KR101187881B1 - Photosensitive resin composition for column spacer and display device having the same - Google Patents

Abstract

An inorganic particle, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent are included, wherein the inorganic particles are provided with a photosensitive resin composition for a column spacer including inorganic metal oxide particles.

Description

Photosensitive resin composition for column spacer and display device having the same

The present invention relates to a photosensitive resin composition for column spacers, and more particularly, to a photosensitive resin for column spacers having excellent elastic recovery and an image display apparatus having the same.

Currently, the flat display market has grown so much that it is difficult to support demand, and the center is plasma display panel (PDP), liquid crystal display (LCD), and organic light emitting display (OLED).

A column spacer or a ball spacer is generally used to prevent a change in the cell gap due to the bending of the flexible substrate due to the physical force and the deformation of the flexible substrate due to the external heat, thereby improving the brightness and the image quality of the display device. When the liquid crystal display is manufactured using the ball spacer, the ball spacer particles are sprayed between the substrates. In this case, the ball spacers are positioned inside the pixels, thereby causing interference of color images of red, green, and blue. On the other hand, when manufacturing a liquid crystal display using the column spacer, the spacer can be formed only in the portion other than the effective pixel by the lysing process using the photosensitive resin composition, an important elastic recovery rate of the required characteristics of the spacer to control the cell gap Lower than ball spacers. Thus, there is a need for the development of improved spacers.

SUMMARY OF THE INVENTION An object of the present invention is to provide a photosensitive resin composition for a column spacer, and to provide a photosensitive resin composition for a column spacer having high elasticity with the advantages of a column spacer made of a conventional ball spacer and a conventional photosensitive resin composition. .

In order to achieve the above objects,

According to one aspect of the present invention, there is provided a photosensitive resin composition for column spacers including inorganic particles, binder resins, photopolymerizable compounds, photopolymerization initiators and solvents.

According to another aspect of the present invention, including inorganic particles, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, the inorganic particles are contained 1 to 70 parts by weight based on 100 parts by weight of the solid content excluding the solvent in the total composition The photopolymerizable compound is provided with a photosensitive resin composition for a column spacer containing 5 to 80 parts by weight based on 100 parts by weight of the total of the binder resin and the photopolymerizable compound based on solid content.

According to another aspect of the present invention, including inorganic particles and a solvent containing silica, the solvent contains 20 to 90 parts by weight based on 100 parts by weight of the total composition, 100 parts by weight of solids excluding the solvent in the total composition With respect to the inorganic particles, there is provided a photosensitive resin composition for column spacers containing 1 to 70 parts by weight.

According to still another aspect of the present invention, there is provided a color filter comprising a column spacer obtained by applying the photosensitive resin composition for any one of the column spacers described above on a substrate and exposing and developing in a predetermined pattern.

According to still another aspect of the present invention, there is provided an image display device having the above-described color filter.

According to this invention, the photosensitive resin composition for column spacers which is excellent in elastic restoring force is provided. When the column spacer is formed using the photosensitive resin composition for the column spacer, a display display device having high elasticity and excellent electrical insulation may be obtained.

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition for column spacers which concerns on this invention contains an inorganic particle (A), binder resin (B), a photopolymerizable compound (C), a photoinitiator (D), and a solvent (E). In addition, the photosensitive resin composition for the column spacer may optionally further include an additive (F).

Hereinafter, each component contained in the photosensitive resin composition for column spacers of this invention is demonstrated in detail.

Inorganic Particles (A)

The inorganic particles (A) may be applied to inorganic metal oxide particles such as silica, alumina, titania, and zirconia. The said inorganic particle (A) can be used individually or in combination of 2 or more types, A silica particle is mentioned as a preferable example of the said inorganic particle (A). The silica (SiO ₂ ) used may be substantially spherical, particles less than 5 microns in size, dispersed in aqueous or other solvent media. The silica particles used in the present invention may be silica particles having an average particle diameter of 10 nm to 5 μm, preferably 100 nm to 3 μm. Average particle size can be determined using transmission electron microscopy. In addition, silica particles generally have a surface area of greater than about 30 m 2 / gram. For maximum improvement in shear value, the particles preferably have a narrow particle size distribution, ie the polydispersity may be 2.0 or less, preferably 1.5 or less. If desired, smaller amounts of larger silica particles may be added, but such addition may not contribute to an increase in shear value.

Specific examples of the silica include, but are not limited to, nano silica (AEROSIL 200, TT 600; manufactured by Degussa) and hydrophobic nano silica (AEROSIL R972; manufactured by Degussa).

In the case of using the inorganic particles (A), the shape of the particles is not limited. The inorganic particles (A) may preferably have a shape having an average particle diameter of 5 μm or less, which can be observed by an electron microscope. The surface of the inorganic particles may be treated with a silane coupling agent or the like. In this case, compatibility with the binder resin and adhesive properties can be improved.

In addition, when applied as a column spacer, the inorganic particles (A) may contain 1 to 70 parts by weight based on 100 parts by weight of solids excluding the solvent in the total composition in order to have a better elastic recovery. When the content of the inorganic particles (A) is less than 1 part by weight, the elastic recovery rate is not sufficient, and when the content of the inorganic particles (A) is more than 70 parts by weight, pattern formation may be difficult.

The binder resin (B)

The binder resin (B) can be applied to those commonly used in the art, in particular, the binder resin (B) is preferably a copolymer of a compound having an unsaturated carboxyl group and other monomers copolymerizable therewith.

The compound having an unsaturated carboxyl group is not limited as long as it is a carboxylic acid compound having an unsaturated double bond that can be polymerized, and each compound can be used alone or in combination of two or more thereof.

Specific examples of the compound having an unsaturated 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; And anhydrides of the dicarboxylic acids; Mono (meth) acrylates of a polymer having a carboxyl group and a hydroxyl group at both terminals such as ω-carboxypolycaprolactone mono (meth) acrylate, monomethyl maleic acid, isoprene sulfonic acid, styrene sulfonic acid, 5-norbornene-2- Carboxylic acid, mono-2-((meth) acryloyloxy) ethyl phthalate, mono-2-((meth) acryloyloxy) ethyl succinate, or a mixture thereof. Among the compounds having an unsaturated carboxyl group exemplified above, acrylic acid and methacrylic acid are preferred because of their excellent copolymerization reactivity and solubility in a developing solution.

Other monomers copolymerizable with the monomer having a carboxyl group are monomers having a carbon-carbon unsaturated bond, and specific examples thereof include aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyltoluene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, benzyl acrylate, benzyl methacrylate Unsaturated carboxylate compounds such as acrylates; Unsaturated aminoalkyl carboxylate compounds such as aminoethyl acrylate; Unsaturated glycidyl carboxylate compounds such as glycidyl methacrylate; Vinyl carboxylate compounds such as vinyl acetate and vinyl propionate; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile and α-chloroacrylonitrile; 3-methyl-3-acryloxymethyloxetane, 3-methyl-3-methacryloxymethyloxetane, 3-ethyl-3-acryloxymethyloxetane, 3-ethyl-3-methacryloxymethyloxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-methyl-3- methacryloxyethyl oxetane, etc. And unsaturated oxetane carboxylate compounds.

The binder resin (B) may be included in an amount of 5 to 90 parts by weight, preferably 10 to 60 parts by weight, based on 100 parts by weight of solids in the photosensitive resin composition. If the binder resin (B) is within the content range on the basis of the above standard, the formation of the pattern is possible, and the residual film ratio is improved.

Photopolymerization  The compound (C)

The said photopolymerizable compound (C) is a compound which can superpose | polymerize by the action | action of light and the photoinitiator mentioned later, A monofunctional monomer, a bifunctional monomer, another polyfunctional monomer, etc. are mentioned. Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinylpyrroli Money, etc.

Specific examples of the bifunctional monomers include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycoldi (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, etc. are mentioned.

Specific examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylol propane tri (meth) acrylate, and pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxylated dipentaeryte Lithol hexa (meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Of these, bifunctional or higher polyfunctional monomers are preferably used.

The photopolymerizable compound (C) may be used in the range of 5 to 80 parts by weight, preferably 10 to 70 parts by weight based on 100 parts by weight of the total of the binder resin (B) and the photopolymerizable compound (C) based on solid content. Can be. If the photopolymerizable compound (C) is in the range of 5 to 80 parts by weight based on the above criteria, the pattern property and the developability with respect to the developing solution become good, which is preferable.

Light curing Initiator (D)

Although the said photoinitiator (D) is not restrict | limited, It is preferable to use at least 1 sort (s) of compound chosen from the group which consists of a triazine type compound, an acetophenone type compound, a biimidazole type compound, and an oxime compound.

As said triazine type compound, it is 2, 4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1, 3, 5- triazine, 2, 4-bis (trichloromethyl)-, for example. 6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4- Bis (trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2 -Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-tri Azine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloro Methyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

As said acetophenone type compound, diethoxy acetophenone, 2-hydroxy-2-methyl-1- phenyl propane- 1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2- Hydroxyethoxy) phenyl] -2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane- 1-one oligomer etc. are mentioned.

In addition, the acetophenone-based compound may be a compound represented by the following formula (1).

≪ Formula 1 >

In Formula 1, R ₁ to R ₄ are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a phenyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, or a benzyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms. Or a naphthyl group which may be substituted by an alkyl group having 1 to 12 carbon atoms.

Specific examples of the compound represented by Formula 1 include 2-methyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-ethyl-2-amino (4-morpholinophenyl) ethane-1 -One, 2-propyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-butyl-2-amino (4-morpholinophenyl) ethan-1-one, 2-methyl-2 -Amino (4-morpholinophenyl) propane-1-one, 2-methyl-2-amino (4-morpholinophenyl) butan-1-one, 2-ethyl-2-amino (4-morpholino Phenyl) propane-1-one, 2-ethyl-2-amino (4-morpholinophenyl) butan-1-one, 2-methyl-2-methylamino (4-morpholinophenyl) propan-1-one , 2-methyl-2-dimethylamino (4-morpholinophenyl) propan-1-one, 2-methyl-2-diethylamino (4-morpholinophenyl) propan-1-one, etc. may be mentioned. .

Examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'- Dichlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, the phenyl group at the 4,4', 5,5 ' An imidazole compound substituted by an alkoxy group, and the like. Among them, 2,2'bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4', 5,5'-tetraphenylbiimidazole can be preferably used.

As said oxime compound, the compound etc. which are represented by following General formula (2)-4 are mentioned, for example.

<Formula 2>

<Formula 3>

&Lt; Formula 4 >

Moreover, in addition to the photoinitiator mentioned above, the other photoinitiator etc. which are normally used in this field can also be used together if it is a grade which does not impair the effect of this invention. As another photoinitiator, a benzoin compound, a benzophenone type compound, a thioxanthone type compound, an anthracene type compound, a polyfunctional thiol compound, etc. are mentioned, for example. These can be used individually or in combination of 2 types or more, respectively.

As said benzoin type compound, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, etc. are mentioned, for example.

As said benzophenone type compound, benzophenone, methyl 0- benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, etc. are mentioned.

As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. Can be mentioned.

Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. Can be mentioned.

Examples of the polyfunctional thiol compound include tris- (3-mercaptopropionyloxy) -ethyl-isocyanurate, trimethylolpropanetris-3-mercaptopropionate, and pentaerythritol tetrakis-3. Mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate, and the like.

Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid Methyl, a titanocene compound, etc. are mentioned as another photoinitiator.

According to this invention, you may use combining the photoinitiator (D) with a photoinitiator adjuvant (D-1). When photopolymerization start adjuvant (D-1) is used together with a photoinitiator (D), since the photosensitive resin composition containing these is more sensitive, productivity at the time of forming a column spacer using this is preferable.

As the photopolymerization initiation assistant (D-1), one or more compounds selected from the group consisting of amine compounds and carboxylic acid compounds can be preferably used.

Specific examples of the amine compound in the photopolymerization initiation assistant (D-1) include aliphatic amine compounds such as triethanolamine, methyldiethanolamine, and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamino Isoamyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoic acid, 2-dimethylaminoethyl benzoic acid, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (commonly known as Michler's ketone), Aromatic amine compounds, such as 4,4'-bis (diethylamino) benzophenone, are mentioned. As the amine compound, an aromatic amine compound is preferably used. Specific examples of the carboxylic acid compound in the photopolymerization initiation assistant (D-1) include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, and dimethoxyphenyl And aromatic heteroacetic acids such as thioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine and naphthoxyacetic acid.

The content of the photopolymerization initiator (D) is 0.1 to 40 parts by weight, preferably 1 to 30 parts by weight based on 100 parts by weight of the total of the binder resin (B) and the photopolymerizable compound (C) based on the solid content. In addition, the content of the photopolymerization initiation assistant (D-1) is 0.1 to 50 parts by weight, preferably 1 to 40 parts by weight based on 100 parts by weight of the total amount of the binder resin (B) and the photopolymerizable compound (C) based on the solid content. Buddha. When the content of the photopolymerization initiator (D) is in the above range on the basis of the above criteria, the photosensitive resin composition is highly sensitive, and thus the strength and smoothness on the surface of the pattern formed using the composition are good. Moreover, since the sensitivity of the photosensitive resin composition becomes higher and the productivity of the column spacer formed using this composition improves, when the usage-amount of a photoinitiation adjuvant (D-1) exists in said range on the said reference | standard.

Solvent (E)

The solvent (E) is not particularly limited, and various organic solvents commonly used in the art may be used.

Specific examples of the solvent (E) 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 dimethyl ether, and diethylene. Diethylene glycol dialkyl ethers such as glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, and propylene glycol Alkoxy alkyl acetates, such as alkylene glycol alkyl ether acetates, such as a monomethyl ether acetate, a propylene glycol monoethyl ether acetate, and a propylene glycol monopropyl ether acetate, a methoxy butyl acetate, and a methoxy pentyl acetate,

Aromatic hydrocarbons such as benzene, toluene, xylene, mesitylene, ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene Alcohols such as glycol and glycerin, esters such as 3-ethoxy propionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone.

Among the solvents described above, organic solvents having a boiling point of 100 to 200 ° C in the solvents are preferable in terms of coating properties and drying properties, and more preferably alkylene glycol alkyl ether acetates, ketones and 3-ethoxypropionic acid. Ester, such as ethyl and 3-methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether acetate, a propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate, 3-methoxy Methyl propionate etc. are mentioned.

These solvents (E) can be used individually or in mixture of 2 or more types, respectively.

Content of the said solvent (E) is 20-90 weight part with respect to 100 weight part of all the photosensitive resin compositions containing it, Preferably it is 60-85 weight part. When content of the said solvent (E) is the range of 20-90 weight part on the said reference | standard, it applied with the coating apparatuses, such as a roll coater, a spin coater, a slit and spin coater, a slit coater (it may be called a die coater), and inkjet. Since applicability | paintability becomes favorable at the time, it is preferable.

Additive (F)

If necessary, the photosensitive resin composition of the present invention may be used alone or in combination with another polymer compound, a curing agent, a pigment dispersant, an adhesion promoter, an antioxidant, an ultraviolet absorber, or an anti-agglomerating agent.

Specific examples of the other high molecular compound include thermosetting resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. Can be mentioned.

The said hardening | curing agent is used in order to raise a deep part hardening and mechanical strength, As a hardening | curing agent, an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, an oxetane compound, etc. are mentioned.

Specific examples of the epoxy compound in the curing agent include a bisphenol A epoxy resin, a hydrogenated bisphenol A epoxy resin, a bisphenol F epoxy resin, a hydrogenated bisphenol F epoxy resin, a noblock type epoxy resin, other aromatic epoxy resins, and an alicyclic epoxy resin. , Aliphatic, cycloaliphatic or aromatic epoxy compounds other than glycidyl ester resins, glycidylamine resins, or brominated derivatives of these epoxy resins, epoxy resins and brominated derivatives thereof, butadiene (co) polymer epoxides, isoprene ( Co) polymer epoxide, glycidyl (meth) acrylate (co) polymer, triglycidyl isocyanurate, and the like.

Specific examples of the oxetane compound in the curing agent include carbonate bis oxetane, xylene bis oxetane, adipate bis oxetane, terephthalate bis oxetane, cyclohexane dicarboxylic acid bis oxetane and the like.

The said hardening | curing agent can use together the hardening auxiliary compound which can make ring-opening-polymerize the epoxy group of an epoxy compound, and the oxetane skeleton of an oxetane compound with a hardening | curing agent. As said hardening auxiliary compound, polyhydric carboxylic acid, polyhydric carboxylic anhydride, an acid generator, etc. are mentioned, for example.

As said carboxylic anhydride, what is marketed can be used as an epoxy resin hardening | curing agent. As said commercially available epoxy resin hardening | curing agent, for example, brand name Adekahadona EH-700 (made by Adeka Industry Co., Ltd.), brand name Rikashitdo HH (manufactured by Nippon Ewha Co., Ltd.), brand name MH-700 (manufactured by Nippon Ewha Co., Ltd.) ), And the like.

The hardening | curing agent and hardening auxiliary compound which were illustrated above can be used individually or in mixture of 2 or more types, respectively.

As said surfactant, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, polyethylene Imine, etc .; KP (Shin-Etsu Chemical Co., Ltd.), Polyflow (POLYFLOW, Kyoeisha Chemical Co., Ltd.), F-Top (EFTOP, Tochem Products), Mega Pack (MEGAFAC) , Dai Nippon Ink Chemical Co., Ltd.), Florad (Flourad, Sumitomo 3M Co., Ltd.), Asahi guard, Suflon (above, Asahi Glass Co., Ltd.), SOLSPERSE, Lubrisol Company), EFKA (made by EFKA Chemicals Co., Ltd.), PB 821 (made by Ajinomoto Co., Ltd.), Disperbyk-series (made by BYK-chemie), etc. are mentioned.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyl tris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- ( 3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercapto propyltrimeth And oxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

Each of the adhesion promoters may be used alone or in combination of two or more thereof, and preferably 0.01 to 10 parts by weight, preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the solids of the photosensitive resin composition.

As a specific example of the said antioxidant, hindered phenol type, such as 2,2'- thiobis (4-methyl-6-t-butylphenol) and 2,6-di-t- butyl- 4-methylphenol, is mentioned.

As a specific example of the said aggregation inhibitor, sodium polyacrylate is mentioned.

The column spacer photosensitive resin composition of this invention can be manufactured by the following method, for example.

After adding an inorganic particle (A), binder resin (B), a photopolymerizable compound (C), and a photoinitiator (D), and an additive (F) as needed, additional solvent may be made into predetermined concentration as needed. Furthermore, it adds and obtains the photosensitive resin composition for column spacers of interest.

As follows, the present invention will be described in more detail based on examples, but the embodiments of the present invention disclosed below are exemplified to the last, and the scope of the present invention is not limited to these embodiments. The scope of the invention is indicated in the appended claims, and moreover, contains all modifications within the meaning and range equivalent to the claims. In addition, the number shown in the table | surface of a following example and a comparative example shows a weight part.

<Examples 1-6, Comparative Examples 1-3>

Each component of the following Table 1 was mixed and the photosensitive resin composition for highly elastic column spacers was obtained.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Silica inorganic particles
(A) 2.13 3.16 3.56 4.06 4.76 5.72 Binder Resin (B) Acrylic resin (CSB-1012)
4.2 Photopolymerization
Compound (C) Dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
4.2 Photopolymerization
Initiator (D) Ethanone-1- [9-ethyl-6- (2-methyl-4tetrahydropyranyloxybenzoyl) -9H-carbazol-3-yl] -1- (O-acetyloxime) (Irgacure OXE02; Cibasa Produce)
1.0 Solvent (E) Propylene Glycol Monomethyl Ether Acetate
51.32 Additive (F1) Epoxy resin (SUMI-EPOXY ESCN-195XL; manufactured by Sumitomo Kagaku Kogyo Co., Ltd.)
0.5 Additive (F2) 3-methacryloxypropyltrimethoxysilane
0.02

<Experimental Example 1>

Two square inches of ITO etched glass substrates were washed sequentially with neutral detergent, water and alcohol and then dried. After coating the photosensitive resin composition according to the above Examples and Comparative Examples on the glass substrate using a spin coating equipment so that the film thickness is 4.0㎛, and dried at 110 ℃ 2 minutes

After exposure using a mask engraved with a spacer pattern (20 μm) at an exposure dose (365 nm) of 100 mJ / cm 2, after developing for 60 seconds using a developer mixed with a KOH mixed solution and DI 1: 100 (KOH mixed solution: DI) After washing with water for 30 seconds, and baking for 30 minutes at 220 ℃ to form a 20 ㎛ pattern.

<Experimental Example 2>

Experiments for measuring the specific dielectric constant is coated using a pattern mask so that the film thickness is not 4.0㎛, and after drying for 2 minutes at 110 ℃ 2 exposed the entire surface without a mask at an exposure dose (365 nm) 100 mJ / ㎠ and then KOH mixing The solution was developed for 60 seconds using a developer mixed with DI 1: 100 (KOH mixed solution: DI), washed with water for 30 seconds, and calcined after 30 minutes at 220 ° C.

1. Measurement of dielectric constant

An aluminum electrode was formed on the substrate made through Experimental Example 2 using an aluminum vacuum deposition apparatus and a mask. At this time, the aluminum electrode was deposited in a thickness of 0.075 ± 0.025 μm on a spacer layer and an uncoated layer (ITO electrode) in a 5 mm diameter circular shape.

Capacitance when an alternating voltage of 1 to 100 kHz, 1 V was applied to the aluminum electrode on the coating layer of the deposited specimen and the aluminum electrode of the non-coating layer using a capacitance meter (trade name LCR meter 4284A, Agilnet). It measured, and the dielectric constant was computed from the value, and is shown in Table 3. It is preferable that the dielectric constant is less than 5.0 as the evaluation criteria.

division Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2 Comparative Example 3 Relative dielectric constant 4.1 4.1 3.8 3.7 3.6 3.5 4.7 4.9 4.7

As shown in Table 2, the photosensitive resin composition for a spacer of an embodiment including silica as insulating particles, and these are included within a preferred range of the present invention has no problem in electrical insulation like a conventional spacer, and rather has better insulation. It can be seen that is obtained.

2. Measurement of elasticity (recovery rate)

The column spacer pattern (20 μm) made through the above <Experimental Example 1> was defined as the shape of basic conditions for measuring mechanical properties, that is, compression displacement and elastic recovery rate. Compression displacement and elastic recovery rate were measured using a Shimatsu Corporation ultra-compact axial hardness meter, and the measurement conditions were as follows.

A flat indenter with a diameter of 50 µm was used as the indenter for pressing the pattern, and the measuring principle was carried out by a load-unload method. Test loading standard was 5gf, load speed was 0.45 gf / sec and holding time was 3 sec.

The spacer formed by the pattern process with the photosensitive resin of this invention has a fixed thickness. When the other substrates are bonded, the thickness of the spacers is reduced by pressing.

 When the force is given, the length of the pattern (D1) means the compression displacement. In addition, when the pressing force (F) is removed, the thickness of the spacer is increased by the restoring force (S2). At this time, the difference between the thickness of the spacer and the initial thickness of the non-compressed spacer is indicated by D2. The elastic recovery rate can be expressed as follows.

Compression Displacement = D1 (㎛)

Elastic recovery rate = [(D1-D2) X 100] / D1

division Compression Displacement / ㎛ Elastic recovery rate /% Example 1 0.51 85 Example 2 0.55 88 Example 3 0.51 88 Example 4 0.49 89 Example 5 0.58 89 Example 6 0.47 90 Comparative Example 1 0.49 78 Comparative Example 2 0.51 77 Comparative Example 3 0.51 77

Claims (14)

delete delete delete delete delete Including inorganic particles, a binder resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, the inorganic particles are contained 1 to 70 parts by weight based on 100 parts by weight of the solid content excluding the solvent in the total composition, the photopolymerizable compound is a solid content 5 to 80 parts by weight based on 100 parts by weight of the total of the binder resin and the photopolymerizable compound are contained,
The said inorganic particle contains silica, the average particle diameter of the said silica is 10 nm-5, polydispersity is 2.0 or less, and the said inorganic particle was the photosensitive resin composition for column spacers treated with the silane coupling agent. delete delete delete The photosensitive resin composition for column spacers according to claim 6, wherein the solvent contains 20 to 90 parts by weight based on 100 parts by weight of the total composition. delete delete A color filter comprising a column spacer obtained by applying a photosensitive resin composition for column spacers according to claim 6 on a substrate, and exposing and developing in a predetermined pattern. An image display apparatus comprising the color filter of claim 13.