KR20080006483A - Radiation-sensitive composition for forming a colored layer, color filter and color liquid crystal display device - Google Patents

Abstract

A radiation-sensitive composition for forming a colored layer is provided to prevent pattern defects such as a loss or undercut of a pattern and produce a color filter having good reliability in electrical characteristics, etc. A radiation-sensitive composition for forming a colored layer includes (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. The (B) alkali-soluble resin comprises a copolymer of (b1) at least one selected from the group consisting of unsaturated carboxylic acids, unsaturated carboxylic acid anhydrides, and unsaturated phenol compounds, (b2) N-substituted maleimide, (b3) an unsaturated compound having an allyl group, and (b4) at least one selected from the group consisting of aromatic vinyl compounds, indene or derivatives thereof, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid aminoalkylester compounds, unsaturated carboxylic acid glycidylester compounds, acrylonitrile compounds, unsaturated amide compounds, carboxylic acid vinylester compounds, vinylester compounds, aliphatic conjugated diene compounds, and macromonomers having mono(meth)acryloyl groups at ends of a polymer molecular chain.

Description

Radiation-sensitive composition, color filter, and color liquid crystal display element for colored layer formation {RADIATION-SENSITIVE COMPOSITION FOR FORMING A COLORED LAYER, COLOR FILTER AND COLOR LIQUID CRYSTAL DISPLAY DEVICE}

[Patent Document 1] Japanese Patent Application Laid-Open No. 2-144502

[Patent Document 2] Japanese Patent Application Laid-Open No. 3-53201

The present invention relates to a radiation-sensitive composition for forming a colored layer, a color filter, and a color liquid crystal display device, and more particularly, a colored layer useful for a color filter used in a transmissive or reflective color liquid crystal display device, a color imaging tube element, or the like. It relates to a radiation sensitive composition used for formation of a color, a color filter having a colored layer formed from the radiation sensitive composition, and a color liquid crystal display device comprising the color filter.

Conventionally, in manufacturing a color filter using a colored radiation-sensitive composition, after applying a colored radiation-sensitive composition on a substrate or a substrate on which a light shielding layer of a desired pattern is formed in advance, the solvent is removed, and then the coating film after the solvent is removed. A method of obtaining pixels of each color by irradiating radiation to a desired pattern shape (hereinafter referred to as "exposure") and developing it (Japanese Patent Laid-Open No. Hei 2-144502 and Japanese Patent Laid-Open No. Hei 3-53201) Is known.

In recent years, in the field of color filter technology, it has become mainstream to reduce the exposure time and shorten the tact time. However, in the conventional colored radiation-sensitive composition, when the exposure amount decreases, the residual film rate decreases after development, or a defect or undercut is caused in the pattern. Since peeling from a board | substrate of a pattern tends to occur easily, it was difficult to obtain the pixel and black matrix of a favorable pattern shape, shortening a tact time. In addition, there is a strong demand for a color liquid crystal display element which does not cause defects such as burnout and residual image over a long period of time, and therefore, improved reliability of electrical characteristics represented by voltage retention and the like for the color filter. Although the demand for this is getting stronger, it is very difficult to meet the demand with the conventional colored radiation-sensitive composition.

The subject of this invention is the radiation sensitive property for the formation of the novel colored layer which can manufacture the color filter which is excellent in the adhesiveness with a board | substrate, and is excellent in adhesiveness with a board | substrate, without a pattern defect, such as a defect and an undercut, in a pattern. It is to provide a composition.

The present invention firstly provides a radiation-sensitive composition for forming a colored layer containing (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, wherein (B) alkali-soluble At least one resin selected from the group consisting of (b1) unsaturated carboxylic acids, unsaturated carboxylic anhydrides and unsaturated phenol compounds, (b2) N-substituted maleimide, (b3) unsaturated compounds having an allyl group, (b4) aromatic vinyl compounds, indenes or derivatives thereof, unsaturated carboxylic ester compounds, unsaturated carboxylic acid aminoalkyl ester compounds, unsaturated carboxylic acid glycidyl ester compounds, vinyl cyanide compounds, unsaturated amide compounds, carboxylic acids A vinyl ester compound, a vinyl ether compound, an aliphatic conjugated diene compound, and a macromonomer having a mono (meth) acryloyl group at the terminal of the polymer molecular chain. Which comprises a colored radiation-sensitive composition for forming a layer comprising a copolymer of at least one member selected from the group.

In the present invention, the colored layer means "pixel and / or black matrix".

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

A third aspect of the present invention includes a color liquid crystal display device comprising the color filter.

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

Colored layer  Forming Radiation  Composition

-(A) colorant-

The coloring agent of this invention is not specifically limited in color tone, It is suitably selected according to the use of the color filter obtained, and can be any of a pigment, dye, or a natural pigment.

Since the color filter requires high-precision fine color development and heat resistance, as the colorant in the present invention, a colorant having high color development and high heat resistance, in particular, a colorant having high thermal decomposition resistance is preferable, and more preferably an organic pigment or an inorganic pigment, Especially preferably organic pigments or carbon blacks are used.

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

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

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

C.I. Pigment Violet 1, C.I. Pigment Violet 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment violet 32, C.I. Pigment Violet 36, C.I. Pigment violet 38;

C.I. Pigment Red 1, C.I. Pigment Red 2, C.I. Pigment Red 3, C.I. Pigment Red 4, C.I. Pigment Red 5, C.I. Pigment Red 6, C.I. Pigment Red 7, C.I. Pigment Red 8, C.I. Pigment Red 9, C.I. Pigment Red 10, C.I. Pigment Red 11, C.I. Pigment Red 12, C.I. Pigment Red 14, C.I. Pigment Red 15, C.I. Pigment Red 16, C.I. Pigment Red 17, C.I. Pigment Red 18, C.I. Pigment Red 19, C.I. Pigment Red 21, C.I. Pigment Red 22, C.I. Pigment Red 23, C.I. Pigment Red 30, C.I. Pigment Red 31, C.I. Pigment Red 32, C.I. Pigment Red 37, C.I. Pigment Red 38, C.I. Pigment Red 40, C.I. Pigment Red 41, C.I. Pigment Red 42, C.I. Pigment Red 48: 1, C.I. Pigment Red 48: 2, C.I. Pigment Red 48: 3, C.I. Pigment Red 48: 4, C.I. Pigment Red 49: 1, C.I. Pigment Red 49: 2, C.I. Pigment Red 50: 1, C.I. Pigment Red 52: 1, C.I. Pigment Red 53: 1, C.I. Pigment Red 57, C.I. Pigment Red 57: 1, C.I. Pigment Red 57: 2, C.I. Pigment Red 58: 2, C.I. Pigment Red 58: 4, C.I. Pigment Red 60: 1, C.I. Pigment Red 63: 1, C.I. Pigment Red 63: 2, C.I. Pigment Red 64: 1, C.I. Pigment Red 81: 1, C.I. Pigment Red 83, C.I. Pigment Red 88, C.I. Pigment Red 90: 1, C.I. Pigment Red 97, C.I. Pigment Red 101, C.I. Pigment Red 102, C.I. Pigment Red 104, C.I. Pigment Red 105, C.I. Pigment Red 106, C.I. Pigment Red 108, C.I. Pigment Red 112, C.I. Pigment Red 113, C.I. Pigment Red 114, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 146, C.I. Pigment Red 149, C.I. Pigment Red 150, C.I. Pigment Red 151, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 170, C.I. Pigment Red 171, C.I. Pigment Red 172, C.I. Pigment Red 174, C.I. Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 178, C.I. Pigment Red 179, C.I. Pigment Red 180, C.I. Pigment Red 185, C.I. Pigment Red 187, C.I. Pigment Red 188, C.I. Pigment Red 190, C.I. Pigment Red 193, C.I. Pigment Red 194, C.I. Pigment Red 202, C.I. Pigment Red 206, C.I. Pigment Red 207, C.I. Pigment Red 208, C.I. Pigment Red 209, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 220, C.I. Pigment Red 224, C.I. Pigment Red 226, C.I. Pigment Red 242, C.I. Pigment Red 243, C.I. Pigment Red 245, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment red 265;

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

C.I. Pigment violet 23;

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

C.I. Pigment Brown 23, C.I. Pigment brown 25;

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

These organic pigments can be purified and used by an appropriate method such as a sulfuric acid recrystallization method, a solvent washing method or a combination thereof.

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

In the present invention, the organic pigments and inorganic pigments may be used alone or in combination of two or more thereof, and organic pigments and inorganic pigments may be used in combination, but when forming a pixel, preferably at least one organic Pigments are used, and when forming a black matrix, preferably two or more organic pigments and / or carbon blacks are used.

In the present invention, each of the pigments may be used by modifying the particle surface thereof with a polymer if desired. As a polymer which modifies the particle surface of a pigment, the polymer of Unexamined-Japanese-Patent No. 8-259876, etc., the polymer for various pigment dispersions, or oligomer etc. are mentioned, for example.

In addition, in the present invention, the colorant may be used together with a dispersant if desired.

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

As said surfactant, For example, Polyoxyethylene alkyl ether, such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether; Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether; Polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; Sorbitan fatty acid esters; Fatty acid modified polyesters; Tertiary amine modified polyurethanes; In addition to polyethyleneimine and the like, KP (produced by Shin-Etsu Chemical Co., Ltd.), polyflow (produced by Kyoeisha Chemical Co., Ltd.), F-Top (manufactured by Tochem Products Co., Ltd.), and Mega Pack (die) Nippon ink Kagaku Kogyo Co., Ltd.), Florade (manufactured by Sumitomo 3M Co., Ltd.), Asahi Gadard, Sufron (above, Asahi Glass Co., Ltd.), BYK, Disperbyk (Sang, Big Chemi Japan) Corporation | KK Corporation | Solpasu (made by Seneca Co., Ltd.), etc. are mentioned.

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

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

In the present invention, the radiation-sensitive resin composition can be produced by an appropriate method, but when using a pigment as a colorant, the pigment is ground in a solvent in the presence of a dispersant, for example, using a bead mill, a roll mill, or the like. It is preferable to make it by mixing and dispersing to make a pigment dispersion liquid, and to add and mix the (B) component, (C) component, and (D) component mentioned later with this, if needed, further adding a solvent and the other additive mentioned later. .

The amount of the dispersant used in preparing the pigment dispersion is preferably 100 parts by weight or less, more preferably 0.5 to 100 parts by weight, still more preferably 1 to 70 parts by weight, particularly preferably 10 based on 100 parts by weight of the pigment. To 50 parts by weight. In this case, when the usage-amount of a dispersing agent exceeds 100 weight part, there exists a possibility that developability etc. may be impaired.

Moreover, as a solvent used when manufacturing a pigment dispersion liquid, the same thing as the solvent illustrated about the liquid composition of the radiation sensitive resin composition mentioned later is mentioned, for example.

The amount of the solvent used when preparing the pigment dispersion is preferably 200 to 1,000 parts by weight, more preferably 300 to 800 parts by weight based on 100 parts by weight of the pigment.

In the production of the pigment dispersion, when producing by 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 containing a pigment, a solvent, and a dispersant is preferably a cooling water. It can carry out by mixing and dispersing, cooling by etc.

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

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

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

-(B) alkali-soluble resin-

The alkali-soluble resin in the present invention is selected from the group consisting of (b1) unsaturated carboxylic acids, unsaturated carboxylic anhydrides and unsaturated phenol compounds (hereinafter collectively referred to as "unsaturated compounds (b1)"). At least a species, (b2) N-substituted maleimide, (b3) an unsaturated compound having an allyl group (hereinafter referred to as an "unsaturated compound (b3)"), (b4) an aromatic vinyl compound, indene or a derivative thereof, Unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid aminoalkyl ester compounds, unsaturated carboxylic acid glycidyl ester compounds, vinyl cyanide compounds, unsaturated amide compounds, carboxylic acid vinyl ester compounds, vinyl ether compounds, aliphatic conjugated diene compounds, and In the group consisting of macromonomers having a mono (meth) acryloyl group at the ends of the polymer molecular chain (hereinafter referred to as "unsaturated compound (b4)") A copolymer containing one or more selected ones (hereinafter referred to as "copolymer (BI)"), which is used in the development treatment step for forming a colored layer, while acting as a binder to the colorant (A). It is a component which has solubility with respect to alkaline developing solution.

In the unsaturated compound (b1), examples of the unsaturated carboxylic acid or unsaturated carboxylic anhydride include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid;

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

Trivalent or higher unsaturated polyvalent carboxylic acid or anhydrides thereof;

Mono [(meth) acryloyloxyalkyl] of bivalent or more polyvalent carboxylic acids, such as monosuccinate mono [2- (meth) acryloyloxyethyl] and phthalate mono [2- (meth) acryloyloxyethyl] ester;

and mono (meth) acrylates of polymers having a carboxyl group and a hydroxyl group at both terminals, such as? -carboxypolycaprolactone mono (meth) acrylate.

Among these unsaturated carboxylic acids and unsaturated carboxylic anhydrides, mono succinate (2-acryloyloxyethyl) and mono phthalate (2-acryloyloxyethyl) are respectively represented by light ester HOA-MS and light ester HOA-MPE ( It is marketed under the trade name of Kyoeisha Chemical Co., Ltd.).

Moreover, as said unsaturated phenol compound, o-vinyl phenol, m-vinyl phenol, p-vinyl phenol, 2-methyl-4- vinyl phenol, 3-methyl-4- vinyl phenol, o-isopropenyl phenol, for example unsaturated phenol compounds such as m-isopropenylphenol and p-isopropenylphenol;

2-vinyl-1-naphthol, 3-vinyl-1-naphthol, 1-vinyl-2-naphthol, 3-vinyl-2-naphthol, 2-isopropenyl-1-naphthol, 3-isopropenyl-1- Unsaturated naphthol compounds, such as naphthol, etc. are mentioned.

In the present invention, examples of the unsaturated compound (b1) include (meth) acrylic acid, monosuccinic acid [2- (meth) acryloyloxyethyl], ω-carboxypolycaprolactone mono (meth) acrylate, p-vinylphenol and the like. This is preferable and especially (meth) acrylic acid is preferable.

Examples of the N-substituted maleimide include N-methyl maleimide, N-ethyl maleimide, Nn-propyl maleimide, Ni-propyl maleimide, Nn-butyl maleimide, Nt-butyl maleimide and Nn-hexyl Maleimide, N-cyclopentyl maleimide, N-cyclohexyl maleimide, N-phenyl maleimide, N-1- naphthyl maleimide, etc. are mentioned.

In the present invention, as the N-substituted maleimide, N-cyclohexyl maleimide, N-phenyl maleimide and the like are preferable, and N-phenyl maleimide is particularly preferable.

The said N-substituted maleimide can be used individually or in mixture of 2 or more types.

As an unsaturated compound (b3), the compound which has only an allyl group as a polymerizable unsaturated bond, the compound which has a polymerizable unsaturated bond different from an allyl group as a polymerizable unsaturated bond (henceforth "unsaturated compound (b3-I)"), etc. are mentioned. Although unsaturated compounds (b3-I) are preferred.

As an unsaturated compound (b3), For example, Unsaturated compounds (b3-I), such as allyl (meth) acrylate, allyl crotonate, allyl alpha-chloroacrylic acid, allyl cinnamic acid, monoallyl maleic acid, and monoallyl fumarate, 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 this invention, allyl (meth) acrylate is especially preferable as an unsaturated compound (b3).

The said unsaturated compound (b3) can be used individually or in mixture of 2 or more types.

As an example of an unsaturated compound (b4), as said aromatic vinyl compound, For example, styrene, (alpha) -methylstyrene, o-vinyl toluene, m-vinyl toluene, p-vinyl toluene, p-chloro styrene, o-methoxy styrene , m-methoxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl Ether, p-vinylbenzyl glycidyl ether and the like;

As said indene derivative, For example, 1-methyl indene etc .;

As said unsaturated carboxylic acid ester compound, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth), for example 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-phenoxy Ethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, Methoxytriethylene glycol (meth) acrylate, methoxypropylene glycol (meth) acrylate, methoxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycerol mono (meth) acrylate, and the like;

As said unsaturated carboxylic acid aminoalkyl ester compound, 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl, for example (Meth) acrylate, 3-aminopropyl (meth) acrylate, 3-dimethylaminopropyl (meth) acrylate, and the like;

As said unsaturated carboxylic acid glycidyl ester compound, For example, glycidyl (meth) acrylate etc .;

As said vinyl cyanide compound, For example, (meth) acrylonitrile, (alpha)-chloro acrylonitrile, vinylidene cyanide etc .;

As said unsaturated amide compound, For example, (meth) acrylamide, (alpha)-chloro acrylamide, N-2-hydroxyethyl (meth) acrylamide, etc .;

As said carboxylic acid vinyl ester compound, For example, vinyl acetate, a vinyl propionate, a vinyl butyrate, a vinyl benzoate;

As said vinyl ether compound, For example, vinyl methyl ether, vinyl ethyl ether, etc .;

As said aliphatic conjugated diene compound, For example, 1, 3- butadiene, isoprene, chloroprene etc .;

As a macromonomer which has a mono (meth) acryloyl group at the terminal of the said polymer molecular chain, For example, polymer molecular chains, such as polystyrene, polymethyl (meth) acrylate, poly-n-butyl (meth) acrylate, polysiloxane, etc. Macromonomers having a mono (meth) acryloyl group at the terminal of the monomer; Etc. can be mentioned.

In the present invention, as the unsaturated compound (b4), an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, a macromonomer, and the like are preferable, and in particular, styrene, methyl (meth) acrylate, n-butyl (meth) acrylate, 2 -Ethyl hexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer, polymethylmethacrylate macromonomer, etc. are preferable. .

The said unsaturated compound (b4) can be used individually or in mixture of 2 or more types.

In the present invention, the copolymer (BI) is one selected from the group consisting of at least one unsaturated compound (b1) containing (meth) acrylic acid as an essential component, and N-cyclohexylmaleimide and N-phenylmaleimide. At least one N-substituted maleimide, at least one unsaturated compound (b3) selected from the group consisting of allyl acrylate and allyl methacrylate, styrene, methyl (meth) acrylate, n-butyl (meth) acryl Latex, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, glycerol mono (meth) acrylate, polystyrene macromonomer and poly Preferred is a copolymer (hereinafter referred to as "copolymer (BII)") with at least one unsaturated compound (b4) selected from the group consisting of methyl methacrylate macromonomers.

As a specific example of a 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 / polymethylmethacrylate Macromonomer copolymers,

(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 copolymers,

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

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

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

(Meth) acrylic acid / mono succinate mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmaleimide / allyl methacrylate / styrene / n-butyl (meth) acrylate / benzyl (meth) acrylate air coalescence,

(Meth) acrylic acid / mono succinate mono [2- (meth) acryloyloxyethyl] / N-cyclohexylmalimide / allyl methacrylate / benzyl (meth) acrylate / glycerol mono (meth) acrylate copolymer,

(Meth) acrylic acid / monosuccinic acid [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene copolymer,

(Meth) acrylic acid / monosuccinic acid [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / n-butyl (meth) acrylate copolymer,

(Meth) acrylic acid / monosuccinic acid [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / 2-hydroxyethyl (meth) acrylate copolymer,

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

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

(Meth) acrylic acid / mono succinate mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / methyl (meth) acrylate / 2-ethylhexyl (meth) acrylate air coalescence,

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

(Meth) acrylic acid / mono succinate [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / 2-ethylhexyl (meth) acrylate / benzyl (meth) acrylate Copolymer,

(Meth) acrylic acid / mono succinate [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate Copolymer,

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

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

(Meth) acrylic acid / mono succinate mono [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / n-butyl (meth) acrylate / 2-hydroxyethyl (meth) Acrylate / benzyl (meth) acrylate copolymers,

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

(Meth) acrylic acid / mono succinate 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 copolymers,

(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,

The copolymer etc. which substituted allyl methacrylate in these copolymers with allyl acrylate are mentioned.

In 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 / monosuccinic acid [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene copolymer,

(Meth) acrylic acid / monosuccinic acid [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / 2-hydroxyethyl (meth) acrylate copolymer,

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

(Meth) acrylic acid / mono succinate [2- (meth) acryloyloxyethyl] / N-phenylmaleimide / allyl methacrylate / styrene / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate Copolymers are preferred.

In the copolymer (BI), the copolymerization ratio of the unsaturated compound (b1) is preferably 1 to 40% by weight, particularly preferably 5 to 30% by weight, and (b2) the copolymerization ratio of the N-substituted maleimide is Preferably it is 1-50 weight%, Especially preferably, it is 5-40 weight%, The copolymerization ratio of an unsaturated compound (b3) becomes like this. Preferably it is 1-70 weight%, Especially preferably, it is 5-40 weight%, Unsaturation The copolymerization ratio of the compound (b4) is preferably 1 to 80% by weight, particularly preferably 5 to 60% by weight.

In this invention, the radiation sensitive composition excellent in a sensitivity, board | substrate adhesiveness, and solvent resistance can be obtained by making the copolymerization ratio of each unsaturated compound in a copolymer (BI) into the said range.

In this invention, another alkali-soluble resin can be used together with a copolymer (BI).

Although it does not specifically limit as said other alkali-soluble resin as long as it has solubility with respect to the alkaline developing solution used at the time of forming a colored layer, acting as a binder with respect to (A) coloring agent, For example, Alkali which has a carboxyl group Soluble resin is preferable, As an example, 1 or more types chosen from the group which consists of unsaturated carboxylic acid and unsaturated carboxylic anhydride illustrated with respect to copolymer (BI), and N-position illustrated with respect to copolymer (BI)- The copolymer with 1 or more types chosen from the group which consists of substituted maleimide and an unsaturated compound (b4), etc. are mentioned.

As another preferable alkali-soluble resin, More specifically, (i) 1 or more types of unsaturated carboxylic acid which has (meth) acrylic acid as an essential component, and (ii) N-cyclohexyl maleimide, N-phenylmaleimide, styrene, methyl (Meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, phenyl (meth) acrylate, The copolymer with 1 or more types chosen from the group which consists of a glycerol mono (meth) acrylate, a polystyrene macromonomer, and a polymethylmethacrylate macromonomer, etc. are mentioned.

In the present invention, the polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the copolymer (BI) and other alkali-soluble resins is preferable. Preferably 2,000 to 300,000, more preferably 3,000 to 100,000.

The polystyrene reduced number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC, elution solvent: tetrahydrofuran) of the copolymer (BI) and other alkali-soluble resins is preferably 3,000, respectively. To 60,000, more preferably 5,000 to 25,000.

In this invention, the radiation sensitive composition excellent in developability by using the copolymer (BI) which has the said specific Mw and Mn, or using together the said copolymer (BI) and the other alkali-soluble resin which has the said specific Mw and Mn together. As a result, a colored layer having sharp patterned ends can be formed, and at the time of development, residues, ground contamination, film residues, etc. on the substrate and the light shielding layer of the unexposed portion are less likely to occur.

Further, the ratio (Mw / Mn) of Mw and Mn of the copolymer (BI) and other alkali-soluble resins is preferably 1 to 5, more preferably 1 to 4, respectively.

In this invention, copolymer (BI) can be used individually or in mixture of 2 or more types, and also the other alkali-soluble resin is the same.

In the present invention, the total amount of the alkali-soluble resin is preferably 10 to 1,000 parts by weight, more preferably 20 to 500 parts by weight with respect to 100 parts by weight of the (A) colorant. In this case, when the total amount of the alkali-soluble resin is less than 10 parts by weight, for example, alkali developability may decrease or background contamination or film residue may occur on the substrate or the light shielding layer of the unexposed portion, When it exceeds 1,000 weight part, since a coloring agent density | concentration falls relatively, there exists a possibility that it may become difficult to achieve the target color density as a thin film.

In addition, the use ratio of the copolymer (BI) in alkali-soluble resin becomes like this. Preferably it is 10-100 weight%, Especially preferably, it is 20-100 weight%. In this case, if the use ratio of copolymer (BI) is less than 10% by weight, the desired effect of the present invention may be impaired.

-(C) polyfunctional monomer-

The multifunctional monomer in the present invention consists of a monomer having two or more polymerizable unsaturated bonds in one molecule.

As a polyfunctional monomer, For example, Di (meth) acrylate of alkylene glycol, such as ethylene glycol and propylene glycol;

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

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

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

Di (meth) acrylate of both terminal hydroxylated polymers such as both terminal hydroxypoly-1,3-butadiene, both terminal hydroxypolyisoprene and both terminal hydroxypolycaprolactone, and tris (2- (meth) Acryloyloxyethyl] phosphate etc. are mentioned.

Of these polyfunctional monomers, poly (meth) acrylates of trivalent or higher polyhydric alcohols and their dicarboxylic acid modified substances, specifically trimethylolpropanetriacrylate, trimethylolpropanetrimethacrylate, pentaerythritol tree Acrylate, pentaerythritol trimethacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, dipentaerythritol hexaacrylic The latent, dipentaerythritol hexamethacrylate, the compound represented by the following general formula (C-1), the compound represented by the following general formula (C-2), and the like are preferable, and trimethylolpropane triacrylate, pentaerythritol triacrylate, and Dipentaerythritol hexaacrylate is high in the strength of the colored layer, And surface smoothness is excellent, it is preferable in the background contamination is difficult to occur, and the film residue and the like on the substrate and the light shielding layer at the unexposed portion of points.

<Formula C-1>

<Formula C-2>

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

The amount of the polyfunctional monomer used in the present invention is preferably 5 to 500 parts by weight, more preferably 20 to 300 parts by weight based on 100 parts by weight of the (B) alkali-soluble resin. In this case, when the usage-amount of a polyfunctional monomer is less than 5 weight part, there exists a tendency for the intensity | strength and surface smoothness of a colored layer to fall, and when it exceeds 500 weight part, alkali developability falls, for example, or the board | substrate of an unexposed part Background contamination, film residues, and the like tend to be easily generated on the phase or the light shielding layer.

In the present invention, a part of the polyfunctional monomer may be substituted with a monofunctional monomer having one polymerizable unsaturated bond in one molecule.

As said monofunctional monomer, the compound similar to the compound illustrated with respect to unsaturated compound (b1), N-substituted maleimide, and unsaturated compound (b4) in (B) alkali-soluble resin, for example, N- (meth) In addition to acryloyl morpholine, N-vinylpyrrolidone, and N-vinyl- epsilon caprolactam, M-5600 (brand name, Toagosei Co., Ltd.) etc. are mentioned as a commercial item.

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

The use ratio of the monofunctional monomer is preferably 90% by weight or less, more 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 a monofunctional monomer exceeds 90 weight%, there exists a possibility that the intensity | strength and surface smoothness of the colored layer obtained may become inadequate.

The total amount of the polyfunctional monomer and the monofunctional monomer in the present invention is preferably 5 to 500 parts by weight, more preferably 20 to 300 parts by weight based on 100 parts by weight of the (B) alkali-soluble resin. In this case, when the total amount is less than 5 parts by weight, the strength and surface smoothness of the colored layer tends to be lowered. On the other hand, when the total amount exceeds 500 parts by weight, for example, alkali developability is lowered, or on the substrate of the unexposed part. Background contamination, film residues, and the like tend to occur on the light shielding layer.

-(D) photoinitiator-

The photopolymerization initiator in the present invention initiates the polymerization of (C) the polyfunctional monomer and the monofunctional monomer used in some cases by exposure to radiation such as visible light, ultraviolet ray, far ultraviolet ray, charged particle beam, and X-ray. It is a component that generates active species.

In the present invention, as the photopolymerization initiator, for example, a compound represented by the following formula (1) (hereinafter referred to as "oxime compound (D1)"), a compound represented by the following formula (2) (hereinafter "oxime compound ( D2) "), a biimidazole compound, a benzoin compound, an acetophenone compound, a benzophenone compound, an α-diketone compound, and a multinucleus having at least one main skeleton represented by the following general formula (3a), (3b) or (3c): Quinone compounds, xanthone compounds, phosphine compounds, triazine compounds and the like.

[In Formula 1 and Formula 2, each R <^1> represents a C1-C12 linear, branched or cyclic alkyl group, or a phenyl group independently of each other, and each R <^2> is a hydrogen atom, a C1-C12 straight line independently of each other, A chain, branched or cyclic alkyl group or a phenyl group, R ³ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and each R ⁴ , each R ⁵ and each R ⁶ is independently hydrogen Linear or branched or cyclic alkyl groups having 1 to 6 carbon atoms, provided that the alkyl groups of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each linear 1 to 6 carbon atoms, It may be substituted with a substituent selected from the group of a branched or cyclic alkoxyl group, a phenyl group and a halogen atom, 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, 1 to 6 carbon atoms Linear, branched That is optionally substituted with substituents selected from the group of cyclic alkoxyl group, a phenyl group and a halogen atom]

In Formula 1 and Formula 2, as a C1-C12 linear, branched or cyclic alkyl group of R <^1> , R <^2> and R <^3> , it is a methyl group, an ethyl group, n-propyl group, i-propyl group, n, for example. -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 -An undecyl group, n-dodecyl group, a cyclopentyl group, a cyclohexyl group, etc. are mentioned.

Moreover, as a C1-C6 linear, branched or cyclic alkyl group of R <^4> , R <^5> and R <^6> , it is a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, i-, for example. A butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, cyclopentyl group, cyclohexyl group, etc. are mentioned.

Linear, branched or cyclic alkoxy having 1 to 6 carbon atoms in the substituent for each alkyl group of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ , and the substituent for each phenyl group of R ¹ and R ² As a real group, a methoxyl group, an ethoxyl group, n-propoxy group, i-propoxyl group, n-butoxyl group, t-butoxyl group etc. are mentioned, for example, As a halogen atom, a fluorine atom, a chlorine, for example is mentioned. Atom etc. are mentioned.

Moreover, as a C1-C6 linear, branched, or cyclic alkyl group in the substituent with respect to each phenyl group of R <^1> and R <^2> , For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group and t-butyl group.

In each alkyl group and each phenyl group, one or more substituents may be present.

In the general formulas (1) and (2), as R ¹ , methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, phenyl group and the like are preferable, and as R ² , hydrogen atom, methyl group, ethyl group, n-propyl group , i-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group and the like are preferred, and R ^{3 is a} hydrogen atom, a methyl group, an ethyl group, an n-propyl group, i-propyl group, n-butyl group, etc. are preferable, and as R <^4> , R <^5> and R <^6> , a hydrogen atom, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, etc. are preferable.

As a specific example of a preferable oxime type compound (D1), for example, 1- [4- (phenylthio) phenyl] -octan-1-one-2-one oxime-O-acetate, 1- [4- (2-methylphenyl Thio) phenyl] -octan-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] -octan-1-one-2-one oxime-O-acetate, 1- [4- (phenylthio) phenyl] -octane-1- On-2-one oxime-O-benzoate, 1- [4- (2-methylphenylthio) phenyl] -octan-1-one-2-one oxime-O-benzoate, 1- [4- (2, 4,6-trimethylphenylthio) phenyl] -octan-1-one-2-one oxime-O-benzoate, 1- [4- (2-ethylphenylthio) phenyl] -octan-1-one-2- Onoxime-0-benzoate etc. are mentioned.

Moreover, as a specific example of a preferable oxime type compound (D2), it is 1- [9-ethyl-6-benzoyl-9.H.-carbazol-3-yl] -octan-1-one oxime-O-acetate, for example. , 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.

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

As said biimidazole compound, it is 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'- tetrakis (4-ethoxycarbonylphenyl) -1,2'-, for example. Biimidazole,

2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetrakis (4-ethoxycarbonylphenyl)-1,2'-biimidazole,

2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2,4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2,4,6-trichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2-bromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2,4-dibromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole,

2,2'-bis (2,4,6-tribromophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole etc. are mentioned.

Among these biimidazole compounds, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2 , 4-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole 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 is preferred.

The biimidazole compound is excellent in solubility in solvents, does not generate foreign matters such as undissolved products, precipitates, etc., and also has high sensitivity, while sufficiently advancing the curing reaction by exposure of a small amount of energy, and having high contrast and minnow. Since no hardening reaction occurs in the miner, the coated film after exposure is clearly divided into an insoluble hardened portion for the developer and an uncured portion having high solubility for the developer, whereby a pixel pattern and a black matrix pattern without undercuts are obtained. It is possible to form a high-precision fine pattern array arranged in accordance with a predetermined arrangement.

As said benzoin compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, methyl 2-benzoyl benzoate etc. are mentioned, for example.

As said acetophenone compound, 2, 2- dimethoxy acetophenone, 2, 2- diethoxy acetophenone, 2, 2- dimethoxy- 2-phenylacetophenone, 2-hydroxy-2-methyl-1, for example -Phenylpropane-1-one, 1- (4-i-propylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl- (4-methylthiophenyl) -2-morpholino -1-Propan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) butan-1-one, 1-hydroxycyclohexylphenyl ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, and the like.

As said benzophenone compound, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, etc. are mentioned, for example.

As said alpha-diketone compound, diacetyl, dibenzoyl, methyl benzoyl formate, etc. are mentioned, for example.

As said polynuclear quinone compound, anthraquinone, 2-ethyl anthraquinone, 2-t- butyl anthraquinone, 1, 4- naphthoquinone, etc. are mentioned, for example.

As said xanthone compound, xanthone, thioxanthone, 2-chloro thioxanthone, etc. are mentioned, for example.

Examples of the phosphine compound include bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, and the like.

Examples of the triazine compound include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine and 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-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-n-butoxyphenyl)- And compounds having halomethyl groups, such as 4,6-bis (trichloromethyl) -s-triazine, a compound represented by the following formula (4), and a compound represented by the following formula (5).

In this invention, as a photoinitiator, an oxime type compound (D1), an oxime type compound (D2), a biimidazole compound, an acetophenone compound, a triazine compound, etc. are preferable, More preferably, an oxime type compound (D1) Or an oxime compound (D2).

In this invention, a photoinitiator can be used individually or in mixture of 2 or more types.

The amount of the photopolymerization initiator used in the present invention is preferably 0.01 to 200 parts by weight, more preferably 1 to 120 parts by weight based on 100 parts by weight of the total amount of the (C) polyfunctional monomer and the monofunctional monomer used in some cases. And particularly preferably 1 to 100 parts by weight. In this case, when the usage-amount of a photoinitiator is less than 0.01 weight part, hardening by exposure may become inadequate, and it may become difficult to obtain the pattern array in which the pixel pattern or the black matrix pattern was arrange | positioned according to a predetermined arrangement, while 200 weight part When it exceeds, the formed colored layer will fall easily from a board | substrate at the time of image development, and a background contamination, a film | membrane residue, etc. will be easy to produce on the board | substrate or the light shielding layer of an unexposed part.

In the present invention, one or more of a sensitizer, a curing accelerator, or a polymer photocrosslinking and sensitizer may be used in combination with the photopolymerization initiator.

-additive-

The radiation sensitive composition for coloring layer formation of this invention may contain various additives as needed.

As said additive, the organic acid or organic amino compound which exhibits the effect which further suppresses the remainder of the undissolved matter after image development, further improving the dissolution characteristic with respect to the alkaline developing solution of a radiation sensitive composition.

As said organic acid, the aliphatic carboxylic acid or phenyl group containing carboxylic acid which has 1 or more carboxyl group in a molecule | numerator is preferable.

As said aliphatic carboxylic acid, For example, monocarboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, valeric acid, pivalic acid, caproic acid, diethyl acetic acid, enanthic acid, caprylic acid;

Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, brasilic 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 and mesaconic acid;

Tricarboxylic acids, such as tricarvalic acid, aconitic acid, and camphoronic acid, etc. are mentioned.

Examples of the phenyl group-containing carboxylic acid include compounds in which a carboxyl group is directly bonded to a phenyl group, and carboxylic acid in which the carboxyl group is bonded to a phenyl group via a carbon chain.

As a phenyl group containing carboxylic acid, For example, Aromatic monocarboxylic acids, such as benzoic acid, toluic acid, cuminic acid, hemelic acid, and mesitylene acid;

Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid;

Trivalent or higher aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, melanoic acid, pyromellitic acid, phenylacetic acid, hydroatroic acid, hydrocinnamic acid, mandelic acid, phenylsuccinic acid, atroic acid, cinnamic acid And cinnamic acid, kumaric acid, and umbelic acid.

Among these organic acids, aliphatic dicarboxylic acids are preferable as the aliphatic carboxylic acid from the viewpoints of alkali solubility, solubility in a solvent to be described later, prevention of background contamination on the substrate or the light shielding layer of the unexposed portion, and film residue. Malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid and the like are preferable. Moreover, as a phenyl group containing carboxylic acid, aromatic dicarboxylic acid is preferable and phthalic acid is especially preferable.

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

The amount of the organic acid used is preferably 15% by weight or less, and more preferably 10% by weight or less based on the whole radiation-sensitive composition. In this case, when the usage-amount of an organic acid exceeds 15 weight%, there exists a tendency for adhesiveness with respect to the board | substrate of the formed colored layer to fall.

Moreover, as said organic amino compound, the aliphatic amine or phenyl group containing amine which has 1 or more amino group in a molecule | numerator is preferable.

As said aliphatic amine, it is n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-, for example. Heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, 2-methylcyclohexylamine, 3-methylcyclohexylamine, 4- Mono (cyclo) alkylamines such as methylcyclohexylamine, 2-ethylcyclohexylamine, 3-ethylcyclohexylamine and 4-ethylcyclohexylamine;

Methylethylamine, diethylamine, methyl n-propylamine, ethyl n-propylamine, di-n-propylamine, di-i-propylamine, di-n-butylamine, di-i-butylamine, di- di (cyclo) alkylamines such as sec-butylamine, di-t-butylamine, di-n-pentylamine, di-n-hexylamine, methylcyclohexylamine, ethylcyclohexylamine and 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, dimethylcyclo Tri (cyclo) alkylamines such as hexylamine, diethylcyclohexylamine, methyldicyclohexylamine, ethyldicyclohexylamine 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 ( Di (cyclo) alkanolamines such as 4-cyclohexanol) 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- Amino (cyclo) alkanediols such as propanediol and 2-diethylamino-1,3-propanediol;

1-aminocyclopentanmethanol, 4-aminocyclopentanmethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanmethanol, 4-diethylaminocyclopentanmethanol, 4-dimethylaminocyclo Amino group-containing cycloalkanethanols such as hexanemethanol and 4-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 And aminocarboxylic acids such as -aminocyclopropanecarboxylic acid, 1-aminocyclohexanecarboxylic acid, and 4-aminocyclohexanecarboxylic acid.

Moreover, as said phenyl group containing amine, the compound etc. which the amino group couple | bonded with the phenyl group directly, the amino group couple | bonded with the phenyl group through the carbon chain, etc. are mentioned, for example.

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 Aromatic amines such as 4-t-butylaniline, 1-naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline and 4-methyl-N, N-dimethylaniline;

Aminobenzyl alcohols such as 2-aminobenzyl alcohol, 3-aminobenzyl alcohol, 4-aminobenzyl alcohol, 4-dimethylaminobenzyl alcohol, and 4-diethylaminobenzyl alcohol;

And aminophenols such as 2-aminophenol, 3-aminophenol, 4-aminophenol, 4-dimethylaminophenol, and 4-diethylaminophenol.

Among these organic amino compounds, mono (cyclo) alkanolamines and amino (cyclo Alkanediol is preferred, especially 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propane Diol, 4-amino-1,2-butanediol, etc. are preferable. Moreover, as a phenyl group containing amine, aminophenol is preferable and 2-aminophenol, 3-aminophenol, 4-aminophenol etc. are especially preferable.

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

The usage-amount of an organic amino compound becomes like this. Preferably it is 15 weight% or less, More preferably, it is 10 weight% or less with respect to 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 adhesiveness with respect to the board | substrate of the formed colored layer to fall.

Moreover, as additives other than the said organic acid and organic amino compound, For example, Dispersion adjuvant, such as blue pigment derivatives, such as a copper phthalocyanine derivative, and a yellow pigment derivative;

Fillers such as glass and alumina;

Polymer compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ether, and poly (fluoroalkyl acrylate);

Surfactants such as nonionic, cationic and anionic;

Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclo Hexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloyloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, etc. Adhesion promoter;

Antioxidants such as 2,6-di-t-butylphenol;

Ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole and alkoxybenzophenone;

Aggregation inhibitors such as sodium polyacrylate;

And thermal radical generators such as 1,1'-azobis (cyclohexane-1-carbonitrile) and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.

menstruum

Although the radiation sensitive composition for colored layer formation of this invention makes the said (A)-(D) component an essential component, and contains the said additive component as needed, Preferably it mixes a solvent and is manufactured as a liquid composition.

The solvent may be appropriately selected and used as long as it does not react with these components while dispersing or dissolving the components (A) to (D) and the additive component constituting the radiation-sensitive composition.

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, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, dipropylene glycol mono-n-butyl ether, (Poly) alkylenes such as tripropylene glycol monomethyl ether and tripropylene glycol monoethyl ether Recall monoalkyl ether;

(Poly) alkylenes 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, and propylene glycol monoethyl ether acetate Glycol monoalkyl ether acetates;

Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether and tetrahydrofuran;

Ketones such as methyl ethyl ketone, cyclohexanone, 2-heptanone, and 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-3-methylbutyrate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n-propyl acetate, i-propyl acetate, N-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, pyruvate other esters such as n-propyl, methyl acetoacetate, ethyl acetoacetate, and ethyl 2-oxobutyrate;

Aromatic hydrocarbons such as toluene and xylene;

Amide compounds or lactam compounds 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, in view of solubility, pigment dispersibility, coating properties, etc. Diethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl lactate, 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate, 3-methyl-3 Methoxybutyl propionate, n-butyl acetate, i-butyl acetate, n-amyl formate, i-amyl acetate, n-butyl propionate, ethyl butyrate, ethyl butyrate i-propyl, n-butyl butyrate, ethyl pyruvate, and the like. desirable.

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

Furthermore, 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 And high boiling point solvents such as diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, and ethylene glycol monophenyl ether acetate.

These high boiling point solvents can be used individually or in mixture of 2 or more types.

Although the usage-amount of a solvent is not specifically limited, From a viewpoint of the applicability | paintability, stability, etc. of the radiation sensitive composition obtained, the total concentration of each component except the solvent of the said composition becomes like this. Preferably it is 5-50 weight%, More preferably, It is preferable that the amount is 10 to 40% by weight.

When using a high boiling point solvent together as a solvent, the use ratio of the high boiling point solvent to the solvent whole quantity becomes like this. Preferably it is 50 weight% or less, More preferably, it is 30 weight% or less.

Color filter

The color filter of this invention has a colored layer formed from the radiation sensitive composition for colored layer formation of this invention.

Below, the method of forming the colored layer in the color filter of this invention is demonstrated.

First, a light shielding layer is formed on the surface of a substrate so as to partition a part which forms a pixel as needed, and after apply | coating the liquid composition of the radiation sensitive composition which red pigment disperse | distributed on this board | substrate, for example, Baking is performed to evaporate the solvent to form a coating film.

Subsequently, after exposing through a photomask to this coating film, it develops using alkaline developing solution, melt | dissolves and removes the unexposed part of a coating film, and then post-bakes to form the pixel array in which the red pixel pattern was arrange | positioned in the predetermined array. do.

Thereafter, using the liquid composition of each radiation-sensitive composition in which the green or blue pigment is dispersed, the liquid pixel composition and the blue pixel array and the blue color are applied in the same manner as described above by applying, prebaking, exposing, developing and post-baking the liquid composition. By sequentially forming pixel arrays on the same substrate, a color filter in which pixel arrays of three primary colors of red, green, and blue are arranged on a substrate is obtained. However, in the present invention, the order of forming the pixels of each color is not limited to the above.

In addition, a black matrix can be formed similarly to the case of said pixel formation using the liquid composition of the radiation sensitive composition which black pigment disperse | distributed, for example.

As a board | substrate used when forming a pixel and / or a black matrix, glass, silicone, a polycarbonate, polyester, aromatic polyamide, polyamideimide, polyimide, etc. are mentioned, for example.

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

When applying the liquid composition of the radiation sensitive composition to the substrate, an appropriate coating method such as spraying, roll coating, spin coating (spin coating), slit die coating, bar coating or inkjet may be employed. In particular, the spin coating method and the slit die coating method are preferable.

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

As radiation used for forming the pixel and / or black matrix, for example, visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray, etc. may be used, but radiation having a wavelength in the range of 190 to 450 nm is preferable. .

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

As the alkaline developer, for example, sodium carbonate, sodium hydroxide, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5- Aqueous solutions, such as diazabicyclo- [4.3.0] -5-nonene, are preferable.

A suitable amount of water-soluble organic solvents such as methanol and ethanol, surfactants, and the like may be added to the alkaline developer. On the other hand, after alkali development, it washes with water preferably.

As the developing treatment method, a shower developing method, a spray developing method, a dip (immersion) developing method, a puddle (liquid dipping) developing method, and the like can be applied. As for image development conditions, 5 to 300 second is preferable at normal temperature.

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

Color liquid crystal display element

The color liquid crystal display element of this invention is equipped with the color filter of this invention.

Moreover, as one form of the color liquid crystal display element of this invention, using the radiation sensitive composition for color layer formation of this invention, forming a pixel and / or a black matrix on a thin film transistor substrate array as above-mentioned, Especially the color liquid crystal display element which has the outstanding characteristic can be manufactured.

Particularly Preferred Embodiments of the Invention

Although the radiation sensitive composition for colored layer formation of this invention contains the said (A)-(D) component as an essential component, it will be as follows (1)-(4) if it specifically illustrates a particularly preferable composition.

(1) The radiation sensitive composition for colored layer formation in which (B) alkali-soluble resin contains a copolymer (BII).

(2) The colored layer of the above (1), wherein the polyfunctional monomer (C) comprises at least one member selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate, and dipentaerythritol hexaacrylate. Radiation-sensitive composition for formation.

(3) Said photoinitiator containing 1 or more types chosen from the group which consists of an oxime type compound (D1), an oxime type compound (D2), a biimidazole type compound, an acetophenone type compound, and a triazine type compound, (1) ) Or a radiation sensitive composition for forming a colored layer of (2).

(4) The radiation sensitive composition for forming a colored layer of the above (1), (2) or (3), wherein the (A) colorant contains an organic pigment or carbon black.

In addition, the preferred color filter of the present invention

(5) It has the pixel and / or black matrix formed from the radiation sensitive composition for colored layer formation of said (1), (2), (3) or (4).

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

(6) provided with the color filter of (5) above,

More preferred color liquid crystal display device of the present invention

(7) The color filter of said (6) is provided on the thin film transistor substrate array.

As described above, the radiation-sensitive composition for forming a colored layer of the present invention is free from pattern defects such as pattern defects and undercuts, and is excellent in adhesion to the substrate, and excellent in electrical properties such as voltage retention and high. It is possible to provide a color filter having reliability.

Therefore, the radiation sensitive composition for colored layer formation of this invention can be used very favorably for manufacture of various color filters including the color filter for color liquid crystal display elements in the electronic industry.

<Example>

Hereinafter, an Example is given and embodiment of this invention is described further more concretely. However, the present invention is not limited to the following examples.

Mw and Mn of resin obtained by each following synthesis example were measured by the gel permeation chromatography (GPC) by the following specification.

Apparatus: GPC-101 (manufactured by Showa Denko Co., Ltd.)

Column: GPC-KF-801, GPC-KF-802, GPC-KF-803 and GPC-KF-804 were used in combination.

Mobile phase: tetrahydrofuran containing 0.5 wt% phosphoric acid

Synthesis Example 1

5 parts by weight of 2,2'-azobisvaleronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 20 parts by weight of methacrylic acid and monosuccinic acid (2-methacryl). 10 parts by weight of loyloxyethyl), 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, followed by nitrogen substitution. The reaction solution was heated to 70 ° C. with gentle stirring, and polymerized for 2 hours while maintaining this temperature. Thereafter, 2 parts by weight of 2,2'-azobisvaleronitrile was added and the polymerization solution was continued for 2 hours to obtain a resin solution (solid content concentration = 32.8 wt%). This resin was Mw = 12,000 and (Mw / Mn) = 2.8.

This resin solution was referred to as "resin solution (in s-1)" and this resin was referred to as "resin (in a-1)".

Synthesis Example 2

5 parts by weight of 2,2'-azobisvaleronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 20 parts by weight of methacrylic acid and monosuccinic acid (2-methacryl). Loyloxyethyl) 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 nitrogen substitution, the reaction solution was heated to 70 ° C. with gentle stirring, and polymerized for 2 hours while maintaining this temperature. Thereafter, 2 parts by weight of 2,2'-azobisvaleronitrile was added and the polymerization solution was continued for 2 hours to obtain a resin solution (solid content concentration = 32.8 wt%). This resin was Mw = 11,000 and (Mw / Mn) = 2.6.

This resin solution was referred to as "resin solution (in s-2)" and this resin was referred to as "resin (in a-2)".

Synthesis Example 3

5 parts by weight of 2,2'-azobisvaleronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by 10 parts by weight of methacrylic acid and 31.2 weight of N-phenylmaleimide. Part, 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, followed by nitrogen replacement. The reaction solution was heated to 70 ° C. with gentle stirring, and polymerized for 2 hours while maintaining this temperature. Thereafter, 2 parts by weight of 2,2'-azobisvaleronitrile was added, and the polymerization solution was further continued for 2 hours to obtain a resin solution (solid content concentration = 32.5% by weight). This resin was Mw = 11,000 and (Mw / Mn) = 2.9.

This resin solution was referred to as "resin solution (in s-3)" and this resin was referred to as "resin (in a-3)".

Synthesis Example 4

5 parts by weight of 2,2'-azobisvaleronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were placed in a flask equipped with a cooling tube and a stirrer, followed by 10 parts by weight of methacrylic acid and 31.2 weight of N-phenylmaleimide. Part, 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 added, and after nitrogen substitution, the reaction solution was stirred with gentle stirring. It heated up at ° C and superposed | polymerized for 2 hours, maintaining this temperature. Thereafter, 2 parts by weight of 2,2'-azobisvaleronitrile was added, and the polymerization solution was further continued for 2 hours to obtain a resin solution (solid content concentration = 31.9% by weight). This resin was Mw = 12,000 and (Mw / Mn) = 2.8.

This resin solution is referred to as "resin solution (in s-4)" and this resin is referred to as "resin (in a-4)".

Synthesis Example 5

5 parts by weight of 2,2'-azobisvaleronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 20 parts by weight of methacrylic acid and monosuccinic acid (2-methacryl). 10 parts by weight of loyloxyethyl), 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, and after nitrogen replacement, gently stirring 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 solution was continued for 2 hours to obtain a resin solution (solid content concentration = 32.8 wt%). This resin was Mw = 12,000 and (Mw / Mn) = 2.8.

This resin solution was referred to as "resin solution (in s-5)" and this resin was referred to as "resin (in a-5)."

Synthesis Example 6

5 parts by weight of 2,2'-azobisvaleronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 20 parts by weight of methacrylic acid and monosuccinic acid (2-methacryl). 10 parts by weight of loyloxyethyl), 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) were added, followed by nitrogen substitution. The reaction solution was heated to 80 ° C. with gentle stirring, and polymerized for 2 hours while maintaining this temperature. Thereafter, the reaction solution was heated to 100 ° C, 2 parts by weight of 2,2'-azobisvaleronitrile was added, and polymerization was continued for 2 hours to obtain a resin solution (solid content concentration = 32.8% by weight). This resin was Mw = 15,000 and (Mw / Mn) = 3.0.

This resin solution was referred to as "resin solution (in s-6)" and this resin was referred to as "resin (in a-6)".

Synthesis Example 7

5 parts by weight of 2,2'-azobisvaleronitrile and 200 parts by weight of propylene glycol monomethyl ether acetate were added to a flask equipped with a cooling tube and a stirrer, followed by 20 parts by weight of methacrylic acid and monosuccinic acid (2-methacryl). 10 parts by weight of loyloxyethyl), 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 added thereto, followed by nitrogen replacement, and the reaction solution was heated to 70 ° C. with gentle stirring. The polymerization was carried out for 2 hours while maintaining this temperature. Thereafter, 2 parts by weight of 2,2'-azobisvaleronitrile was added and the polymerization solution was continued for 2 hours to obtain a resin solution (solid content concentration = 32.8 wt%). This resin was Mw = 12,000 and (Mw / Mn) = 2.8.

This resin solution was referred to as "resin solution (in s-7)" and this resin was referred to as "resin (in a-7)".

[Evaluation of Defects and Adhesiveness]

Example 1

(A) As a coloring agent, C.I. Pigment Red 254 and C.I. 40 parts by weight of a 50/50 (weight ratio) mixture of Pigment Yellow 139, 10 parts by weight of Disperbyk 2001 (manufactured by BICCHEM JAPAN CORPORATION) as a dispersant, and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent. The pigment dispersion liquid was prepared by mixing and disperse | distributing for 12 hours with the diamond fine mill (brand name, the bead mill (Bead diameter 1.0mm) by Mitsubishi Material Corporation).

Subsequently, 100 parts by weight of this pigment dispersion liquid, (B) the amount of the resin solution (in s-1) as the alkali-soluble resin, 70 parts by weight of the resin (in a-1), and (C) dipentaerythritol as the polyfunctional monomer. 80 parts by weight of hexaacrylate, (D) 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime- as a photopolymerization initiator 50 parts by weight of 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).

Next, the liquid composition (r-1) was applied on a soda glass substrate, and prebaked at 80 ° C. for 2 minutes to form a coating film. Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, when the obtained stripe pattern was observed with the scanning electron microscope, the defect of the pattern was not seen and the adhesiveness with the board | substrate was also favorable.

Example 2

A liquid composition (r-2) was prepared in the same manner as in Example 1 except that the resin solution (in s-2) was used in an amount such that the resin (in a-2) was 70 parts by weight instead of the resin solution (in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, when the obtained stripe pattern was observed with the scanning electron microscope, the defect of the pattern was not seen and the adhesiveness with the board | substrate was also favorable.

Example 3

A liquid composition (r-3) was prepared in the same manner as in Example 1 except that the resin solution (in s-3) was used in an amount such that the resin (in a-3) was 70 parts by weight instead of the resin solution (in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, when the obtained stripe pattern was observed with the scanning electron microscope, the defect of the pattern was not seen and the adhesiveness with the board | substrate was also favorable.

Example 4

A liquid composition (r-4) was prepared in the same manner as in Example 1 except that the resin solution (in s-4) was used in an amount such that the resin (in a-4) was 70 parts by weight instead of the resin solution (in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, when the obtained stripe pattern was observed with the scanning electron microscope, the defect of the pattern was not seen and the adhesiveness with the board | substrate was also favorable.

Comparative Example 1

A liquid composition (r-5) was prepared in the same manner as in Example 1 except that the resin solution (in s-5) was used in an amount such that 70 parts by weight of the resin (in a-5) was added instead of the resin solution (in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, when the obtained stripe pattern was observed with the scanning electron microscope, the defect of the pattern was not seen and the adhesiveness with the board | substrate was also favorable.

Example 5

(A) As a pigment, C.I. Pigment Blue 15: 6 and C.I. A mixed liquid containing 40 parts by weight of a 90/10 (weight ratio) mixture of pigment violet 23, 10 parts by weight of Disperbyk 2001 (manufactured by BICKEMI JAPAN) as a dispersant, and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent. The pigment dispersion liquid was prepared by mixing and disperse | distributing for 12 hours with the diamond fine mill (brand name, the bead mill (Bead diameter 1.0mm) by Mitsubishi Material Corporation).

Subsequently, 100 parts by weight of this pigment dispersion liquid, (B) the amount of resin (a-1) in the resin solution (in s-1) as the alkali-soluble resin, and (C) dipentaerythritol as the polyfunctional monomer 70 parts by weight of hexaacrylate, (D) 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime- as a photopolymerization initiator 30 parts by weight of 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).

Next, the liquid composition (r-6) was applied on a soda glass substrate, and prebaked at 80 ° C. for 2 minutes to form a coating film. Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, when the obtained stripe pattern was observed with the scanning electron microscope, the defect of the pattern was not seen and the adhesiveness with the board | substrate was also favorable.

Example 6

A liquid composition (r-7) was prepared in the same manner as in Example 5 except that the resin solution (in s-2) was used in an amount such that the resin (in a-2) was 80 parts by weight instead of the resin solution (in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, when the obtained stripe pattern was observed with the scanning electron microscope, the defect of the pattern was not seen and the adhesiveness with the board | substrate was also favorable.

Example 7

A liquid composition (r-8) was prepared in the same manner as in Example 5 except that the resin solution (in s-3) was used in an amount of 80 parts by weight of the resin (in medium a-3) instead of the resin solution (in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, when the obtained stripe pattern was observed with the scanning electron microscope, the defect of the pattern was not seen and the adhesiveness with the board | substrate was also favorable.

Example 8

A liquid composition (r-9) was prepared in the same manner as in Example 5 except that the resin solution (s-4 in s-4) was used in an amount of 80 parts by weight of the resin (a-4 in resin) instead of the resin solution (s-1 in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, when the obtained stripe pattern was observed with the scanning electron microscope, the defect of the pattern was not seen and the adhesiveness with the board | substrate was also favorable.

Comparative Example 2

A liquid composition (r-10) was prepared in the same manner as in Example 5 except that the resin solution (in s-5) was used in an amount such that the resin (in a-5) was 80 parts by weight instead of the resin solution (in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, when the obtained stripe pattern was observed with the scanning electron microscope, the defect of the pattern was not seen and the adhesiveness with the board | substrate was also favorable.

Example 9

(A) As a pigment, C.I. Pigment Green 36 and C.I. 40 parts by weight of a 50/50 (weight ratio) mixture of Pigment Yellow 150, 10 parts by weight of Disperbyk 2001 (manufactured by Bigchem Japan Japan) as a dispersant, and 100 parts by weight of ethyl 3-ethoxypropionate as a solvent The pigment dispersion liquid was prepared by mixing and disperse | distributing for 12 hours with the diamond fine mill (brand name, the bead mill (Bead diameter 1.0mm) by Mitsubishi Material Corporation).

Subsequently, 100 parts by weight of this pigment dispersion liquid, (B) the amount of resin (a-1) in the resin solution (in s-1) as the alkali-soluble resin, and (C) dipentaerythritol as the polyfunctional monomer 70 parts by weight of hexaacrylate, (D) 1- [9-ethyl-6- (2-methylbenzoyl) -9.H.-carbazol-3-yl] -ethane-1-one oxime- as a photopolymerization initiator 30 parts by weight of 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, the liquid composition (r-11) was applied on a soda glass substrate, and prebaked at 80 ° C. for 2 minutes to form a coating film. Subsequently, radiation containing each wavelength of 365 nm, 405 nm and 436 nm was exposed to the coating film at an exposure dose of 5,000 J / m 2 through a stripe pattern photomask having a width of 90 micrometers using a high pressure mercury lamp. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, when the obtained stripe pattern was observed with the scanning electron microscope, the defect of the pattern was not seen and the adhesiveness with the board | substrate was also favorable.

Example 10

A liquid composition (r-12) was prepared in the same manner as in Example 9 except that the resin solution (in s-2) was used in an amount such that the resin (in a-2) was 80 parts by weight instead of the resin solution (in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, when the obtained stripe pattern was observed with the scanning electron microscope, the defect of the pattern was not seen and the adhesiveness with the board | substrate was also favorable.

Example 11

A liquid composition (r-13) was prepared in the same manner as in Example 9 except that the resin solution (in s-3) was used in an amount of 80 parts by weight of the resin (in medium a-3) instead of the resin solution (in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, when the obtained stripe pattern was observed with the scanning electron microscope, the defect of the pattern was not seen and the adhesiveness with the board | substrate was also favorable.

Example 12

A liquid composition (r-14) was prepared in the same manner as in Example 9 except that the resin solution (in s-4) was used in an amount such that the resin (in a-4) was 80 parts by weight instead of the resin solution (in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, when the obtained stripe pattern was observed with the scanning electron microscope, the defect of the pattern was not seen and the adhesiveness with the board | substrate was also favorable.

Comparative Example 3

A liquid composition (r-15) was prepared in the same manner as in Example 9 except that the resin solution (in s-5) was used in an amount of 80 parts by weight of the resin (in medium a-5) instead of the resin solution (in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, when the obtained stripe pattern was observed with the scanning electron microscope, the defect of the pattern was not seen and the adhesiveness with the board | substrate was also favorable.

Comparative Example 4

A liquid composition (r-16) was prepared in the same manner as in Example 1 except that the resin solution (s-6 in s-6) was used in an amount of 70 parts by weight of the resin (a-6 in resin) instead of the resin solution (s-1 in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, as a result of observing the obtained stripe pattern with a scanning electron microscope, a large number of defects were seen in the pattern, and the part where the pattern was partially peeled from the substrate was also seen.

Comparative Example 5

A liquid composition (r-17) was prepared in the same manner as in Example 1, except that the resin solution (in s-7) was used in an amount of 70 parts by weight of the resin (in medium a-7) instead of the resin solution (in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, as a result of observing the obtained stripe pattern with a scanning electron microscope, a large number of defects were seen in the pattern, and the part where the pattern was partially peeled from the substrate was also seen.

Comparative Example 6

A liquid composition (r-18) was prepared in the same manner as in Example 5 except that the resin solution (s-6 in s-6) was used in an amount of 80 parts by weight of the resin (a-6 in resin) instead of the resin solution (s-1 in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, as a result of observing the obtained stripe pattern with a scanning electron microscope, a large number of defects were seen in the pattern, and the part where the pattern was partially peeled from the substrate was also seen.

Comparative Example 7

A liquid composition (r-19) was prepared in the same manner as in Example 5 except that the resin solution (in s-7) was used in an amount such that the resin (in a-7) was 80 parts by weight instead of the resin solution (in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, as a result of observing the obtained stripe pattern with a scanning electron microscope, a large number of defects were seen in the pattern, and the part where the pattern was partially peeled from the substrate was also seen.

Comparative Example 8

A liquid composition (r-20) was prepared in the same manner as in Example 9 except that the resin solution (s-6 in s-6) was used in an amount of 80 parts by weight of the resin (a-6 in resin) instead of the resin solution (s-1 in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, as a result of observing the obtained stripe pattern with a scanning electron microscope, a large number of defects were observed in the pattern, and a large number of portions in which the pattern was partially separated from the substrate were observed.

Comparative Example 9

A liquid composition (r-21) was prepared in the same manner as in Example 9 except that the resin solution (in s-7) was used in an amount such that the resin (in a-7) was 80 parts by weight instead of the resin solution (in s-1). Was prepared and the coating film of the said composition was formed on the soda glass substrate.

Subsequently, a high-pressure mercury lamp was used to expose the coating film at a exposure amount of 5,000 J / m 2 to the coating film, each wavelength having 365 nm, 405 nm, and 436 nm, through a stripe pattern photomask having a width of 90 micrometers. Then, this board | substrate was immersed and developed for 1 minute in the developing solution containing 0.04 weight% potassium hydroxide aqueous solution at 23 degreeC, and then it wash | cleaned with ultrapure water and air-dried.

Subsequently, as a result of observing the obtained stripe pattern with a scanning electron microscope, a large number of defects were observed in the pattern, and a large number of portions in which the pattern was partially separated from the substrate were observed.

[Evaluation of Voltage Retention Rate]

On the surface of each liquid composition of Examples 1 to 12 and Comparative Examples 1 to 9, a SiO ₂ film was formed on the surface to prevent elution of sodium ions, and a soda glass substrate in which an ITO (indium-tin oxide alloy) electrode was deposited in a predetermined shape. After apply | coating using a spin coater on it, it prebaked for 10 minutes in 90 degreeC clean oven, and formed the coating film of 1.8 micrometers in thickness.

Subsequently, a high pressure mercury lamp was used to expose the radiation containing each wavelength of 365 nm, 405 nm, and 436 nm to the coating film at an exposure amount of 5,000 J / m 2 without passing through the photomask. Thereafter, the substrate was immersed in a developing solution containing a 0.04 wt% potassium hydroxide aqueous solution at 23 ° C. for 1 minute, developed, washed with ultrapure water, air dried, and further subjected to post-baking at 230 ° C. for 30 minutes to cure the coating film. Red pixels were formed on the substrate. The film thickness of this pixel was 1.5 µm.

Subsequently, after bonding the board | substrate which formed this pixel and the board | substrate which only deposited the ITO electrode to the predetermined shape with the sealing agent which mixed 0.018 mm glass beads, liquid crystal MLC6608 (brand name) by a Merck company is injected, and a liquid crystal cell is manufactured. It was.

Subsequently, a liquid crystal cell is put into a 60 degreeC thermostat, and the voltage retention of a liquid crystal cell is a square wave whose applied voltage is 5.0V, and a measurement frequency by the liquid crystal voltage retention measurement system VHR-1A type (brand name) by Toyo Technica. Was measured under the condition of 60 Hz.

Here, voltage retention is a value computed as (potential difference of the liquid crystal cell 16.7 milliseconds after voltage application) / (voltage immediately after voltage application).

The measurement result of voltage retention is shown in following Table 1 with the presence or absence of N-phenylmaleimide and allyl methacrylate in alkali-soluble resin, and the evaluation result of defect and adhesiveness. If the voltage retention of the liquid crystal cell is less than 90%, it means that the liquid crystal cell cannot maintain the applied voltage at a predetermined level and cannot sufficiently align the liquid crystal.

The present invention provides a novel radiation-sensitive composition for forming a colored layer which is capable of producing a color filter having no pattern defects such as defects or undercuts, excellent adhesion to a substrate, and excellent reliability in electrical properties. to provide.

Claims (4)

In the radiation sensitive composition for colored layer formation containing (A) a coloring agent, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoinitiator, (B) alkali-soluble resin is (b1) unsaturated At least one selected from the group consisting of carboxylic acid, unsaturated carboxylic anhydride and unsaturated phenol compound, (b2) N-substituted maleimide, (b3) unsaturated compound having an allyl group, and (b4) aromatic vinyl Compounds, indenes or derivatives thereof, unsaturated carboxylic acid ester compounds, unsaturated carboxylic acid aminoalkyl ester compounds, unsaturated carboxylic acid glycidyl ester compounds, vinyl cyanide compounds, unsaturated amide compounds, carboxylic acid vinyl ester compounds, vinyl ethers Selected from the group consisting of a compound, an aliphatic conjugated diene compound and a macromonomer having a mono (meth) acryloyl group at the ends of the polymer molecular chain A radiation sensitive composition for forming sense of the colored layer comprises a copolymer of at least one. The radiation sensitive composition for forming a colored layer according to claim 1, wherein the photopolymerization initiator of component (D) comprises a compound represented by the following formula (1) and / or a compound represented by the following formula (2). <Formula 1>

<Formula 2>

[In Formula 1 and Formula 2, each R <^1> represents a C1-C12 linear, branched or cyclic alkyl group, or a phenyl group independently of each other, and each R <^2> is a hydrogen atom, a C1-C12 straight line independently of each other, A chain, branched or cyclic alkyl group or a phenyl group, R ³ represents a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 12 carbon atoms, and each R ⁴ , each R ⁵ and each R ⁶ is independently hydrogen Linear or branched or cyclic alkyl groups having 1 to 6 carbon atoms, provided that the alkyl groups of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are each linear 1 to 6 carbon atoms, It may be substituted with a substituent selected from the group of a branched or cyclic alkoxyl group, a phenyl group and a halogen atom, the phenyl group of R ¹ and R ² are each a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms, 1 to 6, linear, branched Or a substituent selected from the group of cyclic alkoxyl groups, phenyl groups and halogen atoms] The color filter which has a colored layer formed from the radiation sensitive composition for colored layer formation of Claim 1 or 2. The color liquid crystal display element provided with the color filter of Claim 3.