, preferably 1 to 60 parts by weight, and more preferably 1 to 40 parts by weight. In this case, if the amount of the acetophenone compound used is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, when the amount exceeds 80 parts by weight, the formed colored layer tends to be detached from the substrate during development.

  Specific examples of the biimidazole compound include 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetrakis (4-ethoxycarbonylphenyl) -1,2′-bi Imidazole, 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'-tetra Phenyl-1,2′-biimidazole, 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole, 2, 2'-bis (2-bromophenyl)- , 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. .

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 preferable, and in particular, 2,2′-bis (2,4-dichlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2 '-Biimidazole is preferred.
These biimidazole compounds are excellent in solubility in solvents, do not generate foreign matters such as undissolved substances and precipitates, have high sensitivity, and sufficiently advance the curing reaction by exposure with a small amount of energy. Since no curing reaction occurs in the exposed area, the coated film after exposure is clearly divided into a cured area that is insoluble in the developer and an uncured area that has high solubility in the developer, Thereby, a high-definition color filter in which a colored layer pattern without an undercut is arranged according to a predetermined arrangement can be formed.
The biimidazole compounds can be used alone or in admixture of two or more.

  In the present invention, the amount used in the case of using a biimidazole compound as a photopolymerization initiator is usually (C) with respect to a total of 100 parts by weight of the polyfunctional monomer and the monofunctional monomer, 0.01 to 40 parts by weight, preferably 1 to 30 parts by weight, more preferably 1 to 20 parts by weight. In this case, if the amount of biimidazole compound used is less than 0.01 parts by weight, curing by exposure may be insufficient, and it may be difficult to obtain a color filter in which a colored layer pattern is arranged according to a predetermined arrangement. On the other hand, when the amount exceeds 40 parts by weight, the developed colored layer tends to fall off from the substrate or the surface of the colored layer tends to come off during development.

In the present invention, when a biimidazole compound is used as a photopolymerization initiator, it is preferable to use a hydrogen donor described below in combination because sensitivity can be further improved.
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.
The hydrogen donor in the present invention is preferably a mercaptan compound or an amine compound defined below.

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-based 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 “ 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.
Further, when the mercaptan-based hydrogen donor has two or more mercapto groups, one or more of the remaining mercapto groups are substituted with an alkyl, aralkyl or aryl group as long as at least one free mercapto group remains. Further, 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 present. It can have structural units linked in the form of disulfides.
Further, the mercaptan-based hydrogen donor may be substituted with a carboxyl group, an alkoxycarbonyl group, a substituted alkoxycarbonyl group, a phenoxycarbonyl group, a substituted 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.

In addition, the amine hydrogen donor can have one or more benzene rings or heterocyclic rings, and can have both a benzene ring and a heterocyclic ring. A ring may or may not be formed.
In addition, in the amine-based hydrogen donor, one or more of the amino groups may be substituted with an alkyl group or a substituted alkyl group. It may be substituted with a carbonyl group, a substituted phenoxycarbonyl group, a 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 thereof include ethyl-4-dimethylaminobenzoate, 4-dimethylaminobenzoic acid, 4-dimethylaminobenzonitrile and the like.
Among these amine hydrogen donors, 4,4′-bis (dimethylamino) benzophenone and 4,4′-bis (diethylamino) benzophenone are preferable, and 4,4′-bis (diethylamino) benzophenone is particularly preferable.
The amine-based hydrogen donor has a function as a sensitizer even in the case of radical generators other than biimidazole compounds.

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 from the substrate during development, and the strength and sensitivity of the colored layer are high.
Specific examples of the 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, and more preferred combinations 2-mercaptobenzothiazole / 4,4′-bis (diethylamino) benzophenone, 2-mercaptobenzoxazole / 4,4′-bis (diethylamino) benzophenone, and a particularly preferred combination is 2-mercaptobenzothiazole / , 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 from 1: 1 to 1: 4, preferably from 1: 1 to 1: 3.

  In the present invention, when the hydrogen donor is used in combination with the biimidazole compound, the amount used is preferably 0 with respect to 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. In this case, if the amount of the hydrogen donor used is less than 0.01 parts by weight, the effect of improving the sensitivity tends to decrease. On the other hand, if it exceeds 40 parts by weight, the formed colored layer is detached from the substrate during development. It tends to be easy to do.

  Specific examples of the triazine 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 (trichloro Methyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (3,4-dimethoxy) Phenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4- Triazine-based compounds having a halomethyl group such as xystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine Can be mentioned.

Of these triazine compounds, 2- [2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine is particularly preferable.
The triazine compounds can be used alone or in admixture of two or more.

  In the present invention, the amount of triazine compound used as the photopolymerization initiator is preferably 0 with respect to 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, and particularly preferably 1 to 20 parts by weight. In this case, if the amount of the triazine compound used is less than 0.01 parts 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 according to a predetermined arrangement. On the other hand, if it exceeds 40 parts by weight, the formed colored layer tends to be easily detached from the substrate during development.

  Specific examples of the O-acyloxime compound include 1- [4- (phenylthio) phenyl] -heptane-1,2-dione 2- (O-benzoyloxime), 1- [4- (phenylthio). Phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [4- (benzoyl) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9 -Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), 1- [9-ethyl-6- (3-methylbenzoyl) -9H-carbazole -3-yl] -ethanone 1- (O-acetyloxime), 1- (9-ethyl-6-benzoyl-9H-carbazol-3-yl) -ethanone 1- (O-acetate) Ruokishimu) ethanone 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranyl Ruben benzoyl) -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-4- (2,2-dimethyl-1,3-dioxolanyl) benzoyl} -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-tetrahydrofuranylmethoxybenzoyl) -9. H. -Carbazol-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-5-tetrahydropyranylmethoxybenzoyl) -9. H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like.

Among these O-acyloxime compounds, in particular, 1- [4- (phenylthio) phenyl] -octane-1,2-dione 2- (O-benzoyloxime), 1- [9-ethyl-6- ( 2-Methylbenzoyl) -9H-carbazol-3-yl] -ethanone 1- (O-acetyloxime), ethanone-1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) -9 . H. -Carbazole-3-yl] -1- (O-acetyloxime), ethanone-1- [9-ethyl-6- {2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl } -9. H. -Carbazol-3-yl] -1- (O-acetyloxime) and the like are preferable.
The O-acyloxime compounds can be used alone or in admixture of two or more.

  In the present invention, the amount used in the case of using an O-acyloxime compound as a photopolymerization initiator is based on 100 parts by weight of the total of (C) the polyfunctional monomer and the monofunctional monomer. Preferably it is 0.01-40 weight part, More preferably, it is 1-30 weight part, Most preferably, it is 1-20 weight part. In this case, if the amount of the O-acyloxime compound used is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it is difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, when the amount exceeds 40 parts by weight, the formed colored layer tends to be detached from the substrate during development.

Examples of the onium salt compounds include diaryliodonium salts, triarylsulfonium salts, diarylphosphonium salts, and the like.
Specific examples of the diaryliodonium salts include diphenyliodonium tetrafluoroborate, diphenyliodonium hexafluorophosphonate, diphenyliodonium hexafluoroarsenate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium trifluoroacetate, diphenyliodonium-p-toluenesulfonate. 4-methoxyphenylphenyliodonium tetrafluoroborate, 4-methoxyphenylphenyliodonium hexafluorophosphonate, 4-methoxyphenylphenyliodonium hexafluoroarsenate, 4-methoxyphenylphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium trifluoro Acetate, 4-methoxyphenylphenyliodonium-p-toluenesulfonate, bis (4-t-butylphenyl) iodonium tetrafluoroborate, bis (4-t-butylphenyl) iodonium hexafluoroarsenate, bis (4-t- Examples thereof include butylphenyl) iodonium trifluoromethanesulfonate, bis (4-tert-butylphenyl) iodonium trifluoroacetate, and bis (4-tert-butylphenyl) iodonium-p-toluenesulfonate.

Specific examples of the triarylsulfonium salts include triphenylsulfonium tetrafluoroborate, triphenylsulfonium hexafluorophosphonate, triphenylsulfonium hexafluoroarsenate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium trifluoroacetate, triphenyl Sulfonium-p-toluenesulfonate, 4-methoxyphenyldiphenylsulfonium tetrafluoroborate, 4-methoxyphenyldiphenylsulfonium hexafluorophosphonate, 4-methoxyphenyldiphenylsulfonium hexafluoroarsenate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyldipheny Sulfonium trifluoroacetate, 4-methoxyphenyldiphenylsulfonium-p-toluenesulfonate, 4-phenylthiophenyldiphenyltetrafluoroborate, 4-phenylthiophenyldiphenylhexafluorophosphonate, 4-phenylthiophenyldiphenylhexafluoroarsenate, 4 -Phenylthiophenyl diphenyl trifluoromethanesulfonate, 4-phenylthiophenyl diphenyl trifluoroacetate, 4-phenylthiophenyl diphenyl-p-toluenesulfonate and the like can be mentioned.
Specific examples of the diarylphosphonium salts include (1-6-η-cumene) (η-cyclopentadienyl) iron hexafluorophosphonate.

  Of these onium salt compounds, diphenyliodonium hexafluorophosphonate, triphenylsulfonium trifluoromethanesulfonate, and the like are particularly preferable. The said onium salt type compound can be used individually or in mixture of 2 or more types.

  In the present invention, the amount used in the case of using an onium salt compound as a photopolymerization initiator is preferably (C) with respect to a total of 100 parts by weight of the polyfunctional monomer and the monofunctional monomer. 0.01 to 40 parts by weight, more preferably 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. In this case, if the amount of the onium salt compound used is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it may be difficult to obtain a color filter in which the colored layer pattern is arranged according to a predetermined arrangement. On the other hand, if it exceeds 40 parts by weight, the formed colored layer tends to be easily detached from the substrate during development.

-Additives-
The radiation-sensitive composition for forming a colored layer of the present invention can contain various additives as necessary.
Examples of the additive include an organic acid or an organic amino compound (excluding the hydrogen donor).

The organic acid and the organic amino compound are components that improve the solubility of the radiation-sensitive composition in an alkaline developer and further suppress the remaining undissolved material after development.
The organic acid is preferably an aliphatic carboxylic acid or a phenyl group-containing carboxylic acid having one or more carboxyl groups in the molecule.
Examples of the aliphatic carboxylic acid include
Monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethylacetic acid, enanthic acid, caprylic acid;
Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, tetramethylsuccinic acid Dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid, mesaconic acid;
And tricarboxylic acids such as tricarballylic acid, aconitic acid, and camphoronic acid.

Examples of the phenyl group-containing carboxylic acid include a compound in which a carboxyl group is directly bonded to the phenyl group, and a carboxylic acid in which the carboxyl group is bonded to the phenyl group via a carbon chain.
Examples of the phenyl group-containing carboxylic acid include
Aromatic monocarboxylic acids such as benzoic acid, toluic acid, cumic acid, hemelic acid, mesitylene acid;
Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid;
Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, merophanic acid, pyromellitic acid,
Examples include phenylacetic acid, hydroatropic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atropic acid, cinnamic acid, cinnamylidene acid, coumaric acid, and umberic acid.

Among these organic acids, aliphatic carboxylic acids are aliphatic from the viewpoints of alkali solubility, solubility in a solvent described later, prevention of soiling and film residue on the substrate or the light-shielding layer in the unexposed area, and the like. Dicarboxylic acids are preferred, and malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are particularly preferred. As the phenyl group-containing carboxylic acid, aromatic dicarboxylic acids are preferable, and phthalic acid is particularly preferable.
The organic acids can be used alone or in admixture of two or more.
The amount of the organic acid used is usually 15% by weight or less, preferably 10% by weight or less, based on the entire solid content of the radiation-sensitive composition. In this case, when the usage-amount of organic acid exceeds 15 weight%, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed colored layer to fall.

The organic amino compound is preferably an aliphatic amine or a phenyl group-containing amine having one or more amino groups in the molecule.
Examples of the aliphatic amine include:
n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4-methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine, 4- Mono (cyclo) alkylamines such as ethylcyclohexylamine;
Methyl ethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di-sec-butylamine, di Di (cyclo) alkylamines such as t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine, dicyclohexylamine;

Dimethylethylamine, methyldiethylamine, triethylamine, dimethyl n-propylamine, diethyl n-propylamine, methyldi-n-propylamine, ethyldi-n-propylamine, tri-n-propylamine, tri-i-propylamine, tri- n-butylamine, tri-i-butylamine, tri-sec-butylamine, tri-t-butylamine, tri-n-pentylamine, tri-n-hexylamine, dimethylcyclohexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexyl Tri (cyclo) alkylamines such as amine and tricyclohexylamine;
2-aminoethanol, 3-amino-1-propanol, 1-amino-2-propanol, 4-amino-1-butanol, 5-amino-1-pentanol, 6-amino-1-hexanol, 4-amino- Mono (cyclo) alkanolamines such as 1-cyclohexanol;

Diethanolamine, di-n-propanolamine, di-i-propanolamine, di-n-butanolamine, di-i-butanolamine, di-n-pentanolamine, di-n-hexanolamine, di (4-cyclo Di (cyclo) alkanolamines such as hexanol) amine;
Triethanolamine, tri-n-propanolamine, tri-i-propanolamine, tri-n-butanolamine, tri-i-butanolamine, tri-n-pentanolamine, tri-n-hexanolamine, tri (4 -Tri (cyclo) alkanolamines such as cyclohexanol) amine;

3-amino-1,2-propanediol, 2-amino-1,3-propanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1, 2-cyclohexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propanediol Amino (cyclo) alkanediols such as 2-diethylamino-1,3-propanediol;
1-aminocyclopentanemethanol, 4-aminocyclopentanemethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanemethanol, 4-diethylaminocyclopentanemethanol, 4-dimethylaminocyclohexanemethanol, 4- Amino group-containing cycloalkanemethanols such as diethylaminocyclohexanemethanol;
β-alanine, 2-aminobutyric acid, 3-aminobutyric acid, 4-aminobutyric acid, 2-aminoisobutyric acid, 3-aminoisobutyric acid, 2-aminovaleric acid, 5-aminovaleric acid, 6-aminocaproic acid, 1-aminocyclo Examples thereof include aminocarboxylic acids such as propanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid.

Examples of the phenyl group-containing amine include compounds in which an amino group is directly bonded to a phenyl group, and compounds in which an amino group is bonded to a phenyl group via a carbon chain.
As the phenyl group-containing amine, for example,
Aniline, 2-methylaniline, 3-methylaniline, 4-methylaniline, 4-ethylaniline, 4-n-propylaniline, 4-i-propylaniline, 4-n-butylaniline, 4-t-butylaniline, Aromatic amines such as 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline, 4-methyl-N, N-dimethylaniline;
Aminobenzyl alcohols such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylaminobenzyl alcohol, 4-diethylaminobenzyl alcohol;
Examples include aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol, and 4-diethylaminophenol.

Furthermore, as an additive other than the above, for example,
Dispersing aids such as blue pigment derivatives and yellow pigment derivatives such as copper phthalocyanine derivatives;
Fillers such as glass and alumina;
Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers, poly (fluoroalkyl acrylates);
Nonionic, cationic and anionic surfactants;
Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3-aminopropyltri Methoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropyl Adhesion promoters such as methyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane;
Antioxidants such as 2,2′-thiobis (4-methyl-6-tert-butylphenol), 2,6-di-tert-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones;
Anti-agglomeration agents such as sodium polyacrylate;
Examples include thermal radical generators such as 1,1′-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

Solvent The radiation-sensitive composition for forming a colored layer according to the present invention comprises the components (A) to (D) as essential components, and contains the additive components as necessary. Prepared as a composition.
As the solvent, the components (A) to (D) and additive components constituting the radiation-sensitive composition are dispersed or dissolved, and do not react with these components and have appropriate volatility. Can be appropriately selected and used.

As such a solvent, for example,
Ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n- Butyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, di Propylene glycol mono Chirueteru, dipropylene glycol mono -n- propyl ether, dipropylene glycol mono -n- butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl (poly) alkylene glycol monoalkyl ethers such as ether;

(Poly) alkylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone;

Lactic acid alkyl esters such as methyl lactate and ethyl lactate;
Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, 2-hydroxy Methyl-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n -Butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate , N-propyl pyruvate, methyl acetoacetate, acetoacetate Le, other esters such as ethyl 2-oxobutanoate;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Of these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol from the viewpoints of pigment dispersibility, solubility of components other than pigment, coatability, etc. Dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methoxybutyl acetate, 3-methyl -3-methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, Ethyl butyrate i- propyl butyrate n- butyl, ethyl pyruvate and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

Along with the solvent, benzyl ethyl ether, di-n-hexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate In addition, a high-boiling solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can be used in combination.
The high boiling point solvents can be used alone or in admixture of two or more.

  The amount of the solvent used is not particularly limited, but the total concentration of each component excluding the solvent of the composition is usually from the viewpoint of applicability, stability, etc. of the resulting radiation-sensitive composition. An amount of 5 to 50% by weight, preferably 10 to 40% by weight, is desirable.

Color filter The color filter of the present invention comprises a colored layer formed using the radiation-sensitive composition for forming a colored layer of the present invention.
Below, the method of forming the colored layer in the color filter of this invention is demonstrated.
First, on the surface of the substrate, if necessary, a light shielding layer is formed so as to partition a portion for forming pixels, and a liquid composition of a radiation sensitive composition in which, for example, a red pigment is dispersed on the substrate. After applying the product, pre-baking is performed to evaporate the solvent, thereby forming a coating film.
Next, after exposing the coating film through a photomask, development using an alkali developer is performed to dissolve and remove the unexposed portion of the coating film, and then post-baking to form a predetermined red pixel pattern. A pixel array arranged in an array is formed.
Thereafter, using the liquid composition of each radiation-sensitive composition in which a green or blue pigment is dispersed, the liquid composition is coated, pre-baked, exposed, developed, and post-baked in the same manner as described above. By sequentially forming the pixel array and the blue pixel array on the same substrate, a color filter in which the pixel arrays of the three primary colors of red, green and blue are arranged on the substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.
In addition, the black matrix can be formed in the same manner as in the case of forming the pixel, for example, using a liquid composition of a radiation sensitive composition in which a black pigment is dispersed.

Examples of the substrate used when forming the pixel and / or the black matrix include glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamideimide, and polyimide.
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.
When applying a liquid composition of a radiation sensitive composition to a substrate, an appropriate application such as a spray method, a roll coating method, a spin coating method (spin coating method), a slit die coating method, a bar coating method, an ink jet method, etc. Although a method can be adopted, a spin coating method, a slit die coating method and the like are particularly preferable.
The coating thickness 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 drying.

As the radiation used when forming the pixel and / or the black matrix, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray or the like can be used, but the wavelength is in the range of 190 to 450 nm. Some radiation is preferred.
Exposure of radiation is preferably 10~10,000J / m ^2.
Examples of the alkali developer include sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, An aqueous solution such as 5-diazabicyclo- [4.3.0] -5-nonene is preferred.
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 applied. The development conditions are preferably 5 to 300 seconds at room temperature.

  The color filter of the present invention thus obtained is extremely useful for, for example, a transmissive or reflective color liquid crystal display element, a color imaging tube element, a color sensor, and the like.

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.

The radiation-sensitive composition for forming a colored layer of the present invention is excellent in adhesion to a substrate, and can form a pixel and a black matrix having a high-definition and excellent pattern shape. In addition, since the detergency with the organic solvent is high, no dry foreign matter is generated when forming the pixels and the black matrix, and a high product yield can be realized.
Therefore, the radiation-sensitive composition for forming a colored layer of the present invention can be very suitably used for the production of various color filters including color filters for color liquid crystal display elements in the electronic industry.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples. Here, parts and% are based on weight.
Mw and Mn of the resin obtained in each of the following synthesis examples were measured by gel permeation chromatography (GPC) according to the following specifications.
Apparatus: GPC-101 (trade name, manufactured by Showa Denko KK)
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 were used in combination.
Elution solvent: tetrahydrofuran containing 0.5% by weight of phosphoric acid.

Synthesis of alkali-soluble resin Synthesis Example 1
A flask equipped with a condenser and a stirrer was charged with 2 parts of 2,2′-azobisisobutyronitrile and 200 parts of propylene glycol monomethyl ether acetate, followed by dehydroabietic acid ester (I-2) (where R is hydrogen) 30 parts of N-phenylmaleimide, 20 parts of methacrylic acid, 20 parts of styrene, and 4 parts of bis (pyrazol-1-ylthiocarbonyl) disulfide as a molecular weight control agent were substituted with nitrogen. Thereafter, the mixture was gently stirred to raise the temperature of the reaction solution to 80 ° C., and this temperature was maintained for 5 hours to perform living radical polymerization to obtain a resin solution. This resin had Mw of 5,500 and Mw / Mn of 1.4.
This resin is referred to as “alkali-soluble resin (B-1)”.

Synthesis example 2
A resin solution was obtained in the same manner as in Synthesis Example 1 except that styrene was used instead of dehydroabietic acid ester (I-2) used in Synthesis Example 1 and the total amount of styrene used was 50 parts. This resin had Mw of 6,000 and Mw / Mn of 1.5.
This resin is referred to as “alkali-soluble resin (B-2)”.

Synthesis example 3
A resin solution was obtained in the same manner as in Synthesis Example 1 except that styrene was used instead of N-phenylmaleimide used in Synthesis Example 1 and the total amount of styrene used was 50 parts. This resin had Mw of 6,200 and Mw / Mn of 1.5.
This resin is referred to as “alkali-soluble resin (B-3)”.

Preparation of pigment dispersion Preparation Example 1
(A) C.I. I. Pigment red 254 / C.I. I. Pigment Red 177 = 80/20 (weight ratio) 20 parts of a mixture, 5 parts of BYK-2001 as a dispersing agent (in terms of solid content), and 75 parts of propylene glycol monomethyl ether acetate as a solvent are treated with a bead mill to obtain a pigment dispersion. (R) was prepared.

Preparation Example 2
(A) C.I. I. Pigment green 36 / C.I. I. Pigment Yellow 150 = 50/50 (weight ratio) mixture, 5 parts of Solsperse 24000 as a dispersant (in terms of solid content), and 75 parts of propylene glycol monomethyl ether acetate as a solvent were treated with a bead mill to obtain a pigment dispersion ( G) was prepared.

Example 1
100 parts of pigment dispersion (R), 15 parts of the alkali-soluble resin (B-1) as the resin solution obtained in Synthesis Example 1 (in terms of solid content), (C) dipentaerythritol hexaacrylate as the polyfunctional monomer 10 parts and 5 parts trimellilol propane triacrylate, (D) 5 parts 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one as a photopolymerization initiator and 4, 4 ′ -3 parts of bis (diethylamino) benzophenone and propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (R) having a solid concentration of 25%.

The liquid composition (R) was evaluated by forming a pattern according to the following procedure.
<Formation of colored layer>
The liquid composition (R) is applied to a soda glass substrate having a silicon dioxide (SiO ₂ ) film formed on its surface to prevent elution of sodium ions using a spin coater, and then applied on a hot plate at 90 ° C. Pre-baking was performed for minutes to form a coating film having a thickness of 1.2 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 of 30 μm) using a high-pressure mercury lamp. The exposure amount at this time was 100 mJ / cm ² . Thereafter, the substrate was immersed in a 0.04% aqueous potassium hydroxide solution at 23 ° C. for 45 seconds, developed, washed with ultrapure water, and air-dried. Thereafter, post-baking was performed in a clean oven at 230 ° C. for 30 minutes to form a red stripe pixel pattern on the substrate.

<Evaluation>
When the pixel array on the substrate was observed with an optical microscope, no development residue was observed on the unexposed portion of the substrate, and no chipping was observed on the edge of the pixel pattern.
Further, when the cross section of the pixel pattern was observed with a scanning electron microscope (SEM), no undercut was observed and a pattern with a line width of 5 μm could be formed.
<Detergency evaluation>
A liquid composition (R) is applied on a glass substrate using a slit nozzle type color filter coating apparatus TR63210S-CL (trade name) manufactured by Tokyo Ohka Kogyo Co., Ltd., and then left to stand at room temperature for 1 hour to dry. Thus, a coating film was formed. Next, after blow-cleaning the slit nozzle of TR63210S-CL used with propylene glycol monomethyl ether acetate, the liquid composition (R) was applied again to a new glass substrate, and foreign matter was generated on the re-formed coating film. It was able to apply without.

Example 2
In Example 1, a green stripe pixel pattern was formed and evaluated in the same manner as in Example 1 except that the pigment dispersion (R) was changed to the pigment dispersion (G).
As a result, undercut was not recognized and a pattern with a line width of 5 μm could be formed. Further, in the cleaning property evaluation, the coating could be applied without generating foreign matter on the re-formed coating film.

Comparative Example 1
In Example 1, a red stripe pattern was formed and evaluated in the same manner as in Example 1 except that the alkali-soluble resin (B-1) was changed to the alkali-soluble resin (B-2).
As a result, no undercut was observed, and in the cleaning property evaluation, coating could be performed without generating foreign matter on the re-formed coating film, but it was impossible to form a pattern with a line width of 5 μm.

Comparative Example 2
In Example 1, except that the alkali-soluble resin (B-1) was changed to the alkali-soluble resin (B-3), evaluation was performed in the same manner as in Example 1 to form a red stripe pattern.
As a result, no undercut was observed, and in the cleaning property evaluation, coating could be performed without generating foreign matter on the re-formed coating film, but it was impossible to form a pattern with a line width of 5 μm.

Claims (5)

In the radiation-sensitive composition for forming a colored layer, comprising (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. A radiation sensitive material for forming a colored layer, wherein the resin contains a polymerizable unsaturated compound having a skeleton represented by the following formula (I) and a copolymer having an N-substituted maleimide as essential constituent components Composition.

  (B) Mw of alkali-soluble resin (where Mw is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran); the same shall apply hereinafter) is 1,000 to 10,000. The radiation-sensitive composition for forming a colored layer according to claim 1.   (B) Mw / Mn of alkali-soluble resin (where Mn is the number average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran); the same applies hereinafter) is 1.0 to 2.0. The radiation-sensitive composition for forming a colored layer according to claim 2, wherein the composition is a radiation-sensitive composition.   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 4.