KR100760459B1 - Radiation Sensitive Composition for Forming Spacers on the Drive Substrate of a Thin Film Transistor Color Liquid Crystal Display Device, Drive Substrate Having Spacers Thereon, Production Process Therefor and Color Liquid Crystal Display Device - Google Patents

Abstract

The photosensitive composition for forming a spacer on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device includes (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator. do. The composition does not irreversibly deform when sealing the panel, there is no display defect due to the gap of the liquid crystal layer, it can provide a spacer excellent in light shielding, mechanical strength and heat resistance.

Photosensitive, Liquid Crystal, Transistor

Description

Photosensitive composition for forming a spacer on a driving substrate of a thin film transistor type color liquid crystal display device, a driving substrate having a spacer, a manufacturing method thereof and a color liquid crystal display device (Radiation Sensitive Composition for Forming Spacers on the Drive Substrate of a Thin Film Transistor Color Liquid Crystal Display Device, Drive Substrate Having Spacers Thereon, Production Process Therefor and Color Liquid Crystal Display Device}

1 is a cross section of an essential part of an example of a thin film transistor (TFT) type color liquid crystal display device;

FIG. 2 is a cross-sectional view taken along the line X-X of FIG. 1.

The present invention relates to a photosensitive composition for forming a spacer on a driving substrate of a thin film transistor (TFT) type color liquid crystal display device of a transmission or reflection type, a driving substrate on which a spacer is formed, a manufacturing method thereof, and a color liquid crystal display device. It is about.

In the manufacture of a color liquid crystal display device including a thin film transistor (TFT) substrate, a color filter substrate for displaying a color image is manufactured separately from a driving substrate on which a thin film transistor (TFT) is formed thereon. Assemble with the board. However, in this system, since the positioning accuracy at the time of assembly is low, it becomes difficult to obtain a high aperture ratio by widening the area of the black matrix (opening ratio for transmitting light).

On the other hand, a colored layer is formed on the surface of the driving substrate on which the thin film transistor (TFT) is formed on the surface directly or through a passivation film such as a silicon nitride film, and the colored layer is formed on the surface. The new system was developed by assembling this substrate with a substrate on which a tin doped indium oxide (ITO) electrode was formed on the surface by sputtering. In this system, since the colored layer including the pixel and the black matrix is formed directly on the driving substrate, the step of assembling the color filter substrate and the driving substrate becomes unnecessary and the aperture ratio is greatly improved compared to the electronic system. A bright high precision display device can be obtained.

Spacers used in the latter system are generally formed from photosensitive compositions by lithography. The spacer must have light shielding property to prevent the thin film transistor TFT from malfunctioning as a switching element by the incident light of the thin film transistor TFT.

In addition, the spacer requires mechanical strength and heat resistance to withstand high temperature and high pressure in the step of sealing the panel after injection of the liquid crystal for preparing the label panel.                         

However, no photosensitive composition for spacers with satisfactory light shielding properties and excellent mechanical strength and heat resistance has been found. Therefore, the gap difference of the liquid crystal layer is formed by irreversible deformation of the spacer when the panel is closed, resulting in display defects.

Disclosure of Invention An object of the present invention is to provide a photosensitive composition for forming a spacer on a driving substrate for a thin film transistor (TFT) type color liquid crystal display device, and the composition provides a spacer having excellent light blocking property and high mechanical strength and heat resistance. It can be formed so that it is not irreversibly deformed during panel sealing and there is no display failure due to gap difference of the liquid crystal layer.

Another object of the present invention is to provide a driving substrate having a spacer formed from the photosensitive composition of the present invention and a method of manufacturing the same.

Still another object of the present invention is to provide a color liquid crystal display device comprising the driving substrate of the present invention.

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

First, the above objects and advantages of the present invention include (A) a colorant, (B) an alkali-soluble resin, (C) a polyfunctional monomer, and (D) a photopolymerization initiator, on a driving substrate of a thin film transistor type color liquid crystal display device. Achieved by a photosensitive composition for forming a spacer.

Secondly, the above objects and advantages of the present invention are achieved by a driving substrate for a thin film transistor type color liquid crystal display device comprising a spacer formed from the photosensitive composition of the present invention.

Third, the above objects and advantages of the present invention

Forming a color film including a colored layer on a driving substrate of the thin film transistor type color liquid crystal display device directly or through a passivation film; And

Forming a spacer from the photosensitive composition of the present invention on the color film

It is achieved by a method of manufacturing a drive substrate having a spacer, comprising a.

Finally, the above objects and advantages of the present invention are achieved by a thin film transistor type color liquid crystal display device comprising the driving substrate of the present invention.

(A) colorant

Colorants used in the present invention are not limited to specific colors, but colorants having specific OD (optical density) values, colorants containing black pigments or colorants containing black pigments and having specific OD values are preferred.

The expression "specific OD value" means that the OD value is at least 2, preferably at least 2.5, particularly preferably at least 3, when a 5 μm thick spacer is formed.

The black pigment may be appropriately selected depending on the application purpose of the spacer. The pigment may be a single pigment of inorganic or organic, or a mixture of two or more pigments. Preferred black pigments are pigments with high color development and high heat resistance, in particular high pyrolysis resistance, with carbon black and / or combinations of two or more organic pigments being particularly preferred.

Examples of carbon blacks used in the present invention include SAF, SAF-HS, ISAF, ISAF-LS, ISAF-HA, HAF, HAF-LS, HAF-HS, NAF, FEF, FEF-HS, SRP, SRF-LM, Furnace blacks such as SRF-LS, GPF, ECF, N-339 and N-351; Thermal blacks such as FT and MT; And acetylene black.

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

Examples of inorganic black pigments other than carbon black used in the present invention include metal oxides such as titanium black, Cu-Fe-Mn-based oxides and synthetic iron black.

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

Further examples of organic pigments used in the present invention include compounds classified into pigment groups according to color index (CI; issued by the Society of Dyers and Colourists), specifically compounds having the following color index (CI) numbers. :

C.I. Pigment Yellow 12, C.I. Pigment Yellow 13, C.I. Pigment Yellow 14, 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 83, C.I. Pigment Yellow 93, C.I. Pigment Yellow 109, C.I. Pigment Yellow 110, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 155, C.I. Pigment Yellow 166, C.I. Pigment Yellow 168 and C.I. Pigment yellow 211;

C.I. Pigment Orange 36, C.I. Pigment Orange 43, C.I. Pigment Orange 51, C.I. Pigment Orange 61 and C.I. Pigment orange 71;                     

C.I. Pigment Red 9, C.I. Pigment Red 97, C.I. Pigment Red 122, C.I. Pigment Red 123, C.I. Pigment Red 149, C.I. Pigment Red 168, C.I. Pigment Red 176, C.I. Pigment Red 177, C.I. Pigment Red 180, C.I. Pigment Red 207, C.I. Pigment Red 208, C.I. Pigment Red 209, C.I. Pigment Red 215, C.I. Pigment Red 224, C.I. Pigment Red 242 and C.I. Pigment red 254;

C.I. Pigment Purple 19, C.I. Pigment Purple 23 and C.I. Pigment purple 29;

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

C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Green 136 and C.I. Pigment green 210;

C.I. Pigment Brown 23 and C.I. Pigment brown 25; And

C.I. Pigment Black 1 and C.I. Pigment Black 7.

These organic pigments are appropriately selected and used to obtain a desired color of the spacer.

In the present invention, organic pigments include C.I. Pigment red 177 and C.I. Pigment blue 15: 4 and C.I. Particular preference is given to mixtures of one or more pigments selected from the group consisting of pigment blue 15: 6.

The organic pigment may be purified by recrystallization, reprecipitation, washing with a solvent, sublimation, vacuum heating or a combination thereof.

Colorants of the present invention may contain extender pigments, if desired.                     

Examples of extender pigments include barium sulfate, barium carbonate, calcium carbonate, silica, basic magnesium carbonate, alumina white, gloss white, satin white and hydrotalcite.

These extender pigments may be used alone or in combination of two or more thereof.

The amount of extender pigment is preferably from 0 to 100 parts by weight, more preferably from 5 to 50 parts by weight, even more preferably from 10 to 40 parts by weight, based on 100 parts by weight of the black pigment.

The pigments can in particular be optionally surface modified by polymers. Examples of polymers for modifying the surface of each pigment particle include polymers disclosed in Japanese Patent No. 8-259876 (the term "Japanese Patent No." used herein means "Unpublished published Japanese patent application", and There are commercially available polymers and oligomers for dispersing pigments.

The colorant of the present invention may optionally be used with a dispersant.

The dispersant is a cationic surfactant, anionic surfactant, nonionic surfactant, amphoteric surfactant, silicone based surfactant or fluorine based surfactant.

Examples of surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether and polyoxyethylene oleyl ether; Polyoxyethylene alkylphenyl ethers such as polyoxyethylene n-octylphenyl ether and polyoxyethylene n-nonylphenyl ether; Polyethylene glycol diesters such as polyethylene glycol dilaurate and polyethylene glycol distearate; Sorbitan fatty acid esters; Polyesters modified with fatty acids; Polyurethanes modified with tertiary amines; And polyethylene imine. These surfactants include the brand name Shin-Etsu Chemical, Co., LTD., Polyflow; Kyoeisha Kagaku Co., Ltd., F Top; Tokem Products Co., Ltd., Megapack. (Megafac; Dainippon Ink and Chemicals, Inc.), Florade; Sumitomo 3M Limited, Disperbyk; Byk Chemie Japan Co., Ltd., Solsperse, Zeneca Co., Ltd., and EFKA (EFKA Chemicals, Co., Ltd.) is commercially available.

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

The amount of the surfactant is preferably 50 parts by weight or less, more preferably 30 parts by weight or less based on 100 parts by weight of the colorant.

(B) alkali soluble resin

Any alkali-soluble resin can be used in the present invention as long as it acts as a binder for the colorant (A) and is soluble in the developer used in the developing step for the formation of the spacer, particularly preferably in the alkaline developer. Examples of alkali-soluble resins are copolymers of polymerizable unsaturated monomers with acidic functional groups such as carboxyl groups, phenolic hydroxyl groups or sulfonic acid groups and other copolymerizable unsaturated monomers (hereinafter referred to as "copolymerizable unsaturated monomers"). .

Examples of polymerizable unsaturated monomers having one or more carboxyl groups in the molecule (hereinafter referred to as “carboxyl group-containing unsaturated monomers”) include unsaturated monocarboxylic acids such as (meth) acrylic acid, crotonic acid, α-chloroacrylic acid and cinnamic acid. ; Unsaturated dicarboxylic acids and 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 polycarboxylic acids and their anhydrides; Mono [(meth) acryloyloxyalkyl of a divalent or higher polycarboxylic acid such as mono [2- (meth) acryloyloxyethyl] succinate and mono [2- (meth) acryloyloxyethyl] phthalate )ester; And mono (meth) acrylates of polymers having carboxyl groups and hydroxyl groups at both ends, such as ω-carboxypolycaprolactone mono (meth) acrylates.

Among these carboxyl group-containing unsaturated monomers, (meth) acrylic acid and mono [2- (meth) acryloyloxyethyl] succinate are particularly preferred.

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

Examples of polymerizable unsaturated monomers having phenolic hydroxyl groups include o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o-hydroxy-α-methylstyrene, m-hydroxy-α-methyl Styrene, p-hydroxy-α-methylstyrene, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide and Np-hydroxyphenylmaleimide.

These polymerizable unsaturated monomers having phenolic hydroxyl groups may be used alone or in combination of two or more thereof.

Examples of polymerizable unsaturated monomers having sulfonic acid groups include isoprenesulfonic acid and p-styrenesulfonic acid.

These polymerizable unsaturated monomers having sulfonic acid groups may be used alone or in combination of two or more thereof.

Examples of copolymerizable unsaturated monomers include macros having mono (meth) acryloyl groups at the ends of the molecular chain of the polymer, such as polystyrene, polymethyl (meth) acrylates, poly-n-butyl (meth) acrylates and polysiloxanes. Monomers (hereinafter referred to as "macromonomers"); N-phenylmaleimide, No-methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide and N- N-substituted maleimides, such as N- (substituted) arylmaleimide, including cyclohexylmaleimide; Styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzylmethyl Aromatic vinyl compounds such as ether, m-vinylbenzylmethyl ether, p-vinylbenzylmethyl ether, o-vinylbenzylglycidyl ether, m-vinylbenzyl glycidyl ether and p-vinylbenzyl glycidyl ether; Indenes such as indene and 1-methylindene; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate , 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, allyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (Meth) acrylate, phenyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, methoxytriethylene glycol (Meth) acrylate, methoxypropylene glycol ( Methacrylate, methoxydipropylene glycol (meth) acrylate, isobornyl (meth) acrylate, dicyclopentadienyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate And unsaturated carboxylic esters such as monomers represented by formula (I) (hereinafter referred to as "glycerol (meth) acrylate"); 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylate, 2-aminopropyl (meth) acrylate, 2-dimethylaminopropyl (meth) acrylate, 3-aminopropyl (meth) acrylic Unsaturated carboxylic acid aminoalkyl esters such as late and 3-dimethylaminopropyl (meth) acrylate; Unsaturated carboxylic acid glycidyl esters such as glycidyl (meth) acrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinylmethyl ether, vinylethyl ether and allylglycidyl ether; Vinyl cyanide compounds such as (meth) acrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as (meth) acrylamide, α-chloroacrylamide and N-2-hydroxyethyl (meth) acrylamide; And aliphatic conjugate dienes such as 1,3-butadiene, isoprene and chloroprene.

In the above formula, R ¹ is a hydrogen atom or a methyl group.

Of these copolymerizable unsaturated monomers, macromonomers, N-substituted maleimides, 2-hydroxyethyl (methyl) acrylates, benzyl (meth) acrylates and glycerol (meth) acrylates are preferred. Of these macromonomers, polystyrene macromonomers and polymethyl (meth) acrylate macromonomers are particularly preferred. Particular preference is given to N-phenylmaleimide and N-cyclohexylmaleimide among N-substituted maleimides.

The copolymerizable unsaturated monomers may be used alone or in combination of two or more thereof.

As the alkali-soluble resin (B) in the present invention, a copolymer of an unsaturated monomer copolymerizable with a carboxyl group-containing unsaturated monomer (hereinafter, simply referred to as a "carboxyl group-containing copolymer") is preferable.

The carboxyl group-containing copolymer includes (a) a carboxyl group-containing unsaturated monomer, (b) a macromonomer having a mono (meth) acryloyl group at the molecular chain terminal, an N-substituted maleimide, 2-hydroxy (meth) acrylate, benzyl ( One or more monomers selected from the group consisting of meth) acrylate and glycerol (meth) acrylate and optionally (c) from the group consisting of styrene, methyl (meth) acrylate, allyl (meth) acrylate and phenyl (meth) acrylate Preference is given to copolymers of at least one monomer selected. (1) carboxyl group-containing unsaturated monomer, (2) polystyrene macromonomer, polymethyl (meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, At least one monomer selected from the group consisting of benzyl (meth) acrylate and glycerol (meth) acrylate and optionally (3) styrene, methyl (meth) acrylate, allyl (meth) acrylate and phenyl (meth) acrylate More preferred are copolymers of monomer mixtures containing one or more monomers selected from the group (hereinafter referred to as "carboxyl group-containing copolymer (I)"). (1) A carboxyl group-containing unsaturated monomer component containing (meth) acrylic acid or a combination of (meth) acrylic acid and mono [2- (meth) acryloyloxyethyl] succinate, (2) polystyrene macromonomer, polymethyl ( One selected from the group consisting of meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol (meth) acrylate Copolymers of monomer mixtures containing at least one monomer and optionally at least one monomer selected from the group consisting of (3) styrene, methyl (meth) acrylate, allyl (meth) acrylate and phenyl (meth) acrylate. Particular preference is given to carboxyl group-containing copolymer (II) ".

Examples of the carboxyl group-containing copolymer (II) include copolymers of (meth) acrylic acid, benzyl (meth) acrylate and polystyrene macromonomers; Copolymers of (meth) acrylic acid, benzyl (meth) acrylate and polymethyl (meth) acrylate macromonomers; Copolymers of (meth) acrylic acid, N-phenylmaleimide, benzyl (meth) acrylate and styrene; Copolymers of (meth) acrylic acid, mono [2- (meth) acryloyloxyethyl] succinate, N-phenylmaleimide, styrene and allyl (meth) acrylate; Copolymers of (meth) acrylic acid, mono [2- (meth) acryloyloxyethyl] succinate, N-phenylmaleimide, benzyl (meth) acrylate and styrene; Copolymers of (meth) acrylic acid, N-cyclohexylmaleimide, benzyl (meth) acrylate and styrene; Copolymers of (meth) acrylic acid, mono [2- (meth) acryloyloxyethyl] succinate, N-cyclohexylmaleimide, styrene and allyl (meth) acrylate; Copolymers of (meth) acrylic acid, mono [2- (meth) acryloyloxyethyl] succinate, N-cyclohexylmaleimide, benzyl (meth) acrylate and styrene; Copolymers of (meth) acrylic acid, benzyl (meth) acrylate and glycerol mono (meth) acrylate; Copolymers of (meth) acrylic acid, mono [2- (meth) acryloyloxyethyl] succinate, benzyl (meth) acrylate and glycerol mono (meth) acrylate; Copolymers of (meth) acrylic acid and 2-hydroxyethyl (meth) acrylate; Copolymers of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate and styrene; Copolymers of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate and benzyl (meth) acrylate; Copolymers of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate and phenyl (meth) acrylate; Copolymers of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate, and polystyrene macromonomers; Copolymers of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and polymethyl (meth) acrylate macromonomers; Copolymers of (meth) acrylic acid, N-phenylmaleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and styrene; And copolymers of (meth) acrylic acid, N-phenylmaleimide, benzyl (meth) acrylate, glycerol mono (meth) acrylate and styrene.

Alkali-soluble resins of the present invention include copolymers of (meth) acrylic acid, mono [2- (meth) acryloyloxyethyl] succinate, N-phenylmaleimide, benzyl (meth) acrylate and styrene; Copolymers of (meth) acrylic acid, 2-hydroxyethyl (meth) acrylate and benzyl (meth) acrylate; And copolymers of (meth) acrylic acid, N-phenylmaleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and styrene are particularly preferred.

The amount of the carboxyl group-containing unsaturated monomer contained in the carboxyl group-containing copolymer of the present invention is preferably 5 to 50% by weight, more preferably 10 to 40% by weight. When the amount of the carboxyl group-containing unsaturated monomer is less than 5% by weight, the solubility of the monomer in the alkaline developer of the obtained photosensitive composition may be low, and when the amount is more than 50% by weight, the solubility of the monomer in the alkaline developer is too high. The spacers can be easily released from the substrate during the development process with the alkaline developer.

The polystyrene reduced weight average molecular weight (hereinafter referred to as "Mw") measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran) of the alkali-soluble resin in the present invention is preferably 20,000 or less, more preferably 3,000 to 20,000, particularly preferably 5,000 to 20,000.

The glass transition temperature of the alkali-soluble resin (hereinafter referred to as "Tg") is preferably 110 ° C or higher, more preferably 110 to 200 ° C, particularly preferably 110 to 180 ° C.

It is especially preferable to adjust Mw of alkali-soluble resin contained in the photosensitive composition to 20,000 or less, and to adjust Tg to 110 degreeC or more. When post-baking for the formation of the spacer, the photosensitive composition retains satisfactory heat resistance and improves its fluidity, whereby the spacer is tapered in the normal direction and its heat resistance and mechanical strength can be easily obtained simultaneously. When the spacers are tapered in opposite directions, they may be difficult to obtain their mechanical strength and heat resistance at the same time, and may be removed when rubbing the alignment film to produce the display panel.

In the combination of Mw and Tg of alkali-soluble resin, More preferably, Mw is 3,000-20,000, Tg is 110-200 degreeC, Especially preferably, Mw is 5,000-20,000 and Tg is 110-180 degreeC.

The polystyrene reduced number average molecular weight (hereinafter referred to as "Mn") measured by gel permeation chromatography (GPC, solvent: tetrahydrofuran) of the alkali-soluble resin is preferably 1,500 to 10,000.

The ratio (Mw / Mn) of Mw to Mn of the alkali-soluble resin is preferably 1 to 5, more preferably 1 to 4.

In the present invention, the alkali-soluble resin can be used alone or in combination of two or more.

The amount of the alkali-soluble resin is preferably 10 to 1,000 parts by weight, more preferably 20 to 500 parts by weight based on 100 parts by weight of the colorant (A). When the amount of alkali-soluble resin is less than 10 parts by weight, alkali developability may be lowered, or stains or film residues may be present on some substrates or light shielding layers not exposed to radiation. When the amount is more than 1,000 parts by weight, it may be difficult to obtain a target color concentration for the light shielding spacer because the concentration of the colorant is relatively low.

(C) polyfunctional monomer

The multifunctional monomer of the present invention is a monomer having two or more polymerizable unsaturated bonds.

Examples of the multifunctional monomers include di (meth) acrylates of alkylene glycols such as ethylene glycol and propylene glycol; Di (meth) acrylates of polyalkylene glycols such as polyethylene glycol and polypropylene glycol; Poly (meth) acrylates of trihydric or higher polyhydric alcohols such as glycerin, trimethylolpropane, pentaerythritol and dipentaerythritol and their dicarboxylic acid modified products; Oligo (meth) acrylates such as polyesters, epoxy resins, urethane resins, alkyd resins, silicone resins and spiran resins; Di (meth) acrylates of polymers hydroxylated at both ends, such as poly-1,3-butadiene, polyisoprene and polycaprolactone having hydroxyl groups at both ends; And tris [2- (meth) acryloyloxyethyl] phosphate.

Among these polyfunctional monomers, poly (meth) acrylates of trihydric or higher polyhydric alcohols and their dicarboxylic acid modified products such as trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the compound represented by the following formula (2) are preferred, of which trimethylolpropane triacrylate Pentaerythritol triacrylate and dipentaerythritol hexaacrylate are particularly preferred because they provide high strength spacers and hardly form stains or film residues on some unexposed substrates and light shielding layers.

In the above formula, R ² is a hydrogen atom or a methyl group.

These functional monomers can be used individually or in combination of 2 or more types.

The amount of the multifunctional 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 alkali-soluble resin (B). When the amount of the polyfunctional monomer is less than 5 parts by weight, the strength of the spacer may be lowered. When the amount is more than 500 parts by weight, the alkali developability may be lowered, or on some substrates or light shielding layers not exposed to radiation. There may be stains or film residues on the surface.

In the present invention, the monofunctional monomer having one polymerizable unsaturated bond can be used in combination with the polyfunctional monomer.

Examples of monofunctional monomers include carboxyl group-containing unsaturated monomers; Copolymerizable unsaturated monomers listed for alkali-soluble resins (B); N-vinylsuccinimide, N-vinylpyrrolidone, N-vinylphthalimide, N-vinyl-2-piperidine, N-vinyl-ε-caprolactam, N-vinylpyrrole, N-vinylpyrrolidone Dean, N-vinylimidazole, N-vinylimidazolidine, N-vinylindole, N-vinylindolin, N-vinylbenzimidazole, N-vinylcarbazole, N-vinylpiperidine, N- N-vinyl derivatives such as vinylpiperazine, N-vinylmorpholine and N-vinylphenoxazine; And N- (meth) acryloyl morpholine. As the monofunctional monomer, trade names M-5300, M-5400 and M-5600 (Toagosei Chemical Industry Co., Ltd.) are commercially available.

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

The amount of the monofunctional monomer is preferably 90% by weight or less, more preferably 50% by weight or less based on 100 parts by weight of the total of the multifunctional monomer and the monofunctional monomer. When the amount of the monofunctional monomer is greater than 90% by weight, the strength of the spacer may be lowered.

(D) photoinitiator

In the present invention, the photopolymerization initiator is a monofunctional monomer (C), and optionally a monofunctional used for irradiation such as visible light irradiation, ultraviolet irradiation, far ultraviolet irradiation, electron beam and X-ray radiation (hereinafter referred to as "exposure"). Compounds capable of forming active species capable of initiating the polymerization of the monomers.

Examples of photopolymerization initiators include acetophenone compounds, biimidazole compounds, triazine compounds, benzoin compounds, benzophenone compounds, α-diketone compounds, polynuclear quinone compounds, xanthone compounds and diazo compounds.                     

In the present invention, the photopolymerization initiator may be used alone or in combination of two or more. In the present invention, the photopolymerization initiator is preferably at least one compound selected from the group consisting of an acetophenone compound, a biimidazole compound, and a triazine compound.

The amount of the photopolymerization initiator in the present invention is preferably 0.01 to 80 parts by weight, more preferably 1 to 60 parts by weight based on a total of 100 parts by weight of the multifunctional monomer (C) and the monofunctional monomer. When the amount of the photopolymerization initiator is less than 0.01 part by weight, it may be difficult to obtain a spacer arranged in a predetermined pattern due to incomplete curing by exposure, and when the amount is more than 80 parts by weight, the formed spacer is easily removed from the substrate during development. Can come off.

Examples of the acetophenone compound in the preferred photopolymerization initiator in the present invention include 1-phenyl-2-hydroxy-2-methylpropan-1-one and 1- [4- (methylthio) phenyl] -2-methyl-2-mor Polynopropane-1-one, 1- (4-morpholinophenyl) -2-benzyl-2-dimethylaminobutan-1-one, 1-hydroxycyclohexylphenyl ketone and 2,2-dimethoxy- 1,2-diphenylethan-1-one.

1- [4- (methylthio) phenyl] -2-methyl-2-morpholinopropane-1-one and 1- (4-morpholinophenyl) -2-benzyl-2-dimethyl among these acetophenone compounds Aminobutan-1-one is particularly preferred.

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

When the acetophenone compound is used as the photopolymerization initiator in the present invention, the amount of the acetophenone compound is preferably 0.01 to 80 parts by weight, more preferably based on 100 parts by weight of the total of the multifunctional monomer (C) and the monofunctional monomer. 1 to 60 parts by weight, even more preferably 1 to 30 parts by weight. When the amount of acetophenone compound is less than 0.01 part by weight, it may be difficult to obtain a spacer arranged in a predetermined pattern due to incomplete curing by exposure, and when the amount is more than 80 parts by weight, the formed spacer is removed from the substrate during development. It can come off easily.

Examples of biimidazole compounds include

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

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

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

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

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

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

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

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

There is this.

Among these biimidazole compounds,

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

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

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

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

This is particularly preferred.

The biimidazole compound exhibits good solubility in solvents, does not form foreign materials such as insoluble products and precipitates, exhibits high sensitivity, fully promotes curing reactions upon exposure to small amounts of energy, and partially unexposed Does not cause a curing reaction. Therefore, since the coating film after exposure is clearly divided into a cured portion which is insoluble in the developer and an uncured portion which is highly soluble in the developer, it is possible to form high precision spacers arranged in a predetermined pattern without undercut.

The biimidazole compound may be used alone or in combination of two or more thereof.

When the biimidazole compound is used as the photopolymerization initiator in the present invention, the amount of the biimidazole compound is preferably 0.01 to 40 parts by weight, more preferably based on 100 parts by weight of the total of the multifunctional monomer (C) and the monofunctional monomer. Is 1 to 30 parts by weight, even more preferably 1 to 20 parts by weight. When the amount of the biimidazole compound is less than 0.01 part by weight, it may be difficult to obtain a spacer arranged in a predetermined pattern due to incomplete curing by exposure, and when the amount is more than 40 parts by weight, the formed spacer may be formed during development. It can easily come off from the substrate.

Hydrogen donor

When a biimidazole compound is used as a photoinitiator in this invention, it is preferable to use it in combination with the following hydrogen donor in order to raise a sensitivity further.

As used herein, the term “hydrogen donor” means a compound capable of providing hydrogen atoms to radicals formed from biimidazole compounds by exposure.

Preferred hydrogen donors in the present invention are mercaptan compounds or amine compounds as defined below.

The mercaptan compound is a compound having a benzene ring or a heterocyclic ring as a parent nucleus, and a mercapto group of at least one, preferably 1 to 3, more preferably 1 or 2, is directly bonded to the mother nucleus (after , Called "mercaptan hydrogen donor").

The amine compound is a compound having a benzene ring or a heterocyclic ring as a parent nucleus, and in which at least one, preferably 1 to 3, more preferably 1 or 2 amine group is directly bonded to the mother nucleus (hereinafter, “ Amine hydrogen donor ".

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

The following detailed description of the invention describes these hydrogen donors.

The mercaptan hydrogen donor may have at least one benzene ring or heterocyclic ring, or these simultaneously. When the mercaptan hydrogen donor has two or more rings, fused rings can be formed.

   When the mercaptan hydrogen donor has two or more mercapto groups, at least one free mercapto group may be substituted with an alkyl, aralkyl or aryl group if at least one free mercapto group remains. In addition, if at least one free mercapto group remains, the mercaptan hydrogen donor may be a structural unit having two sulfur atoms bonded by a divalent organic group such as an alkylene group, or a structural unit having two sulfur atoms bonded in the form of disulfide. Can have

In addition, the mercaptan hydrogen donor may be substituted at a position other than the mercapto group with a carboxyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, phenoxycarbonyl group, substituted phenoxycarbonyl group or nitrile group.

Examples of mercaptan hydrogen donors include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzoimidazole, 2,5-dimercapto-1,3,4-thiadiazole and 2- Mercapto-2,5-dimethylaminopyridine.

Among these mercaptan hydrogen donors, 2-mercaptobenzothiazole and 2-mercaptobenzooxazole are preferred, and 2-mercaptobenzothiazole is particularly preferred.

The amine hydrogen donor may have at least one benzene ring or heterocyclic ring, or these simultaneously. When the amine hydrogen donor has two or more rings, fused rings may be formed.

At least one amine group of the amine hydrogen donor may be substituted with an alkyl group or a substituted alkyl group, or the amine hydrogen donor may have a carboxyl group, alkoxycarbonyl group, substituted alkoxycarbonyl group, phenoxycarbonyl group, substituted phenoxycarbonyl group, or a moiety other than an amine group. It may be substituted with a nitrile group.                     

Examples of amine hydrogen donors include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 4-diethylaminoacetophenone, 4-dimethylaminopropiophenone, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate and 4-dimethylaminobenzonitrile.

Among these amine hydrogen donors, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone are preferable, and 4,4'-bis (diethylamino) benzophenone is Particularly preferred.

The amine hydrogen donor acts as a sensitizer for photopolymerization initiators other than biimidazole compounds.

In the present invention, the hydrogen donor may be used alone or in combination of two or more. Combinations of one or more mercaptan hydrogen donors with one or more amine hydrogen donors are particularly preferred because the spacers formed are difficult to emerge from the substrate during the development process and exhibit high strength and sensitivity.

The combination of mercaptan hydrogen donor and amine hydrogen donor includes 2-mercaptobenzothiazole / 4,4'-bis (dimethylamino) benzophenone, 2-mercaptobenzothiazole / 4,4'-bis (diethyl Amino) benzophenone, 2-mercaptobenzooxazole / 4,4'-bis (dimethylamino) benzophenone, or 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzophenone is preferred Do. As the above formulation, 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone or 2-mercaptobenzooxazole / 4,4'-bis (diethylamino) benzophenone is more preferable. 2-mercaptobenzothiazole / 4,4'-bis (diethylamino) benzophenone is particularly preferred.                     

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

When the biimidazole compound is used in combination with the hydrogen donor in the present invention, the amount of the hydrogen donor is preferably 0.01 to 40 parts by weight, more preferably based on 100 parts by weight of the total of the multifunctional monomer (C) and the monofunctional monomer. Is 1 to 30 parts by weight, particularly preferably 1 to 20 parts by weight. When the amount of the hydrogen donor is less than 0.01 part by weight, the effect of improving the sensitivity may be low, and when the amount is more than 40 parts by weight, the formed spacer may easily come off the substrate during development.

Examples of triazine compounds include 2,4,6-tris (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (trichloromethyl) -s-triazine, 2- [2- ( 5-methylfuran-2-yl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [2- (furan-2-yl) ethenyl] -4,6-bis (Trichloromethyl) -s-triazine, 2- [2- (4-diethylamino-2-methylphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- [ 2- (3,4-dimethoxyphenyl) ethenyl] -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl ) -s-triazine, 2- (4-ethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine and 2- (4-n-butoxyphenyl) -4,6- There are triazine compounds with halomethyl groups, such as bis (trichloromethyl) -s-triazine.

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

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

When the triazine compound is used as the photopolymerization initiator in the present invention, the amount of the triazine compound is preferably 0.01 to 40 parts by weight, more preferably 1 based on 100 parts by weight of the total of the multifunctional monomer (C) and the monofunctional monomer. To 30 parts by weight, particularly preferably 1 to 20 parts by weight. If the amount of triazine compound is less than 0.01 part by weight, it may be difficult to obtain a spacer arranged in a predetermined pattern due to incomplete curing by exposure, and when the amount is more than 40 parts by weight, the spacer formed is removed from the substrate during development. It can come off easily.

<Additive>

The photosensitive composition of the present invention may contain various additives if necessary.

Such additives include organic acids or organic amino compounds (except for the hydrogen donors) which exhibit the function of further increasing solubility in the alkaline developer of the photosensitive composition, and further inhibiting the presence of undissolved product after development.

<Organic acid>

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

Examples of the aliphatic carboxylic acids include aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, valerian, pivalic acid, caproic acid, diethylacetic acid, enanthic acid and 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, Aliphatic dicarboxylic acids such as cyclohexanedicarboxylic acid, itaconic acid, citraconic acid, maleic acid, fumaric acid and mesaconic acid; And aliphatic tricarboxylic acids such as tricarvalrylic acid, aconitic acid and camphoronic acid.

The phenyl group-containing carboxylic acid is, for example, a compound in which a carboxyl group is directly bonded to a phenyl group, or a compound in which a carboxyl group is bonded to a phenyl group through a carbon chain.

Examples of the phenyl group-containing carboxylic acid include aromatic monocarboxylic acids such as benzoic acid, toluic acid, cuminic acid, hemelitic acid and mesitylic acid; Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid; Trivalent or more aromatic polycarboxylic acids such as trimellitic acid, trimesic acid, melanoic acid and pyromellitic acid; Phenylacetic acid; Hydroatroic acid; Hydrocinnamic acid; Mandelic acid; Phenylsuccinic acid; Atroic acid; Cinnamic acid; Cinnamylic acid; Coumaric acid; And umbelic acid.

In view of alkaline solubility, solubility in a solvent to be described later, and prevention of stains and film residues on some unexposed substrates and light-shielding layers, aliphatic dicarboxylic acids among these organic acids are preferred as aliphatic carboxylic acids, and these Of the aliphatic dicarboxylic acids, malonic acid, adipic acid, itaconic acid, citraconic acid, fumaric acid and mesaconic acid are particularly preferred. Aromatic dicarboxylic acid is preferable as a phenyl group containing carboxylic acid, and phthalic acid is especially preferable among these aromatic dicarboxylic acids.                     

The organic acid may be used alone or in combination of two or more thereof.

The amount of the organic acid is preferably 15 wt% or less, more preferably 10 wt% or less, based on the total amount of the photosensitive composition. When the amount of the organic acid is greater than 15 wt%, the extent to which the formed spacer adheres to the substrate may be low.

<Organic amino compound>

The organic amino compound is preferably an aliphatic amine or phenyl group containing amine having at least one amino group in the molecule.

Examples of the aliphatic amines include n-propylamine, i-propylamine, n-butylamine, i-butylamine, sec-butylamine, t-butylamine, n-pentylamine, n-hexylamine, n-heptylamine , n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, cyclohexylamine, o-methylcyclohexylamine, m-methylcyclohexylamine, p-methylcyclo Mono (cyclo) alkylamines such as hexylamine, o-ethylcyclohexylamine, m-ethylcyclohexylamine and p-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, methyl di-n-propylamine, ethyl di-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 and 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 and 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 and tri (4 Tri (cyclo) alkanolamines such as -cyclohexanol) amine; 3-amino-1,2-propanediol, 2-amino-1,3-butanediol, 4-amino-1,2-butanediol, 4-amino-1,3-butanediol, 4-amino-1,2-cyclo Hexanediol, 4-amino-1,3-cyclohexanediol, 3-dimethylamino-1,2-propanediol, 3-diethylamino-1,2-propanediol, 2-dimethylamino-1,3-propane Amino (cyclo) alkanediols such as diol and 2-diethylamino-1,3-propanediol; 1-aminocyclopentanmethanol, 4-aminocyclopentanmethanol, 1-aminocyclohexanemethanol, 4-aminocyclohexanemethanol, 4-dimethylaminocyclopentanmethanol, 4-diethylaminocyclopentanmethanol, 4-dimethylaminocyclo Cycloalkanethanol with amino groups, such as hexanemethanol and 4-diethylaminocyclohexanemethanol; And 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, Aminocarboxylic acids such as 1-aminocyclopropanecarboxylic acid, 1-iminocyclohexanecarboxylic acid and 4-aminocyclohexanecarboxylic acid.                     

The phenyl group-containing amine is, for example, a compound in which an amino group is directly bonded to a phenyl group, or a compound in which an amino group is bonded to a phenyl group through a carbon chain.

Examples of phenyl group-containing amines include aniline, o-methylaniline, m-methylaniline, p-methylaniline, p-ethylaniline, pn-propylaniline, pi-propylaniline, pn-butylaniline, pt-butylaniline, 1- Aromatic amines such as naphthylamine, 2-naphthylamine, N, N-dimethylaniline, N, N-diethylaniline and p-methyl-N, N-dimethylaniline; o-aminobenzyl alcohol; aminobenzyl alcohols such as m-aminobenzyl alcohol, p-aminobenzyl alcohol, p-dimethylaminobenzyl alcohol and p-diethylaminobenzyl alcohol; aminophenols such as o-aminophenol, m-aminophenol, p-aminophenol, p-dimethylaminophenol and p-diethylaminophenol; And aminobenzoic acids (derivatives) such as m-aminobenzoic acid, p-aminobenzoic acid, p-dimethylaminobenzoic acid and p-diethylaminobenzoic acid.

In view of the solubility in the solvents to be described later and the prevention of stains and film residues on some unexposed substrates and light-shielding layers, mono (cyclo) alkanolamines and amino (cyclo) alkanediols of these organic amino compounds Preferred as aliphatic amines, of which 2-aminoethanol, 3-amino-1-propanol, 5-amino-1-pentanol, 3-amino-1,2-propanediol, 2-amino-1,3-propane Particular preference is given to diols and 4-amino-1,2-butanediol. As aminophenol, a phenol group containing amine is preferable and o-aminophenol, m-aminophenol, and p-aminophenol are especially preferable among the said aminophenols.

The organic amino compound may be used alone or in combination of two or more thereof.                     

The amount of the organic amino compound is preferably 15% by weight or less, more preferably 10% by weight or less based on the total amount of the photosensitive composition. When the amount of the organic amino compound is greater than 15% by weight, the degree of adhesion of the formed spacer to the substrate may be lowered.

Additives other than the above include, for example, dispersing aids such as blue pigment derivatives or yellow pigment derivatives such as copper phthalocyanine derivatives; Fillers such as glass or alumina; Polymeric compounds such as polyvinyl alcohol, polyethylene glycol monoalkyl ethers or poly (fluoroalkylacrylates); Nonionic surfactants, cationic surfactants or anionic surfactants; Vinyl trimethoxysilane, vinyl triethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-amino Ethyl) -3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-glycidoxypropyl trimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3, 4-epoxycyclohexyl) ethyl trimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyl trimethoxysilane, 3-methacryloxypropyl trimethoxysilane or 3-mercaptopropyl trimeth Adhesion promoters such as oxysilane; Antioxidants such as 2,2-thiobis (4-methyl-6-t-butylphenol) or 2,6-di-t-butylphenol; Ultraviolet light absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole or alkoxybenzophenone; Anticoagulants such as sodium polyacrylate; And thermal radical generators such as 1,1'-azobis (cyclohexane-1-carbonitrile) or 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile.                     

<Solvent>

The photosensitive composition of this invention contains the said coloring agent (A), alkali-soluble resin (B), a polyfunctional monomer (C), and a photoinitiator as an essential component, It is preferable to prepare the said liquid composition by mixing these components with a solvent. .

Any solvent is acceptable as long as it disperse or dissolve the components (A) to (D) and the additive components and do not react with these components and have the appropriate volatility.

Examples of such solvents include 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, di Ethylene 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, tripropylene glycol Monomethyl Ether and Tripropylene Gly (Poly) alkylene glycol monoalkyl ethers such as monomethyl 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 methylethyl 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 2-hydroxypropionate and ethyl 2-hydroxypropionate; Ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl Ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, 3-methyl-3-methoxybutylacetate, 3-methyl-3-methoxybutylpropionate, ethyl acetate, n -Propyl acetate, i-propyl acetate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, n-propyl butyrate, i-propyl butyrate, other esters such as n-butyl butyrate, methyl pyruvate, ethyl pyruvate, n-propyl pyruvate, methyl acetoacetate, ethyl acetoacetate and ethyl 2-oxybutanoate; Aromatic hydrocarbons such as toluene and xylene; And amides such as N-methylpyrrolidone, N, N-dimethylformamide and N, N-dimethylacetamide.

In view of solubility, pigment dispersibility and applicability, of 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, di Ethylene glycol methyl ethyl ether, cyclohexanone, 2-heptanone, 3-heptanone, ethyl 2-hydroxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3- Ethoxypropionate, 3-methyl-3-methoxybutylpropionate, n-butyl acetate, i-butyl acetate, n-pentyl formate, i-pentyl acetate, n-butyl propionate, ethyl butyrate, Preference is given to i-propyl butyrate, n-butyl butyrate and ethyl pyruvate.

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

In addition, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, di High boiling point solvents such as ethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate or ethylene glycol monophenyl ether acetate may also be used in combination with the above solvents.

The high boiling point solvent may be used alone or in combination of two or more thereof.

The amount of the solvent is not particularly limited, but from the viewpoint of the applicability and stability of the obtained liquid composition, the total amount of all components except for the solvent of the liquid composition is preferably 5 to 50% by weight, particularly preferably 10 to 40 wt%.

<How to form a spacer>

The photosensitive composition of the present invention is a driving substrate on which a thin film transistor (TFT) for a thin film transistor (TFT) system color liquid crystal display device is formed on a surface by lithography (hereinafter referred to as a "TFT liquid crystal driving substrate") Used to form spacers on the substrate.

The spacer is formed on the TFT liquid crystal driving substrate on which the colored layer is formed. As used herein, the term "colored layer" means containing only display pixels, containing only black matrices, or both.

In order to form a colored layer on a TFT liquid crystal drive substrate, liquid photosensitive for the colored layer containing (a) a coloring agent, (b) alkali-soluble resin, (c) polyfunctional monomer, (d) photoinitiator, and optionally an additive component. Preference is given to using the composition.

The components (a) to (d) may be the same as each of the (A) colorant, (B) alkali-soluble resin, (C) polyfunctional monomer and (D) photopolymerization initiator of the photosensitive composition of the present invention. When the colored layer comprises a pixel, it is preferable to use at least one organic pigment as the colorant (a), and when the colored layer comprises a black matrix, at least two organic pigments and / or carbon blacks may be used as the colorant (a Is preferably used. The Mw of the alkali-soluble resin (b) is preferably 3,000 to 300,000, more preferably 5,000 to 100,000, and the Mn of the alkali-soluble resin (b) is preferably 3,000 to 60,000, more preferably 5,000 to 25,000, Mw / Mn of the said resin (b) becomes like this. Preferably it is 1-5, More preferably, it is 1-4.

The additive component used in the photosensitive composition for colored layers is the same as described for the photosensitive composition of the present invention. Examples of the solvent used in the preparation of the liquid photosensitive composition for the colored layer are the same as those described for the photosensitive composition of the present invention.

The method of forming the colored layer and the spacer on the TFT liquid crystal drive substrate will be described below.

In the case of pixel formation, first, a light shielding layer for defining a portion on which a pixel is to be formed is required on a substrate having a passivation film such as a TFT liquid crystal driving substrate, or a silicon nitride film formed on the surface of the driving substrate, if necessary. After forming in, for example, a coating film is formed by applying a liquid photosensitive composition for a colored layer, in which a red pigment is dispersed, to the substrate and pre-baking to evaporate the solvent.

The coating is then exposed to light through a photomask, developed with an alkaline developer to dissolve and remove the unexposed portions of the coating, and then post-baked to form an array of red pixels arranged in a predetermined pattern. The photomask used has a pattern for forming pixels and a pattern for forming through holes or U-shaped cavities.

Thereafter, the liquid photosensitive composition for the coloring layer, in which the green pigment is dispersed, and the liquid photosensitive composition for the coloring layer, in which the blue pigment is dispersed, are applied, pre-baked, exposed, developed, and the same as above. Post-baking in such a manner that an array of green pixels and an array of blue pixels are formed on substantially the same substrate, thereby forming red, green on the TFT liquid crystal driving substrate through holes or U-shaped cavities formed inside the substrate. And a color liquid crystal display device in which a pixel array in which blue is the main color is formed.

The black matrix can be formed in the same manner as the pixel.

Except that the liquid photosensitive composition of the present invention is applied to the TFT liquid crystal driving substrate having the colored layer formed inside the substrate as described above, instead of the liquid photosensitive composition for the colored layer, and that the photomask for the spacer is used. Spacers may be formed in the same manner as the pixel.

The substrate for TFT liquid crystal drive is made of glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamide imide, polyimide and the like. The substrate is optionally suitably treated with a chemical treatment such as a silane coupling agent or the like, pretreatment such as plasma treatment, ion plating, sputtering, vapor phase reaction or vacuum deposition.

In order to apply the liquid photosensitive composition to the substrate to form the colored layer and the spacer, a suitable coating agent such as a rotating coating agent, a casting coating agent or a roll coating agent can be used.

The coating film thickness after drying for forming a colored layer becomes like this. Preferably it is 0.1-10 micrometers, More preferably, it is 0.2-5.0 micrometers, Especially preferably, it is 0.2-3.0 micrometers.

The coating film thickness after drying for forming the spacer is preferably 0.1 to 20 µm, more preferably 0.2 to 10 µm, particularly preferably 0.2 to 8 µm.

The radiation used to form the colored layer and the spacer is selected from visible light, ultraviolet light, far ultraviolet light, electron beam, X-ray and the like, but is preferably radiation having a wavelength of 190 to 450 nm.

The amount exposed to radiation is preferably 10 to 10,000 J / m ² .

The alkaline developer used to form the colored layer and the spacer includes aqueous sodium carbonate, aqueous sodium hydroxide, aqueous potassium hydroxide, aqueous tetramethylammonium hydroxide, aqueous dimethylethanolamine, aqueous chlorine, 1,8-diazabicyclo- [ 5.4.0] -7-undecane aqueous solution, 1,5-diazabicyclo- [4.3.0] -5-nonene, etc. are preferable.

A suitable amount of water soluble organic solvent or surfactant such as methanol or ethanol can be added to the alkaline developer. The coating film is preferably developed with an alkaline developer and washed with water.

The development may be a shower phenomenon, a spray phenomenon, a dip phenomenon, a puddle phenomenon, or the like. As for the developing conditions, it is preferable to perform the development for 5 to 300 seconds at the normal temperature.

1 and 2 illustrate a core cross section of an example of a thin film transistor (TFT) type color liquid crystal display having pixels and spacers formed as described above. Fig. 1 is a cross section of the device, and Fig. 2 shows a cut plane cut along the line X-X of Fig. 1 and shows the device before the alignment film is formed. 1 is a substrate (TFT liquid crystal driving substrate), 2 is an electrode, 3 is a red pixel, 4 is a green pixel, 5 is a blue pixel, 6 is a spacer, 7 is an ITO film, 8 is an alignment film, and 9 is a liquid crystal layer. Indicates.

The color liquid crystal display in which the colored layer and the spacer are formed as described above may have a transmission form or a reflection form. The photosensitive composition of the present invention is useful as a spacer for thin film transistor (TFT) type color pickup tube elements and color detectors.

The following examples are provided for the purpose of further illustrating the invention but are not intended to limit the scope of the invention.

In the Examples, the OD value was measured as follows.

<OD value>

The liquid photosensitive composition for the spacer was applied to the surface of the glass substrate with a rotary coating and pre-baked for 10 minutes in a clean oven heated to 90 ° C. to form a coating film. Thereafter, the substrate was cooled to room temperature and the entire coating film was exposed to 5,000 J / m ² of ultraviolet rays having wavelengths of 365 nm, 405 nm and 436 nm using a high pressure mercury lamp. The substrate was then immersed in a 0.1 wt% tetramethylammonium hydroxide aqueous solution at 23 ° C. for 1 minute to develop, washed with ultra pure water and dried with air. The substrate was then post-baked in a clean oven heated to 220 ° C. for 25 minutes to form a 5 μm thick coating on the substrate. The OD value of this coating film was measured by the optical density meter (McBeth TR927, Sakata Inks Co., Ltd.).

<Example>

Example 1

Preparation of the photosensitive composition for pixels

(a) C.I. wherein the weight ratio is 65:35 as colorant. Pigment Red 177 and C.I. 100 parts by weight of a mixture of pigment red 224; (b) Methacrylic acid / N-phenylmaleimide / benzyl methacrylate / glycerol monomethacrylate / styrene as alkali-soluble resin (weight ratio = 15: 25: 35: 10: 15, Mw = 30,000, Mn = 10,000) 70 parts by weight of copolymer of; (c) 80 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer; (d) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator; And 1,000 parts by weight of propylene glycol monomethyl ether acetate as a solvent to prepare a liquid photosensitive composition for red pixels (R1).

Formation of pixel array

Applying the liquid composition (R1) to the surface of the substrate prepared by forming a silicon nitride on the surface of the TFT liquid crystal drive substrate with a rotating coating agent, and pre-baked for 10 minutes in a clean oven heated to 90 ℃ thickness A coating film having a thickness of 1.7 μm was formed.

Thereafter, the substrate was cooled to room temperature, and the coating film was exposed to ultraviolet light 2,000 J / m ² having a wavelength of 365 nm, 405 nm, and 436 nm through a photomask using a high pressure mercury lamp. The substrate was then immersed in 23 wt. The substrate was then post-baked in a clean oven heated to 220 ° C. for 25 minutes to form a stripe-like array of red pixels on the substrate.

Preparation of liquid photosensitive composition for spacer

(A) C.I., wherein the weight ratio is 60:20:20 as colorant. Pigment Red 177, C.I. Pigment blue 15: 4 and C.I. 160 parts by weight of a mixture of pigment yellow 150 and 20 parts by weight of barium sulfate; (B) methacrylic acid / mono (2-acryloyloxyethyl) succinate as alkali-soluble resin / N-phenylmaleimide / benzyl methacrylate / styrene (weight ratio = 30: 15: 35: 10: 10, Mw = 19,000, Tg = 130 ° C.), 70 parts by weight of the copolymer; (C) 80 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer; (D) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator; And 1,000 parts by weight of propylene glycol monomethylether acetate as a solvent to prepare a liquid photosensitive composition for spacers (BK1).

Formation of spacers

The liquid composition (BK1) is applied to the surface of the TFT liquid crystal driving substrate having the pixel array as described above with a rotary coating agent, and pre-baked for 10 minutes in a clean oven heated to 90 ° C. to have a thickness of 6.0 μm. A coating film was formed.

Thereafter, the substrate was cooled to room temperature, and the coating was exposed to ultraviolet light of 5,000 J / m ² having a wavelength of 365 nm, 405 nm and 436 nm through a photomask using a high pressure mercury lamp. The substrate was then immersed in 23 wt. The substrate was then post-baked in a clean oven heated to 220 ° C. for 25 minutes to form a spacer 5 μm thick on the substrate.

evaluation

When the display panel was manufactured using a substrate obtained according to a commonly used method, the thin film transistor (TFT) did not malfunction, and the difference in the cell gap was ± 0.19 μm. The spacers were not irreversibly deformed when the panel was closed, and no display defects occurred due to gaps between the liquid crystal layers. The OD value of the coating film whose thickness was 5 micrometers formed on the surface of another glass substrate using the said liquid composition (BK1) was 3.3.

Example 2

Preparation of liquid photosensitive composition for spacer

(A) C.I., wherein the weight ratio is 60:20:20 as colorant. Pigment Red 177, C.I. Pigment blue 15: 4 and C.I. 160 parts by weight of a mixture of pigment yellow 150 and 20 parts by weight of barium sulfate; (B) methacrylic acid / mono (2-acryloyloxyethyl) succinate as alkali-soluble resin / N-phenylmaleimide / benzyl methacrylate / styrene (weight ratio = 30: 10: 35: 15: 10, Mw = 16,000, Tg = 125 ° C.) 70 parts by weight of copolymer; (C) 80 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer; (D) 20 parts by weight of 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropanone-1 as a photopolymerization initiator; 15 parts by weight of 4,4'-bis (diethylamino) benzophenone as a sensitizer; And 1,000 parts by weight of propylene glycol monomethylether acetate as a solvent to prepare a liquid photosensitive composition for spacers (BK2).

Formation of spacers

A pixel array and a spacer were formed on the surface of the TFT liquid crystal drive substrate in the same manner as in Example 1 except that the liquid composition (BK2) was used instead of the liquid composition (BK1).

evaluation

When the display panel was manufactured using a substrate obtained according to a commonly used method, the thin film transistor (TFT) did not malfunction, and the difference in the cell gap was ± 0.33 μm. The spacers were not irreversibly deformed when the panel was sealed, and no display error occurred due to the gap difference between the liquid crystal layers. The OD value of the coating film of 5 micrometers in thickness formed on the surface of another glass substrate using the said liquid composition (BK2) was 3.3.

Example 3

Preparation of liquid photosensitive composition for spacer

(A) C.I., wherein the weight ratio is 60:20:20 as colorant. Pigment Red 177, C.I. Pigment Green 7 and C.I. 200 parts by weight of a mixture of pigment blue 15: 6; (B) methacrylic acid / mono (2-acryloyloxyethyl) succinate as alkali-soluble resin / N-phenylmaleimide / benzyl methacrylate / styrene (weight ratio = 30: 15: 35: 10: 10, Mw = 19,000, Tg = 130 ° C.), 75 parts by weight of copolymer; (C) 75 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer; (D) 6 parts by weight of 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-bisimidazole as a photopolymerization initiator; 6 parts by weight of 4,4'-bis (diethylamino) benzophenone as the amine-based hydrogen donor, and 3 parts by weight of 2-mercaptobenzothiazole as the mercaptan-based hydrogen donor; And 700 parts by weight of propylene glycol monomethyl ether acetate and 300 parts by weight of cyclohexanone as a solvent to prepare a liquid photosensitive composition for spacers (BK3).

Formation of spacers

A pixel array and a spacer were formed on the surface of the TFT liquid crystal drive substrate in the same manner as in Example 1 except that the liquid composition (BK3) was used instead of the liquid composition (BK1).

evaluation

When the display panel was manufactured using a substrate obtained according to a commonly used method, the thin film transistor (TFT) did not malfunction, and the difference in the cell gap was ± 0.25 μm. The spacers were not irreversibly deformed when the panel was sealed, and no display error occurred due to the gap difference between the liquid crystal layers. The OD value of the coating film of thickness 5 micrometers formed on the surface of another glass substrate using the said liquid composition (BK3) was 3.5.

Example 4

Preparation of liquid photosensitive composition for spacer

(A) C.I., whose weight ratio is 70:30 as a coloring agent. Pigment Red 177 and C.I. 200 parts by weight of a mixture of pigment blue 15: 6; (B) methacrylic acid / mono (2-acryloyloxyethyl) succinate as alkali-soluble resin / N-phenylmaleimide / benzyl methacrylate / styrene (weight ratio = 30: 10: 35: 15: 10, Mw = 16,000, Tg = 125 ° C.) 75 parts by weight of copolymer; (C) 75 parts by weight of dipentaerythritol hexaacrylate as a polyfunctional monomer; (D) 10 parts by weight of a triazine compound as a photopolymerization initiator; 700 parts by weight of propylene glycol monomethyl ether acetate and 300 parts by weight of cyclohexanone were mixed as a solvent to prepare a liquid photosensitive composition for spacers (BK4).

Formation of spacers                     

A pixel array and a spacer were formed on the surface of the TFT liquid crystal drive substrate in the same manner as in Example 1 except that the liquid composition (BK4) was used instead of the liquid composition (BK1).

evaluation

When the display panel was manufactured using a substrate obtained according to a commonly used method, the thin film transistor (TFT) did not malfunction, and the difference in the cell gap was ± 0.22 μm. The spacers were not irreversibly deformed when the panel was sealed, and no display error occurred due to the gap difference between the liquid crystal layers. The OD value of the coating film of thickness 5 micrometers formed on the surface of another glass substrate using the said liquid composition (BK4) was 3.5.

Example 5

Preparation of liquid photosensitive composition for spacer

(A) C.I., wherein the weight ratio is 60:20:20 as colorant. Pigment Red 177, C.I. Pigment blue 15: 4 and C.I. 160 parts by weight of a mixture of pigment yellow 150 and 20 parts by weight of barium sulfate; (B) 70 parts by weight of copolymer of methacrylic acid / 2-hydroxyethyl methacrylate / benzyl methacrylate (weight ratio = 30: 10: 60, Mw = 9,500, Tg = 80 ° C.) as alkali-soluble resin; (C) 80 parts by weight of dipentaerythritol hexaacrylate as the polyfunctional monomer; (D) 50 parts by weight of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butanone-1 as a photopolymerization initiator; And 1,000 parts by weight of propylene glycol monomethylether acetate as a solvent to prepare a liquid photosensitive composition for spacers (BK5).

Formation of spacers

A pixel array and a spacer were formed on the surface of the TFT liquid crystal drive substrate in the same manner as in Example 1 except that the liquid composition (BK5) was used instead of the liquid composition (BK1).

evaluation

When the display panel was manufactured using a substrate obtained according to a commonly used method, the thin film transistor (TFT) did not malfunction, and the difference in the cell gap was ± 0.60 μm. The spacers were not irreversibly deformed when the panel was sealed, and no display error occurred due to the gap difference between the liquid crystal layers. The OD value of the coating film of thickness 5 micrometers formed on the surface of another glass substrate using the said liquid composition (BK5) was 3.3.

Characteristic of the photosensitive composition of the present invention is that the spacer made from the composition exhibits excellent light shielding property, mechanical strength and heat resistance, the thin film transistor is not malfunctioned, the gap of the cell gap is extremely small, and the spacer is formed when the display panel is produced. When sealing, it does not irreversibly deform under high temperature and high pressure conditions, and display error does not occur due to gap difference of the liquid crystal layer.

Accordingly, the photosensitive composition of the present invention can provide a high quality thin film transistor (TFT) type color liquid crystal display device having excellent reliability.

Claims (13)

(A) a colorant, (B) alkali-soluble resin, (C) polyfunctional monomer, and (D) photoinitiator, wherein said colorant (A) comprises at least one member selected from the group consisting of an organic pigment and carbon black. And a polystyrene reduced weight average molecular weight of the alkali-soluble resin (B), measured by gel permeation chromatography, of 3,000 to 20,000, and a glass transition temperature of 110 ° C to 200 ° C for driving the thin film transistor type color liquid crystal display device. A photosensitive composition for forming a light shielding spacer on a substrate. delete delete The polymerizable unsaturated monomer according to claim 1, wherein the alkali-soluble resin (B) is at least one carboxyl group in the molecule (a), (b) a macromonomer having a mono (meth) acryloyl group at the terminal of the molecular chain, N- At least one monomer selected from the group consisting of substituted maleimide, 2-hydroxy (meth) acrylate, benzyl (meth) acrylate and a compound represented by the following formula (1); And optionally (c) a copolymer of one or more monomers selected from the group consisting of styrene, methyl (meth) acrylate, allyl (meth) acrylate and phenyl (meth) acrylate. <Formula 1>

In the above formula, R ¹ is a hydrogen atom or a methyl group. The method of claim 1, wherein the alkali-soluble resin (B) is (1) a carboxyl group-containing unsaturated monomer; (2) polystyrene macromonomer, polymethyl (meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol ( At least one monomer selected from the group consisting of meth) acrylates; And (3) at least one monomer selected from the group consisting of styrene, methyl (meth) acrylate, allyl (meth) acrylate and phenyl (meth) acrylate. The method of claim 1, wherein the alkali-soluble resin (B) is selected from the group consisting of (1) (meth) acrylic acid and a combination of meth (acrylic acid) and mono [2- (meth) acryloyloxyethyl] succinate. Carboxyl group-containing unsaturated monomer components; (2) polystyrene macromonomer, polymethyl (meth) acrylate macromonomer, N-phenylmaleimide, N-cyclohexylmaleimide, 2-hydroxyethyl (meth) acrylate, benzyl (meth) acrylate and glycerol ( At least one monomer selected from the group consisting of meth) acrylates; And (3) at least one monomer selected from the group consisting of styrene, methyl (meth) acrylate, allyl (meth) acrylate and phenyl (meth) acrylate. The composition of claim 1, wherein the multifunctional monomer (C) is at least one compound selected from the group consisting of trimethylolpropane triacrylate, pentaerythritol triacrylate and dipentaerythritol hexaacrylate. The composition of claim 1, wherein the photopolymerization initiator (D) is one or more compounds selected from the group consisting of acetophenone compounds, biimidazole compounds, and triazine compounds. The composition according to claim 1, wherein the photopolymerization initiator (D) is a biimidazole compound and is used in combination with a hydrogen donor selected from the group consisting of mercaptan hydrogen donors, amine hydrogen donors and combinations thereof. 10. The composition of claim 9, wherein the photopolymerization initiator (D) further comprises one or more compounds selected from the group consisting of acetonephenone compounds and triazine compounds. A driving substrate for a thin film transistor system color liquid crystal display device having a spacer formed from the photosensitive composition of any one of claims 1 and 4 to 10. 1) forming a color film containing a colored layer on a driving substrate of a thin film transistor type color liquid crystal display device directly or through a passivation film; And 2) forming a spacer with the photosensitive composition of any one of claims 1 and 4 to 10 on the color film; Method of manufacturing a substrate for driving with a spacer comprising a. A thin film transistor type color liquid crystal display device having a driving substrate manufactured according to claim 12.

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