KR102001683B1 - Polyfunctional acrylate compounds, a photosensitive resin composition, color filter and display device comprising the same - Google Patents

Abstract

The present invention relates to a novel multifunctional acrylic compound and a photosensitive resin composition, wherein the photosensitive resin composition comprises an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, To a photosensitive resin composition.

Description

TECHNICAL FIELD [0001] The present invention relates to a polyfunctional acryl compound, a photosensitive resin composition containing the same, a color filter and a display device,

The present invention relates to a polyfunctional acrylic compound, a photosensitive resin composition containing the same, a color filter, and a display device.

BACKGROUND ART Color filters are widely used in image pickup devices, liquid crystal display devices (LCDs), and the like, and their application range is rapidly expanding. A color filter used for a color liquid crystal display device or an image pickup element is generally formed by spin coating a colored photosensitive resin composition containing a pigment corresponding to each color of red, green and blue on a substrate on which a black matrix is pattern- The coating film formed by uniformly applying and then drying by heating (hereinafter also referred to as pre-baking) is exposed and developed, and if necessary, further heat curing (hereinafter also referred to as post-baking) And then repeatedly forming pixels of each color.

In recent years, a photosensitive resin composition having an equivalent sensitivity and adhesion at a low exposure dose and having excellent heat flowability has been required in order to improve process yield.

In order to improve the problem of developing residue of a photosensitive resin and to improve heat flowability, conventional techniques generally include a method of adjusting the acid value and molecular weight of the binder resin or the acid value of the binder resin and the composition, but their application range is limited, There is a limitation in that it is difficult to solve problems such as lack of adhesion or surface defects and resolution of residues remaining on a metal oxide film or a silicon nitride film.

Korean Patent No. 10-0655044 Korean Patent No. 10-1265313

An object of the present invention is to improve the heat flowability of a pattern and improve the straightness of a pattern by preparing a novel polyfunctional acrylic compound and a photosensitive resin composition containing the same.

In order to achieve the above object,

There is provided a compound represented by the following formula (1).

[Chemical Formula 1]

Wherein R &_lt; 1 > is an alkyl group having 1 to 10 carbon atoms,

And m is an integer of 0 to 4.

The present invention also provides a photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the photopolymerizable compound comprises the compound of the general formula (1).

The present invention also provides a color filter which is manufactured from the photosensitive resin composition.

Further, the present invention provides a display device including the color filter.

The photosensitive resin composition comprising the novel multifunctional acrylic compound of the present invention is excellent in developability, residual film ratio, heat resistance, and chemical resistance, and particularly has excellent heat flowability and can improve the straightness of the pattern.

Fig. 1 is a photograph showing the pattern forming property of the photosensitive resin composition prepared in Example 1. Fig.
Fig. 2 is a photograph showing the pattern forming property of the photosensitive resin composition prepared in Example 2. Fig.
3 is a photograph showing the pattern forming property of the photosensitive resin composition prepared in Example 3. Fig.
4 is a photograph showing the pattern forming property of the photosensitive resin composition prepared in Example 4. Fig.
5 is a photograph showing the pattern forming property of the photosensitive resin composition prepared in Comparative Example 1. Fig.
6 is a photograph showing the pattern forming property of the photosensitive resin composition prepared in Comparative Example 2. Fig.

Hereinafter, the present invention will be described in more detail.

The present invention relates to a compound represented by the following general formula (1).

[Chemical Formula 1]

Wherein R &_lt; 1 > is an alkyl group having 1 to 10 carbon atoms,

And m is an integer of 0 to 4.

The compound of Formula 1 is characterized by containing a fluorene group as a polyfunctional acrylic compound. By including a structurally rigid fluorene group, it is possible to improve the straightness of the color filter made of the photosensitive resin composition containing the compound of the formula (1).

The present invention also relates to a photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the photopolymerizable compound comprises the compound of the formula (1). Further, it may further contain additives if necessary.

Hereinafter, the photosensitive resin composition of the present invention will be described in detail for each component.

(A) an alkali-soluble resin

And is copolymerized with an ethylenically unsaturated monomer having a carboxyl group as an essential component in order to obtain solubility in an alkali developing solution used in a development process for forming a pattern.

Specific examples of the ethylenically unsaturated monomer having a carboxyl group include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; Dicarboxylic acids such as fumaric acid, mesaconic acid and itaconic acid; Anhydrides of dicarboxylic acids; (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as? -carboxypolycaprolactone mono (meth) acrylate, and acrylic acid and methacrylic acid are preferable.

As a method for imparting hydroxyl groups to the alkali-soluble resin, there may be mentioned a method of copolymerizing an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group, a method of copolymerizing an ethylenically unsaturated monomer having a carboxyl group with a glycidyl group A method in which the compound is further reacted with a compound having a glycidyl group in addition to a copolymer of an ethylenically unsaturated monomer having a carboxyl group and an ethylenically unsaturated monomer having a hydroxyl group, and the like.

Specific examples of the compound having a glycidyl group include butyl glycidyl ether, glycidyl propyl ether, glycidyl phenyl ether, 2-ethylhexyl glycidyl ether, glycidyl butylate, glycidyl methyl ether, Ethyl glycidyl ether, glycidyl isopropyl ether, t-butyl glycidyl ether, benzyl glycidyl ether, glycidyl 4-t-butyl benzoate, glycidyl stearate, And glycidyl methacrylate. Of these, butyl glycidyl ether, aryl glycidyl ether, and methacrylic acid glycidyl ester are preferable, and two or more kinds of these may be used in combination.

The unsaturated monomers copolymerizable in the preparation of the alkali-soluble resin are exemplified below, but are not limited thereto.

Specific examples of the polymerizable monomer having an unsaturated bond capable of copolymerization include styrene, vinyltoluene,? -Methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, Aromatic vinyl compounds such as methyl ether, m-vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether;

N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm -phenyl maleimide, phenyl maleimide Np-, No- methoxyphenyl maleimide, Nm- methoxyphenyl maleimide, Np- methoxy-N- substituted maleimide-based compounds such as phenyl maleimide;

Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate;

(Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl Hydroxyethyl (meth) acrylates such as hydroxyethyl acrylamide;

Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate;

3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds.

The above-exemplified monomers may be used alone or in combination of two or more.

In order to ensure compatibility of the alkali-soluble resin and storage stability of the photosensitive resin composition, the acid value is preferably 30 to 150 mgKOH / g. When the acid value of the alkali-soluble resin is less than 30 mgKOH / g, the development speed of the photosensitive resin composition is slow. When the acid value is more than 150 mgKOH / g, the adhesion with the substrate is decreased to cause a short circuit. A problem occurs and the viscosity tends to rise.

The content of the alkali-soluble resin is 0.5 to 45% by weight, preferably 1 to 35% by weight based on the total weight of the photosensitive resin composition. When the content of the alkali-soluble resin is 0.5 to 45% by weight, the solubility of the developer is excellent and the pattern formation is easy. In the development, the reduction of the film thickness of the pixel portion of the exposed portion is prevented.

(B) Photopolymerization  compound

The photopolymerizable compound is a compound capable of polymerizing under the action of the photopolymerization initiator (C) described below and includes the polyfunctional acrylic compound of the above formula (1). The invention can use a monofunctional monomer, bifunctional monomer or multi-functional monomer may be used, and preferably at least bi-functional polyfunctional monomer with the polyfunctional acrylic compound of the formula (1).

Specific examples of the monofunctional monomer include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate and N- But are not limited thereto.

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) , Bis (acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate, but are not limited thereto.

Specific examples of the polyfunctional monomer include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate, pentaerythritol Acrylate, trimethylolpropane trimethacrylate, tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like, but are not limited thereto.

The photopolymerizable compound is preferably contained in an amount of 0.5 to 35% by weight, and more preferably 1 to 35% by weight based on the total weight of the photosensitive resin composition. When the photopolymerizable compound is contained in an amount of 0.5 to 35% by weight, the strength of the pixel portion is excellent and the smoothness is improved.

(C) Light curing Initiator

The photopolymerization initiator can be used without particular limitation as long as it can polymerize the photopolymerizable compound (B). Particularly, from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, and cost, the photopolymerization initiator is preferably used in combination with an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, It is preferable to use at least one compound selected from the group consisting of compounds.

The specific examples of the acetophenone based compounds is diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-methylcyclohexyl phenyl ketone, 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Specific examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'- -Butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, (Trichloromethyl) -6- [2- (5-methylfuran-2- (4-methoxystyryl) -1,3,5-triazine, Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan- , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) , 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) 4 ', 5,5'-tetraphenyl-1,2'-biimidazole or an imidazole compound in which the phenyl group at the 4,4', 5,5 'position is substituted by a carboalkoxy group. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 2,2-bis (2,6-dichlorophenyl) -4,4'5,5'-tetraphenyl-1,2'-biimidazole is preferably used do.

Specific examples of the oxime compounds include o-ethoxycarbonyl-α-oximino-1-phenylpropan-1-one and the like. Commercially available products include OXE01 and OXE02 of BASF.

Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4- have.

The photopolymerization initiator may further include a photopolymerization initiator to improve the sensitivity of the photosensitive resin composition of the present invention. Since the photosensitive resin composition according to the present invention contains a photopolymerization initiator, the sensitivity can be further increased and the productivity can be improved.

As the photopolymerization initiation auxiliary (C-1), for example, at least one compound selected from the group consisting of an amine compound, a carboxylic acid compound and an organic sulfur compound having a thiol group can be preferably used.

As the amine compound, an aromatic amine compound is preferably used. Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid, 2-ethylhexyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone ), 4,4'-bis (diethylamino) benzophenone, and the like.

The carboxylic acid compound is preferably an aromatic heteroacetic acid, and more specifically, it is preferably an aromatic heteroaromatic acid such as phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid and the like.

Specific examples of the organic sulfur compound having a thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl) 1,3,5-triazine -2,4,6 (1H, 3H, 5H) - one tree, trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (3-mercapto-butyl (3-mercaptopropionate), dipentaerythritol hexacis (3-mercaptopropionate), and tetraethylene glycol bis (3-mercaptopropionate) .

The photopolymerization initiator may be contained in an amount of 0.01 to 15% by weight, preferably 0.1 to 10% by weight based on the total weight of the photosensitive resin composition of the present invention. When the photopolymerization initiator is in the range of 0.01 to 15% by weight, the sensitivity of the photosensitive resin composition becomes high and the exposure time is shortened, so that productivity is improved and high resolution can be maintained. Further, the strength of the pixel portion formed using the photosensitive resin composition under the above-described conditions and the smoothness on the surface of the pixel portion can be improved. When the photopolymerization initiator includes the photopolymerization initiator, the photopolymerization initiator comprises 10 to 100% by weight, preferably 20 to 100% by weight based on the total weight of the photopolymerization initiator. If the content of the photopolymerization initiator is less than 10% by weight, the decrease in sensitivity due to the dye can not be overcome and the pattern is likely to be short-circuited during the development process. When the photopolymerization initiator is further used, the photopolymerization initiator may include 0.01 to 15% by weight, preferably 0.1 to 10% by weight based on the total weight of the photosensitive resin composition of the present invention. When the amount of the photopolymerization initiator is within the range of 0.01 to 15% by weight, the sensitivity of the photosensitive resin composition becomes higher and the productivity of the color filter formed using the photosensitive resin composition is improved.

(D) Solvent

The solvent used in the conventional photosensitive resin composition is not particularly limited as long as it is effective in dissolving the other components contained in the photosensitive resin composition. The solvent may be selected from ethers, aromatic hydrocarbons, ketones, alcohols, Amides and the like are preferable.

Examples of the solvent include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether and diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, and methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate; And cyclic esters such as? -Butyrolactone.

The solvent is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C on the application and drying surface, more preferably an organic solvent such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, and the like can be used.

The solvents exemplified above may be used alone or in combination of two or more. The solvent may be contained in an amount of 10 to 90% by weight, preferably 60 to 85% by weight based on the total weight of the photosensitive resin composition of the present invention. When the above-mentioned solvent is in the range of 10 to 90% by weight, the coating property is good when applied with a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) Provides a resolution effect.

(E) Additive

The additive can be cited as being optionally be added, as needed, for example, another polymer compound, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and coagulation preventing agent, and the like.

Specific examples of the other polymer compound include a curable resin such as epoxy resin and maleimide resin, a thermoplastic resin such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, polyurethane and the like .

The curing agent is used for deep curing and for increasing mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Aliphatic, alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides, isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of the above epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.

Specific examples of the oxetane compound in the curing agent include carbonates bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like.

The curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound. The curing assistant compound includes, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the epoxy resin curing agent include Adekahadona EH-700 (manufactured by Adeka Kogyo Co., Ltd.), Rikashido HH (manufactured by Shin-Nihon Ehwa Co., Ltd.), MH-700 have. The curing agents exemplified above may be used alone or in combination of two or more.

The surfactant may be used for further improving the film formation of the photosensitive resin composition, and a fluorine-based surfactant or a silicone-based surfactant may be preferably used.

Examples of the silicone surfactant include DC3PA, DC7PA, SH11PA, SH21PA and SH8400 from Dow Corning Toray Silicone Co., Ltd. and TSF-4440, TSF-4300, TSF-4445, TSF-4446 and TSF-4460 , And TSF-4452. Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated. The above-exemplified surfactants may be used alone or in combination of two or more.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, 3- 3-isocyanatopropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. The adhesion promoters exemplified above may be used alone or in combination of two or more. The adhesion promoter may be contained in an amount of usually 0.01 to 10% by weight, preferably 0.05 to 2% by weight based on the total weight of the solid content in the photosensitive resin composition.

Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t-butyl-4-methylphenol.

Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole and alkoxybenzophenone.

Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.

The present invention provides a color filter made of a photosensitive resin composition and a display device having the same.

The photosensitive resin composition may be coated on a substrate as described below and photocured and developed to form a pattern.

First, a photosensitive resin composition is coated on a substrate (usually glass) or a layer composed of a solid content of a previously formed photosensitive resin composition, followed by heating and drying to remove volatile components such as a solvent to obtain a smooth coated film.

The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coating method, a slit coating method or the like. After application, heating and drying (prebaking), or drying under reduced pressure to evaporate the volatile components such as solvent. Here, the heating temperature is usually 70 to 200 占 폚, preferably 80 to 130 占 폚. The thickness of the coating film after heat drying is usually about 1 to 8 mu m. Ultraviolet rays are applied to the thus obtained coating film through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and accurately align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.

The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto. When the coating film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, a spacer having a desired pattern shape can be obtained.

The developing method may be any of a liquid addition method, a dipping method, and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or an organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like.

These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkali developer is preferably 0.01 to 10% by weight, and more preferably 0.03 to 5% by weight.

The surfactant in the alkali developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. These surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight. After development, it may be washed with water and, if necessary, subjected to post-baking at 150 to 230 ° C for 10 to 60 minutes.

By using the photosensitive resin composition of the present invention, a specific pattern can be formed on the substrate through each of the steps as described above.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail with reference to examples. However, the embodiments according to the present invention can be modified into various other forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

< Multifunctional  Preparation of acrylic compound (Formula 1)

Synthetic example  One.

(1-ethyl- (3- (3-dimethylamino) propyl) -carbodiimide hydrochloride) with one equivalent of di-acid type fluorene derivative known to synthesize 2 equivalents of PETA (pentaerithritol triacrylate) And the coupling reaction was carried out at room temperature for 20 hours. Then, work-up was carried out using water and methylene chloride, and the compound of formula (2) in the form of a highly viscous liquid was obtained in a yield of about 80% by using silica gel column chromatography. The results of the reaction and structural analysis are as follows.

¹ H NMR

_{(400MHz, CDCl 3): δ} 7.86 (d, 4H), 7.80 (d, 2H), 7.55 (d, 2H), 7.40 (d, 2H), 7.30 (d, 2H), 7.18 (d, 2H), (S, 4H), 4.05 (s, 12H), 2.35 (s, 6H)

[Reaction Scheme 1]

Synthetic example  2.

(1-ethyl- (3- (3-dimethylamino) propyl) -carbodiimide hydrochloride) with one equivalent of di-acid type fluorene derivative known to synthesize 2 equivalents of PETA (pentaerithritol triacrylate) And the coupling reaction was carried out at room temperature for 20 hours. After work-up with water and methylene chloride, the compound of formula 3 in the form of a highly viscous liquid was obtained in about 85% yield using silica gel column chromatography. The results of the reaction and structural analysis are as follows.

¹ H NMR

_{(400MHz, CDCl 3): δ} 7.85 (d, 2H), 7.70 (d, 2H), 7.55 (d, 2H), 7.38 (d, 2H), 7.30 (d, 2H), 7.03 (d, 2H), (S, 4H), 4.05 (s, 12H), 2.35 (s, 6H)

[Reaction Scheme 2]

&Lt; Preparation of Photosensitive Resin Composition &

Each component described in Table 1 below was injected into a reaction mixing vessel equipped with an ultraviolet ray breaker and a stirrer, and a photosensitive resin composition was prepared by a conventional method.

(Unit: wt%) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 (A) an alkali-soluble resin 11.5 11.5 8.5 8.5 11.5 8.5 (B) a photopolymerizable compound (B-1) 3.8 - 6.8 - - - (B-2) - 3.8 - 6.8 - - (B-3) - - - - 3.8 6.8 (C) a photopolymerization initiator 0.8 0.8 0.8 0.8 0.8 0.8 (D) Solvent 83.9 83.9 83.9 83.9 83.9 83.9

(A) Alkali-soluble resin: copolymer of methacrylic acid and benzyl methacrylate (molar ratio 27:73, acid value 97, weight average molecular weight 15,000)

(B) Photopolymerizable compound:

(B-1) Compound (2) prepared in Synthesis Example 1

(B-2) Compound (3) prepared in Synthesis Example 2

(B-3) KAYARD DPHA (manufactured by Nippon Kayaku Co., Ltd.)

(C) Photopolymerization initiator: Irgacure OXE01 (manufactured by BASF)

(D) Solvent: Propylene glycol monomethyl ether acetate

Experimental Example  1. Manufacture of color filters

The photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2 were applied on a 2 inch glass substrate ("EAGLE XG", manufactured by Corning Incorporated) by spin coating, placed on a heating plate and heated at 100 ° C. for 3 minutes To form a thin film. Subsequently, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% to a step-like pattern and a line / space pattern of 1 to 50 m was placed on the thin film and the distance between the test photomask and the test photomask was set to 100 m. Respectively. At this time, the ultraviolet light source was irradiated with a high pressure mercury lamp of 1 KW containing g, h and i lines at an illuminance of 100 mJ / cm 2, and no special optical filter was used. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the thin film was washed with distilled water, and then blown with nitrogen gas, dried, and heated in a heating oven at 200 ° C for 25 minutes to prepare a color filter. The film thickness of the color filter prepared above was 2.0 mu m.

Experimental Example  2. Property Evaluation of Photosensitive Resin Composition

Using the photosensitive resin compositions of Examples 1 to 4 and Comparative Examples 1 and 2, the following tests were performed on each color filter prepared by the method of Experimental Example 1 to evaluate the physical properties of the photosensitive resin composition.

Developability  ( Residual properties )

After development, the presence or absence and remaining amount of remnants remained without being washed away were observed. It was evaluated as good when there was no residue and when it was remained, it was evaluated as defective.

Residual film ratio

The thickness was measured before and after the post-heat treatment, and the difference in thickness was evaluated by the following equation (1). The larger the residual film ratio, the better.

[Equation 1]

Residual film ratio = (film thickness after post-heat treatment) / (film thickness before post-heat treatment) x 100 (%)

Thermal resistance

After the pattern was finally formed, the thickness change due to the thermal impact was confirmed by the following equation (2). It can be said that when the heat is given at a high temperature, the change of the thickness after a certain period of time is not enough. When heat is applied at 240 캜 for 1 hour, the thickness change ratio is 90% or more, and when it is less than 90%, the thickness is poor.

&Quot; (2) &quot;

Thickness change ratio = (film thickness after heat treatment) / (film thickness before heat treatment) x 100 (%)

Chemical resistance

When the color filter was left in 10% NaOH aqueous solution, 10% aqueous HCl solution and NMP, the change of thickness was measured and chemical resistance was examined. The rate of change in thickness was calculated by Equation (2).

Similar to thermal tolerance, the better the exposure to chemicals is, the less the rate of change in thickness. When each chemical substance was immersed at 40 DEG C for 10 minutes at room temperature, it was judged that the change rate was excellent when the change rate was 0.5% or less, and it was judged that the change rate was less than 1%.

Mechanical properties

When the pattern is deformed by 10% (or depending on conditions) of the thickness, the degree of return is referred to as the elastic restoration ratio, which varies greatly depending on the condition of the pattern. The results of Examples 1 to 4 and Comparative Examples 1 and 2 in which a pattern was formed under the same conditions were compared to each other to give a poor result.

Pattern straightness

Pattern formation of the final patterns prepared using the photosensitive resin compositions prepared in Examples 1 to 4 and Comparative Examples 1 and 2 was observed with an optical microscope. FIGS. 1 to 4 are optical microscopic photographs of the pattern-forming properties of the photosensitive resin compositions according to Examples 1 to 4, respectively. FIGS. 5 to 6 show the results of observing the pattern forming properties of the photosensitive resin compositions according to Comparative Examples 1 and 2 It is an optical microscope photograph.

The pattern formation criterion is as follows.

◎: Excellent pattern formation property

Good: Excellent pattern formation property

DELTA: Good pattern formation property

X: poor pattern formation property

The results of the physical properties measurement of Experimental Example 2 are shown in Table 2 below.

Composition Developability Residual film ratio Heat resistance Chemical resistance Mechanical properties Pattern straightness Example 1 Great 97.5%
: Great 95.6%
: Great 0.4%
: Great Great ○ Example 2 Great 98.3%
: Great 94.5%
: Great 0.3%
: Great Very good ◎ Example 3 Great 96.5%
: Great 95.3%
: Great 0.3%
: Great Great ◎ Example 4 Great 98.1%
: Great 93.2%
: Good 0.2%
: Great Very good ◎ Comparative Example 1 Good 95.2%
: Good 91.5%
: Good 0.8%
: Good Good △ Comparative Example 2 Bad 97.0%
: Great 93.0%
: Good 0.4%
: Great Great X

From the results shown in Table 2, the color filters prepared from the photosensitive resin compositions of Examples 1 to 4 using the compound of the formula 1 as the photopolymerizable compound satisfied all of the physical properties of Experimental Example 2. In particular, the linearity of the developmental pattern was excellent. On the other hand, the color filters prepared from the photosensitive resin compositions of Comparative Examples 1 and 2, which did not use the compound of Chemical Formula 1, showed poor results in terms of development and pattern straightness. Therefore, it was found from the above results that the pattern straightness of the photosensitive resin composition using the compound of Formula 1 as the photopolymerizable compound was very excellent.

Claims (5)

A compound represented by the following formula (1).
[Chemical Formula 1]

Wherein R &_lt; 1 &gt; is an alkyl group having 1 to 10 carbon atoms,
And m is an integer of 0 to 4. 1. A photosensitive resin composition comprising an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, wherein the photopolymerizable compound comprises the compound of the formula (1). The photosensitive resin composition according to claim 2, which comprises 0.5 to 45% by weight of an alkali-soluble resin, 0.5 to 35% by weight of a photopolymerizable compound, 0.01 to 15% by weight of a photopolymerization initiator, and 10 to 90% Wherein the photosensitive resin composition is a photosensitive resin composition. A color filter produced by the photosensitive resin composition of claim 2. A display device comprising the color filter of claim 4.

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