JP4752649B2 - Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element - Google Patents

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 having a colored layer formed from the radiation-sensitive composition, and a color liquid crystal display device 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 color filter technical field, it has become the mainstream to reduce the exposure amount to shorten the tact time. However, in the conventional colored radiation-sensitive composition, if the exposure amount decreases, the remaining after development. It is difficult to obtain pixels and a black matrix with good pattern shape while shortening the tact time because the film rate is reduced, the pattern is chipped or undercut, and the pattern is easily peeled off from the substrate. . In terms of display performance, a color liquid crystal display element that does not cause defects such as image sticking and afterimage over the long term is strongly demanded. For this reason, the color filter has a reliability related to electrical characteristics such as voltage holding ratio. Although the demand for improving the property is increasing, it is actually difficult to meet the demand with the conventional colored radiation-sensitive composition.

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

  An object of the present invention is to provide a novel colored layer that is capable of producing a color filter that has no pattern defects such as chipping or undercut, has excellent adhesion to the substrate, and has excellent electrical characteristics and the like. The object is to provide a forming radiation-sensitive composition.

〔式（１）および式（２）において、各Ｒ ¹ は相互に独立に炭素数１〜１２の直鎖状、分岐状もしくは環状のアルキル基またはフェニル基を示し、各Ｒ ² は相互に独立に水素原子、炭素数１〜１２の直鎖状、分岐状もしくは環状のアルキル基またはフェニル基を示し、Ｒ ³ は水素原子または炭素数１〜１２の直鎖状、分岐状もしくは環状のアルキル基を示し、各Ｒ ⁴ 、各Ｒ ⁵ および各Ｒ ⁶ は相互に独立に水素原子または炭素数１〜６の直鎖状、分岐状もしくは環状のアルキル基を示す。但し、Ｒ ¹ 、Ｒ ² 、Ｒ ³ 、Ｒ ⁴ 、Ｒ ⁵ およびＲ ⁶ のアルキル基はそれぞれ、炭素数１〜６の直鎖状、分岐状もしくは環状のアルコキシル基、フェニル基およびハロゲン原子の群から選ばれる置換基で置換されてもよく、Ｒ ¹ およびＲ ² のフェニル基はそれぞれ、炭素数１〜６の直鎖状、分岐状もしくは環状のアルキル基、炭素数１〜６の直鎖状、分岐状もしくは環状のアルコキシル基、フェニル基およびハロゲン原子の群から選ばれる置換基で置換されてもよい。〕
本発明において、着色層とは、「画素および／またはブラックマトリックス」を意味する。 The present invention, first,
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. The resin has a copolymerization ratio of at least one selected from the group of (b1) unsaturated carboxylic acid or acid anhydride and unsaturated phenol compound, and (b2) a copolymer of N-substituted maleimide . The polymerization rate is 5 to 40% by weight , (b3) the copolymerization rate of the unsaturated compound having an allyl group is 5 to 40% by weight , and (b4) the copolymerization rate of the other unsaturated compound is 5 to 60% by weight. % and look containing a copolymer of, (D) a photopolymerization initiator, wherein the compound containing Mukoto represented by the compounds and / or the following formula represented by the following formula (1) (2) A radiation-sensitive composition for forming a colored layer.

[In the formulas (1) and (2), each R ¹ independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a phenyl group, and each R ² is independent from each other. Represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a phenyl group, and R ³ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. However, the alkyl groups of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each a group of straight, branched or cyclic alkoxyl groups having 1 to 6 carbon atoms, phenyl groups and halogen atoms. And the phenyl groups of R ¹ and R ² are each a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear group having 1 to 6 carbon atoms. Further, it may be substituted with a substituent selected from the group consisting of a branched or cyclic alkoxyl group, a phenyl group and a halogen atom. ]
In the present invention, the colored layer means “pixel and / or black matrix”.

The present invention secondly,
It consists of a color filter having a colored layer formed from the radiation-sensitive composition for forming the colored layer.

Third, the present invention
A color liquid crystal display element 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 a color index (CI; The Society of
Dyers and Colorists, Inc.) are classified as Pigment, and specifically, those having the following color index (CI) numbers are given.

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 violet 23;
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 inorganic pigments 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 green. , Cobalt green, amber, titanium black, synthetic iron black, carbon black and the like.

  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, 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 resin composition can be prepared by an appropriate method. When a pigment is used as a colorant, the pigment is used in a solvent in the presence of a dispersant, such as a bead mill or a roll mill. And mixing and dispersing while pulverizing to obtain a pigment dispersion, which may be (B) component, (C) component and (D) component described later, and additional solvent or other components described later if necessary. It is preferable to prepare by adding an additive and mixing.

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. 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 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 1,000 parts by weight, preferably 300 to 800 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 mixed solution 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 is selected from the group of (b1) unsaturated carboxylic acid or acid anhydride and unsaturated phenol compound (hereinafter these compounds are collectively referred to as “unsaturated compound (b1)”). At least one, (b2) an N-substituted maleimide, (b3) an unsaturated compound having an allyl group (hereinafter referred to as “unsaturated compound (b3)”), and (b4) an unsaturated compound other than the above. (Hereinafter referred to as “unsaturated compound (b4)”) (hereinafter referred to as “copolymer (BI)”), (A) acts as a binder for the colorant, and It is a component that is soluble in an alkaline developer used in the development processing step when forming the colored layer.

Among the unsaturated compounds (b1), as the unsaturated carboxylic acid or acid anhydride thereof, 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.
Of these unsaturated carboxylic acids or acid anhydrides thereof, succinic acid mono (2-acryloyloxyethyl) and phthalic acid mono (2-acryloyloxyethyl) are respectively light ester HOA-MS and light ester HOA-MPE ( As mentioned above, it is marketed under the trade name of Kyoeisha Chemical Co., Ltd.

Examples of the unsaturated phenol compound include:
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.

  In the present invention, the unsaturated compound (b1) includes (meth) acrylic acid, succinic acid mono [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, p-vinylphenol, and the like. Particularly preferred is (meth) acrylic acid.

  Examples of the N-substituted maleimide include N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, Ni-propylmaleimide, Nn-butylmaleimide, Nt-butylmaleimide, N- Examples thereof include n-hexylmaleimide, N-cyclopentylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-1-naphthylmaleimide and the like.

In the present invention, as the N-substituted maleimide, N-cyclohexylmaleimide, N-phenylmaleimide and the like are preferable, and N-phenylmaleimide is particularly preferable.
The N-substituted maleimides can be used alone or in admixture of two or more.

As the unsaturated compound (b3), a compound having only an allyl group as a polymerizable unsaturated bond, a compound having an allyl group and another polymerizable unsaturated bond as a polymerizable unsaturated bond (hereinafter referred to as “unsaturated compound ( b3-I) ")) and the like, and an unsaturated compound (b3-I) is preferable.
Examples of the unsaturated compound (b3) include unsaturated compounds (b3-I) such as allyl (meth) acrylate, allyl crotonate, allyl α-chloroacrylate, allyl cinnamate, monoallyl maleate, monoallyl fumarate and the like. And allyl acetate, allyl propionate, allyl butyrate, allyl benzoate, monoallyl succinate, monoallyl phthalate, allyl methyl ether, allyl ethyl ether, allyl glycidyl ether, p-allyl benzyl methyl ether, p-allyl benzyl glycidyl ether, etc. Can be mentioned.
In the present invention, as the unsaturated compound (b3), allyl (meth) acrylate is particularly preferable.
The unsaturated compound (b3) can be used alone or in admixture of two or more.

As the unsaturated compound (b4), 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-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl ( (Meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydi Unsaturated carboxylic acid esters such as propylene glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and glycerol mono (meth) acrylate Kind;

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;
Vinyl ethers such as vinyl methyl ether and vinyl ethyl 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 present invention, the unsaturated compound (b4) is preferably an aromatic vinyl compound, an unsaturated carboxylic acid ester, a macromonomer or the like, and particularly styrene, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer, polymethylmethacrylate macromonomer and the like are preferable.
The unsaturated compound (b4) can be used alone or in admixture of two or more.

  In the present invention, the copolymer (B1) is at least one selected from the group of at least one unsaturated compound (b1) having (meth) acrylic acid as an essential component, N-cyclohexylmaleimide and N-phenylmaleimide. One N-substituted maleimide, at least one unsaturated compound (b3) selected from the group of allyl acrylate and allyl methacrylate, styrene, methyl (meth) acrylate, n-butyl (meth) acrylate, 2- A small amount selected from the group of ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer. Kutomo one unsaturated compound (b4), a copolymer (hereinafter, referred to as "copolymer (BII)".) Are preferred.

As specific examples of the copolymer (BII),
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / methyl (meth) acrylate / n-butyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / methyl (meth) acrylate / 2-ethylhexyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / methyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / n-butyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / 2-ethylhexyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / n-butyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / methyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / 2-hydroxyethyl (meth) acrylate copolymer (meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / n-butyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / phenyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,

(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / methyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / methyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / methyl (meth) acrylate / n-butyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / methyl (meth) acrylate / n-butyl (meth) acrylate / polymethyl methacrylate macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / n-butyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / n-butyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,

(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer,

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

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / n-butyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / methyl (meth) acrylate / n-butyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / methyl (meth) acrylate / 2-ethylhexyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / n-butyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / 2-ethylhexyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,

(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / methyl (meth) acrylate / n-butyl (meth) acrylate / 2-hydroxyethyl (meta ) Acrylate copolymer, (meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / methyl (meth) acrylate / 2-ethylhexyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth ) Acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / 2-ethylhexyl (meth) acrylate / 2-hydroxyethyl (meth) acrylate / benzyl (meth ) Acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / n-butyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate Coalescence,

(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-cyclohexylmaleimide / allyl methacrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / allyl methacrylate / styrene / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,
(Meth) acrylic acid / ω-carboxypolycaprolactone mono (meth) acrylate / N-phenylmaleimide / allyl methacrylate / styrene / n-butyl (meth) acrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer Or
Examples include copolymers in which allyl methacrylate in these copolymers is replaced with allyl acrylate.

Of the copolymer (BII),
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / N-phenylmaleimide / allyl methacrylate / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / 2-hydroxyethyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / benzyl (meth) acrylate copolymer,
(Meth) acrylic acid / succinic acid mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate copolymer is preferred. .

In copolymer (BI), the copolymerization ratio of unsaturated compound (b1) is 5 to 30% by weight, the copolymerization ratio of N-substituted maleimide is 5 to 40% by weight, and unsaturated compound The copolymerization ratio of (b3) is 5 to 40% by weight, and the copolymerization ratio of the unsaturated compound (b4) is 5 to 60% by weight.
In the present invention, by setting the copolymerization ratio of each unsaturated compound in the copolymer (BI) to the above range, a radiation-sensitive composition excellent in sensitivity, substrate adhesion, and solvent resistance can be obtained. .

In the present invention, other alkali-soluble resins can be used in combination with the copolymer (BI).
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 is preferable, and examples thereof include at least one selected from the group of unsaturated carboxylic acids exemplified for the copolymer (BI) and acid anhydrides thereof. And a copolymer with at least one selected from the group of N-substituted maleimides and unsaturated compounds (b4) exemplified for the copolymer (BI).

  More specifically, other preferable alkali-soluble resins include (i) at least one unsaturated carboxylic acid having (meth) acrylic acid as an essential component, and (ii) N-cyclohexylmaleimide and N-phenylmaleimide. , Styrene, methyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) ) A copolymer with at least one selected from the group of acrylate, polystyrene macromonomer and polymethyl methacrylate macromonomer.

In the present invention, polystyrene-converted weight average molecular weights (hereinafter referred to as “Mw”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the copolymer (BI) and other alkali-soluble resins are respectively shown. Usually, it is 2,000 to 300,000, preferably 3,000 to 100,000.
The number average molecular weight in terms of polystyrene (hereinafter referred to as “Mn”) measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the copolymer (BI) and other alkali-soluble resins is usually as follows. It is 3,000-60,000, preferably 5,000-25,000.
In the present invention, the copolymer (BI) having the specific Mw and Mn is used, or the copolymer (BI) and another alkali-soluble resin having the specific Mw and Mn are used in combination. Thus, 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 on the unexposed portion of the substrate and the light-shielding layer during development. Residues, dirt, film residue, etc. are less likely to occur.
Moreover, the ratio (Mw / Mn) of Mw and Mn of the copolymer (BI) and other alkali-soluble resins is preferably 1 to 5, and more preferably 1 to 4, respectively.

In this invention, a copolymer (BI) 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 decrease, or there is a possibility that background stain 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 (BI) in alkali-soluble resin becomes like this. Preferably it is 10-100 weight%, Most preferably, it is 20-100 weight%. In this case, if the proportion of the copolymer (BI) 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,

Compound represented by the following formula (3)

And a compound represented by the following formula (4):

In particular, trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate have high strength of the colored layer, excellent surface smoothness of the colored layer, and on the unexposed substrate and the light shielding layer. It is preferable in that ground stains, film residues and the like are hardly generated on the top.
The said 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, 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 the compounds exemplified for the unsaturated compound (b1), N-substituted maleimide and unsaturated compound (b4) in the alkali-soluble resin, N- In addition to (meth) acryloylmorpholine, N-vinylpyrrolidone, N-vinyl-ε-caprolactam, commercially available products include M-5600 (trade name, manufactured by Toagosei Co., Ltd.) and the like.
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, 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.

  The total use amount of the polyfunctional monomer and the monofunctional monomer in the present invention is usually 5 to 500 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the (B) alkali-soluble resin. Part. 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 a compound represented by the formula (1) (hereinafter referred to as “oxime compound (D1)”) and / or a compound represented by the formula (2) (hereinafter, “ Oxime-based compound (D2) ”), and exposure to radiation such as visible light, ultraviolet light, far ultraviolet light, charged particle beam, X-ray, etc. It consists of components that generate active species capable of initiating polymerization of functional monomers.
In the present invention, as a photopolymerization initiator other than the oxime compound (D1) and the oxime compound (D2) (hereinafter referred to as “other photopolymerization initiator”) , for example, the following formula (5-1), Biimidazole compound having at least one main skeleton represented by formula (5-2) or formula (5-3), benzoin compound, acetophenone compound, benzophenone compound, α-diketone compound, polynuclear quinone compound Examples include compounds, xanthone compounds, phosphine compounds, triazine compounds, and the like.

In formula (1) and formula (2), examples of the linear, branched or cyclic alkyl group having 1 to 12 carbon atoms of R ¹ , R ² and R ³ include, for example, a methyl group, an ethyl group, n- Propyl group, i-propyl group, n-butyl group, i-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, cyclopentyl group, cyclohexyl group and the like can be mentioned.

Examples of the linear, branched or cyclic alkyl group having 1 to ⁶ carbon atoms of R ⁴ , R ⁵ and R ⁶ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n -Butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like can be mentioned.

Of the substituents for the alkyl groups of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , and the substituents for the phenyl groups of R ¹ and R ² , a straight chain having 1 to 6 carbon atoms Examples of the branched or cyclic alkoxyl group include a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, an n-butoxy group, and a t-butoxy group. As the halogen atom, For example, a fluorine atom, a chlorine atom, etc. can be mentioned.
Among the substituents for each phenyl group of R ¹ and R ² , examples of the linear, branched or cyclic alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, an n-propyl group, An i-propyl group, an n-butyl group, a t-butyl group, etc. can be mentioned.
In each alkyl group and each phenyl group, one or more substituents can be present.

In Formula (1) and Formula (2), R ¹ is preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a phenyl group or the like, and R ² is a hydrogen atom , methyl group, ethyl group, n- propyl group, i- propyl, n- butyl, n- pentyl, n- hexyl, n- heptyl, preferably such as n- octyl group, a R ³ is A hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group and the like are preferable. Further, as R ⁴ , R ⁵ and R ⁶ , a hydrogen atom, a methyl group, an ethyl group, n- A propyl group, i-propyl group, n-butyl group and the like are preferable.

  Specific examples of the preferred oxime compound (D1) include 1- [4- (phenylthio) phenyl] -octane-1-one-2-oneoxime-O-acetate, 1- [4- (2-methylphenylthio) Phenyl] -octane-1-one-2-one oxime-O-acetate, 1- [4- (2,4,6-trimethylphenylthio) phenyl] -octane-1-one-2-one oxime-O-acetate, 1- [4- (2-Ethylphenylthio) phenyl] -octane-1-one-2-one oxime-O-acetate, 1- [4- (phenylthio) phenyl] -octane-1-one-2-one oxime- O-benzoate, 1- [4- (2-methylphenylthio) phenyl] -octane-1-one-2-oneoxime-O-benzoate, 1- [4 (2,4,6-trimethylphenylthio) phenyl] -octane-1-one-2-oneoxime-O-benzoate, 1- [4- (2-ethylphenylthio) phenyl] -octane-1-one-2 -Onoxime-O-benzoate and the like can be mentioned.

  Specific examples of preferred oxime compounds (D2) include 1- [9-ethyl-6-benzoyl-9. H. -Carbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2,4,6-trimethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-n-butyl-6- (2-ethylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-benzoate and the like.

  Of these oxime compounds (D1) and oxime compounds (D2), oxime compounds (D2) are more preferred, and in particular, 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate is preferred.

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′-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,
Examples include 2,2′-bis (2,4,6-tribromophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole.

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 and 2,2′-bis (2,4,6-trichlorophenyl) -4,4 ′, 5 , 5′-tetraphenyl-1,2′-biimidazole is preferred, in particular 2,2′-bis (2-chlorophenyl) -4,4 ′, 5,5′-tetraphenyl-1,2′-biimidazole. Imidazole is preferred.
The biimidazole compound is excellent in solubility in a solvent, does not generate foreign matters such as undissolved substances and precipitates, has high sensitivity, sufficiently advances the curing reaction by exposure with a small amount of energy, and has a contrast. It is high and does not cause a curing reaction in the unexposed area. Accordingly, it is possible to form a high-definition pattern array in which pixel patterns and black matrix patterns without undercuts are arranged according to a predetermined arrangement.

Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and methyl 2-benzoylbenzoate.
Examples of the acetophenone compounds include 2,2-dimethoxyacetophenone, 2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2-hydroxy-2-methyl-1-phenylpropane-1- ON, 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 phenyl ketone 2,2-dimethoxy-1,2-diphenylethane-1-one and the like.

Examples of the benzophenone compounds 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, 2-chlorothioxanthone, and the like.
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-ethoxy) Styryl) -4,6-bis (trichloromethyl) -s-triazine, 2-(4-n-butoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine,

Compound represented by the following formula (6)

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。 And a compound represented by the following formula (7):

Examples thereof include compounds having a halomethyl group.

In the present invention, other photopolymerization initiator, biimidazole compounds, acetophenone compounds, triazine-based compounds have preferred.
In the present invention, the oxime compound (D1) and the oxime compound (D2) can be used alone or in admixture of two or more, and the other photopolymerization initiators can be used alone or in combination of two kinds. The above can be mixed and used.
The amount of the photopolymerization initiator used in the present invention is usually 0.01 to 200 with respect to a total of 100 parts by weight of (C) the polyfunctional monomer and the monofunctional monomer optionally used. Part by weight, preferably 1 to 120 parts by weight, particularly preferably 1 to 100 parts by weight. In this case, if the amount of the photopolymerization initiator used is less than 0.01 parts by weight, curing by exposure becomes insufficient, and it becomes 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.
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 photopolymerization initiator as necessary.

-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 that has an action of further improving the solubility characteristics of the radiation-sensitive composition in an alkaline developer and further suppressing the residual of undissolved material after development. Can do.

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 thereof 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 whole 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;
Methylethylamine, 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.

Among these organic amino compounds, mono (cyclo) alkanolamines are used as aliphatic amines from the viewpoints of solubility in the solvent described later, prevention of soiling and film residue on the unexposed portion of the substrate or the light shielding layer, and the like. And amino (cyclo) alkanediols are preferred, in particular 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino -1,3-propanediol, 4-amino-1,2-butanediol and the like are preferable. Moreover, as a phenyl group containing amine, aminophenols are preferable and 2-aminophenol, 3-aminophenol, 4-aminophenol, etc. are especially preferable.
The organic amino compounds can be used alone or in admixture of two or more.
The amount of the organic amino compound used is usually 15% by weight or less, preferably 10% by weight or less, based on the whole radiation-sensitive composition. In this case, when the usage-amount of an organic amino compound exceeds 15 weight%, there exists a tendency for the adhesiveness with respect to the board | substrate of the formed colored layer to fall.

Furthermore, as an additive other than the organic acid and the organic amino compound, 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 2,6-di-t-butylphenol;
UV absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, alkoxybenzophenones;
Anti-agglomeration agents such as sodium polyacrylate;
Examples thereof 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 contains 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-methyl-3-methoxybutyl acetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, n-butyl acetate, i-acetate Butyl, 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, ethyl acetoacetate, ethyl 2-oxobutanoate Other esters;
Aromatic hydrocarbons such as toluene and xylene;
Examples include amides or lactams such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methylpyrrolidone.

Among these solvents, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl from the viewpoints of solubility, pigment dispersibility, coatability, etc. Ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-acetate -Butyl, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, i-propyl butyrate, n-butyl butyrate, Ethyl Rubin acid 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 point solvent such as diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can be used in combination.
These high-boiling 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 has a colored layer formed from 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, the coating film is exposed through a photomask, and then developed using an alkali developer to dissolve and remove the unexposed portions of the coating film, and then post-baked to form a 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.
Further, the black matrix can be formed in the same manner as in the case of forming the pixel by using a liquid composition of a radiation sensitive composition in which a black pigment is dispersed, for example.

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 employed, a spin coating method and a slit die coating method 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, 1, 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 contains the components (A) to (D) as essential components. Specific examples of particularly preferred compositions are as follows. (D)
(A) (B) A radiation-sensitive composition for forming a colored layer, wherein the alkali-soluble resin contains a copolymer (BII).
(B) (C) The radiation sensitive material for forming a colored layer according to (a), wherein the polyfunctional monomer is at least one selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate. Sex composition.
(C) The radiation-sensitive composition for forming a colored layer according to (a) or (b), wherein the other photopolymerization initiator is at least one selected from the group consisting of biimidazole compounds, acetophenone compounds, and triazine compounds. .
(D) (A) The radiation-sensitive composition for forming a colored layer according to (a), (b) or (c) above, wherein the colorant comprises an organic pigment or carbon black.

Further, the preferred color filter of the present invention is
(E) It has a pixel and / or a black matrix formed from the radiation-sensitive composition for forming a colored layer of the above (a), (b), (c) or (d).

The preferred color liquid crystal display element of the present invention is
(F) comprising the color filter of (e),
Further preferred color liquid crystal display elements of the present invention are:
(G) The color filter described in (e) is provided on the thin film transistor substrate array.

The radiation-sensitive composition for forming a colored layer of the present invention is free of pattern defects such as chipping and undercutting, and has excellent adhesion to the substrate, and in addition, excellent electrical characteristics such as voltage holding ratio, A color filter having high reliability can be provided.
Therefore, the radiation-sensitive composition for forming a colored layer of the present invention can be used very suitably for the production of various color filters including color filters for color liquid crystal display elements in the electronic industry.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the following examples.
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 (manufactured by Showa Denko KK).
Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 were used in combination.
Mobile phase: Tetrahydrofuran containing 0.5% by weight of phosphoric acid.

Synthesis example 1
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobisvaleronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 20 parts by weight of methacrylic acid and mono (2-methacryloyloxyethyl succinate). ) 10 parts by weight, 31.2 parts by weight of N-phenylmaleimide, 20 parts by weight of allyl methacrylate, 18.8 parts by weight of styrene, and 7 parts by weight of α-methylstyrene dimer as a chain transfer agent. The reaction solution was heated to 70 ° C. while stirring and polymerized for 2 hours while maintaining this temperature. Thereafter, 2 parts by weight of 2,2′-azobisvaleronitrile was added, and the polymerization was further continued for 2 hours to obtain a resin solution (solid content concentration = 32.8% by weight). This resin had Mw = 12,000 and (Mw / Mn) = 2.8.
This resin solution is referred to as “resin solution (heavy s-1)”, and this resin is referred to as “resin (heavy a-1)”.

Synthesis example 2
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobisvaleronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 20 parts by weight of methacrylic acid and mono (2-methacryloyloxyethyl succinate). ) 5.0 parts by weight, 31.2 parts by weight of N-phenylmaleimide, 20 parts by weight of allyl methacrylate, 18.8 parts by weight of styrene, 5.0 parts by weight of benzyl methacrylate and 7 parts by weight of α-methylstyrene dimer, After substituting with nitrogen, the reaction solution was heated to 70 ° C. while gently stirring and polymerized for 2 hours while maintaining this temperature. Thereafter, 2 parts by weight of 2,2′-azobisvaleronitrile was added, and the polymerization was further continued for 2 hours to obtain a resin solution (solid content concentration = 32.8% by weight). This resin had Mw = 11,000 and (Mw / Mn) = 2.6.
This resin solution is referred to as “resin solution (heavy s-2)”, and this resin is referred to as “resin (heavy a-2)”.

Synthesis example 3
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobisvaleronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 10 parts by weight of methacrylic acid and 31.2 parts by weight of N-phenylmaleimide. , 20 parts by weight of allyl methacrylate, 18.8 parts by weight of styrene, 15 parts by weight of 2-hydroxyethyl methacrylate, 5.0 parts by weight of benzyl methacrylate and 5 parts by weight of α-methylstyrene dimer, and after the nitrogen substitution, While stirring, the temperature of the reaction solution was raised to 70 ° C., and polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, 2 parts by weight of 2,2′-azobisvaleronitrile was added, and polymerization was continued for another 2 hours to obtain a resin solution (solid content concentration = 32.5% by weight). This resin had Mw = 11,000 and (Mw / Mn) = 2.9.
This resin solution is referred to as “resin solution (heavy s-3)”, and this resin is referred to as “resin (heavy a-3)”.

Synthesis example 4
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobisvaleronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 10 parts by weight of methacrylic acid and 31.2 parts by weight of N-phenylmaleimide. Then, 30 parts by weight of allyl methacrylate, 18.8 parts by weight of styrene, 10 parts by weight of 2-hydroxyethyl methacrylate, and 7 parts by weight of α-methylstyrene dimer were charged, and after replacing with nitrogen, the reaction solution was stirred while gently stirring. The temperature was raised to 0 ° C., and this temperature was maintained for polymerization for 2 hours. Thereafter, 2 parts by weight of 2,2′-azobisvaleronitrile was added, and the polymerization was further continued for 2 hours to obtain a resin solution (solid content concentration = 31.9% by weight). This resin had Mw = 12,000 and (Mw / Mn) = 2.8.
This resin solution is referred to as “resin solution (heavy s-4)”, and this resin is referred to as “resin (heavy a-4)”.

Synthesis example 5
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobisvaleronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 20 parts by weight of methacrylic acid and mono (2-methacryloyloxyethyl succinate). ) 10 parts by weight, 31.2 parts by weight of N-phenylmaleimide, 20 parts by weight of benzyl methacrylate, 18.8 parts by weight of styrene, and 7 parts by weight of α-methylstyrene dimer were substituted with nitrogen, and then gently stirred. The reaction solution was heated to 70 ° C. and polymerized for 2 hours while maintaining this temperature. Thereafter, 2 parts by weight of 2,2′-azobisvaleronitrile was added, and the polymerization was further continued for 2 hours to obtain a resin solution (solid content concentration = 32.8% by weight). This resin had Mw = 12,000 and (Mw / Mn) = 2.8.
This resin solution is referred to as “resin solution (heavy s-5)”, and this resin is referred to as “resin (heavy a-5)”.

Synthesis Example 6
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobisvaleronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 20 parts by weight of methacrylic acid and mono (2-methacryloyloxyethyl succinate). 10 parts by weight, 20 parts by weight of allyl methacrylate, 18.8 parts by weight of styrene, 31.2 parts by weight of benzyl methacrylate and 7 parts by weight of α-methylstyrene dimer (chain transfer agent) While stirring, the temperature of the reaction solution was raised to 80 ° C., and this temperature was maintained for polymerization for 2 hours. Thereafter, the temperature of the reaction solution was raised to 100 ° C., 2 parts by weight of 2,2′-azobisvaleronitrile was added, and polymerization was continued for another 2 hours to obtain a resin solution (solid content concentration = 32.8 wt. %). This resin had Mw = 15,000 and (Mw / Mn) = 3.0.
This resin solution is referred to as “resin solution (heavy s-6)”, and this resin is referred to as “resin (heavy a-6)”.

Synthesis example 7
A flask equipped with a condenser and a stirrer was charged with 5 parts by weight of 2,2′-azobisvaleronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate, followed by 20 parts by weight of methacrylic acid and mono (2-methacryloyloxyethyl succinate). ) 10 parts by weight, 18.8 parts by weight of styrene, 51.2 parts by weight of benzyl methacrylate and 7 parts by weight of α-methylstyrene dimer were charged, and after replacing with nitrogen, the reaction solution was raised to 70 ° C. while gently stirring. The polymerization was carried out for 2 hours while maintaining the temperature. Thereafter, 2 parts by weight of 2,2′-azobisvaleronitrile was added, and the polymerization was further continued for 2 hours to obtain a resin solution (solid content concentration = 32.8% by weight). This resin had Mw = 12,000 and (Mw / Mn) = 2.8.
This resin solution is referred to as “resin solution (heavy s-7)”, and this resin is referred to as “resin (heavy a-7)”.

[Evaluation of chipping and adhesion]
Example 1
(A) C.I. I. Pigment red 254 and C.I. I. A mixture of 40 parts by weight of a 50/50 (weight ratio) mixture with Pigment Yellow 139, 10 parts by weight of Disperbyk 2001 as a dispersant, and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent was added to Diamond Fine Mill (trade name). A pigment dispersion was prepared by mixing and dispersing for 12 hours using a bead mill (bead diameter: 1.0 mm) manufactured by Mitsubishi Materials Corporation.
Next, 100 parts by weight of this pigment dispersion, (B) an amount of resin solution (heavy s-1) as an alkali-soluble resin, 70 parts by weight of resin (heavy a-1), and (C) a polyfunctional monomer As dipentaerythritol hexaacrylate, and (D) 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (r-1). .
Subsequently, after apply | coating a liquid composition (r-1) on a soda glass substrate, each wavelength of 365 nm, 405 nm, and 436 nm is included in a coating film through a 90 micron stripe pattern photomask using a high pressure mercury lamp. radiation was exposed at an exposure amount of 5,000J / m ^2. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, no chipping of the pattern was observed, and the adhesion with the substrate was good.

Example 2
A liquid composition was obtained in the same manner as in Example 1 except that the resin solution (heavy s-2) was used in an amount that would result in 70 parts by weight of the resin (heavy a-2) instead of the resin solution (heavy s-1). A product (r-2) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, no chipping of the pattern was observed, and the adhesion with the substrate was good.

Example 3
A liquid composition was obtained in the same manner as in Example 1 except that the resin solution (heavy s-3) was used in such an amount that the resin (heavy a-3) was 70 parts by weight instead of the resin solution (heavy s-1). A product (r-3) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, no chipping of the pattern was observed, and the adhesion with the substrate was good.

Example 4
A liquid composition was obtained in the same manner as in Example 1 except that the resin solution (heavy s-4) was used instead of the resin solution (heavy s-1) in such an amount that the resin (heavy a-4) was 70 parts by weight. A product (r-4) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, no chipping of the pattern was observed, and the adhesion with the substrate was good.

Comparative Example 1
A liquid composition was obtained in the same manner as in Example 1 except that the resin solution (heavy s-5) was used instead of the resin solution (heavy s-1) in such an amount that the resin (heavy a-5) was 70 parts by weight. A product (r-5) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, no chipping of the pattern was observed, and the adhesion with the substrate was good.

Example 5
(A) C.I. I. Pigment blue 15: 6 and C.I. I. Diamond Fine Mill (trade name) was prepared by mixing 40 parts by weight of a 90/10 (weight ratio) mixture with Pigment Violet 23, 10 parts by weight of Disperbyk 2001 as a dispersant, and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent. A pigment dispersion was prepared by mixing and dispersing for 12 hours using a bead mill (bead diameter: 1.0 mm) manufactured by Mitsubishi Materials Corporation.
Next, 100 parts by weight of this pigment dispersion, (B) resin solution (heavy s-1) as an alkali-soluble resin, amount of resin (heavy a-1) to be 80 parts by weight, (C) polyfunctional monomer As dipentaerythritol hexaacrylate and (D) 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (r-6). .
Subsequently, after apply | coating a liquid composition (r-6) on a soda glass substrate, each wavelength of 365 nm, 405 nm, and 436 nm is included in a coating film through a 90 micron stripe pattern photomask using a high pressure mercury lamp. radiation was exposed at an exposure amount of 5,000J / m ^2. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, no chipping of the pattern was observed, and the adhesion with the substrate was good.

Example 6
A liquid composition was obtained in the same manner as in Example 5 except that the resin solution (heavy s-2) was used instead of the resin solution (heavy s-1) in an amount such that the resin (heavy a-2) was 80 parts by weight. A product (r-7) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, no chipping of the pattern was observed, and the adhesion with the substrate was good.

Example 7
A liquid composition was obtained in the same manner as in Example 5 except that the resin solution (heavy s-3) was used instead of the resin solution (heavy s-1) in such an amount that the resin (heavy a-3) was 80 parts by weight. A product (r-8) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, no chipping of the pattern was observed, and the adhesion with the substrate was good.

Example 8
A liquid composition was obtained in the same manner as in Example 5 except that the resin solution (heavy s-4) was used instead of the resin solution (heavy s-1) in such an amount that the resin (heavy a-4) was 80 parts by weight. A product (r-9) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, no chipping of the pattern was observed, and the adhesion with the substrate was good.

Comparative Example 2
A liquid composition was obtained in the same manner as in Example 5 except that the resin solution (heavy s-5) was used instead of the resin solution (heavy s-1) in such an amount that the resin (heavy a-5) was 80 parts by weight. A product (r-10) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, no chipping of the pattern was observed, and the adhesion with the substrate was good.

Example 9
(A) C.I. I. Pigment Green 36 and C.I. I. A mixture of 40 parts by weight of a 50/50 (weight ratio) mixture with Pigment Yellow 150, 10 parts by weight of Disperbyk 2001 as a dispersant, and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent was added to Diamond Fine Mill (trade name). A pigment dispersion was prepared by mixing and dispersing for 12 hours using a bead mill (bead diameter: 1.0 mm) manufactured by Mitsubishi Materials Corporation.
Next, 100 parts by weight of this pigment dispersion, (B) resin solution (heavy s-1) as an alkali-soluble resin, amount of resin (heavy a-1) to be 80 parts by weight, (C) polyfunctional monomer As dipentaerythritol hexaacrylate and (D) 1- [9-ethyl-6- (2-methylbenzoyl) -9. H. -Carbazol-3-yl] -ethane-1-one oxime-O-acetate and 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent were mixed to prepare a liquid composition (r-11). .
Next, after applying the liquid composition (r-11) onto a soda glass substrate, the coating film contains wavelengths of 365 nm, 405 nm, and 436 nm through a 90 micron stripe pattern photomask using a high-pressure mercury lamp. radiation was exposed at an exposure amount of 5,000J / m ^2. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, no chipping of the pattern was observed, and the adhesion with the substrate was good.

Example 10
A liquid composition was obtained in the same manner as in Example 9 except that the resin solution (heavy s-2) was used instead of the resin solution (heavy s-1) in such an amount that the resin (heavy a-2) was 80 parts by weight. A product (r-12) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, no chipping of the pattern was observed, and the adhesion with the substrate was good.

Example 11
A liquid composition was obtained in the same manner as in Example 9 except that the resin solution (heavy s-3) was used instead of the resin solution (heavy s-1) in such an amount that the resin (heavy a-3) was 80 parts by weight. A product (r-13) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, no chipping of the pattern was observed, and the adhesion with the substrate was good.

Example 12
A liquid composition was obtained in the same manner as in Example 9 except that the resin solution (heavy s-4) was used instead of the resin solution (heavy s-1) in such an amount that the resin (heavy a-4) was 80 parts by weight. A product (r-14) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, no chipping of the pattern was observed, and the adhesion with the substrate was good.

Comparative Example 3
A liquid composition was obtained in the same manner as in Example 9 except that the resin solution (heavy s-5) was used instead of the resin solution (heavy s-1) in such an amount that the resin (heavy a-5) was 80 parts by weight. A product (r-15) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, no chipping of the pattern was observed, and the adhesion with the substrate was good.

Comparative Example 4
A liquid composition was obtained in the same manner as in Example 1 except that the resin solution (heavy s-6) was used instead of the resin solution (heavy s-1) in such an amount that the resin (heavy a-6) was 70 parts by weight. A product (r-16) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, a large number of chips were observed in the pattern, and a portion where the pattern was partially peeled off from the substrate was also observed.

Comparative Example 5
A liquid composition was obtained in the same manner as in Example 1 except that the resin solution (heavy s-7) was used instead of the resin solution (heavy s-1) in an amount such that the resin (heavy a-7) was 70 parts by weight. A product (r-17) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, a large number of chips were observed in the pattern, and a portion where the pattern was partially peeled off from the substrate was also observed.

Comparative Example 6
A liquid composition was obtained in the same manner as in Example 5 except that the resin solution (heavy s-6) was used instead of the resin solution (heavy s-1) in an amount such that the resin (heavy a-6) was 80 parts by weight. A product (r-18) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, a large number of chips were observed in the pattern, and a portion where the pattern was partially peeled off from the substrate was also observed.

Comparative Example 7
A liquid composition was obtained in the same manner as in Example 5 except that the resin solution (heavy s-7) was used instead of the resin solution (heavy s-1) in such an amount that the resin (heavy a-7) was 80 parts by weight. A product (r-19) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, a large number of chips were observed in the pattern, and a portion where the pattern was partially peeled off from the substrate was also observed.

Comparative Example 8
A liquid composition was obtained in the same manner as in Example 9 except that the resin solution (heavy s-6) was used instead of the resin solution (heavy s-1) in such an amount that the resin (heavy a-6) was 80 parts by weight. A product (r-20) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, a large number of chips were observed in the pattern, and a number of locations where the pattern was partially peeled off from the substrate were observed.

Comparative Example 9
A liquid composition was obtained in the same manner as in Example 9 except that the resin solution (heavy s-7) was used instead of the resin solution (heavy s-1) in such an amount that the resin (heavy a-7) was 80 parts by weight. A product (r-21) was prepared and applied on a soda glass substrate.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² through a 90-micron stripe pattern photomask. Thereafter, the substrate was immersed in a developer composed of a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, and air-dried.
Next, when the obtained stripe pattern was observed with a scanning electron microscope, a large number of chips were observed in the pattern, and a number of locations where the pattern was partially peeled off from the substrate were observed.

[Evaluation of voltage holding ratio]
Each liquid composition of Examples 1-12 and Comparative Examples 1-9 was formed with a SiO ₂ film to prevent elution of sodium ions on the surface, and further deposited an ITO (indium-tin oxide alloy) electrode in a predetermined shape. After coating on a soda glass substrate using a spin coater, prebaking was performed in a clean oven at 90 ° C. for 10 minutes to form a coating film having a thickness of 1.8 μm.
Next, using a high-pressure mercury lamp, the coating film was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure amount of 5,000 J / m ² without using a photomask. Thereafter, the substrate is immersed in a developer comprising a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air-dried, and further post-baked at 230 ° C. for 30 minutes. And the coating film was cured to form red pixels on the substrate. The film thickness of this pixel was 1.5 μm.
Next, the substrate on which this pixel is formed and the substrate on which the ITO electrode is simply deposited in a predetermined shape are bonded together with a sealing agent mixed with 0.018 mm glass beads, and then a liquid crystal MLC6608 (trade name) manufactured by Merck is used. The liquid crystal cell was manufactured by pouring.
Next, the liquid crystal cell was placed in a constant temperature layer of 60 ° C., and the voltage holding ratio of the liquid crystal cell was measured by a liquid crystal voltage holding ratio measuring system VHR-1A type (trade name) manufactured by Toyo Technica Co., Ltd. Were measured under the conditions of a square wave and a measurement frequency of 60 Hz.
Here, the voltage holding ratio is a value calculated by (potential difference of liquid crystal cell 16.7 milliseconds after voltage application) / (voltage immediately after voltage application).
The measurement results of the voltage holding ratio are shown in Table 1 together with the presence / absence of N-phenylmaleimide and allyl methacrylate in the alkali-soluble resin, and the evaluation results of chipping and adhesion. When the voltage holding ratio of the liquid crystal cell is 90% or less, the liquid crystal cell cannot hold the applied voltage at a predetermined level, which means that the liquid crystal cannot be sufficiently aligned.

Claims (3)

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. The resin has a copolymerization ratio of at least one selected from the group of (b1) unsaturated carboxylic acid or acid anhydride and unsaturated phenol compound, and (b2) a copolymer of N-substituted maleimide . The polymerization rate is 5 to 40% by weight , (b3) the copolymerization rate of the unsaturated compound having an allyl group is 5 to 40% by weight , and (b4) the copolymerization rate of the other unsaturated compound is 5 to 60% by weight. % and look containing a copolymer of, (D) a photopolymerization initiator, wherein the compound containing Mukoto represented by the compounds and / or the following formula represented by the following formula (1) (2) A radiation-sensitive composition for forming a colored layer.

[In the formulas (1) and (2), each R ¹ independently represents a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a phenyl group, and each R ² is independent from each other. Represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms or a phenyl group, and R ³ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms. R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. However, the alkyl groups of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each a group of straight, branched or cyclic alkoxyl groups having 1 to 6 carbon atoms, phenyl groups and halogen atoms. And the phenyl groups of R ¹ and R ² are each a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, or a linear group having 1 to 6 carbon atoms. Further, it may be substituted with a substituent selected from the group consisting of a branched or cyclic alkoxyl group, a phenyl group and a halogen atom. ]   A color filter having a colored layer formed from the radiation-sensitive composition for forming a colored layer according to claim 1. A color liquid crystal display device comprising the color filter according to claim 2 .