KR20050070638A - Composition for forming column-spacer with high recovery ratio - Google Patents

Abstract

The present invention relates to a composition for forming a column spacer having an excellent elastic recovery rate, and more particularly, to a column which exhibits excellent mechanical strength and elastic modulus and can control and maintain a constant interval of the planar body of the liquid crystal part for a long time in a large liquid crystal display device. The present invention relates to a photopolymerizable resin composition capable of providing a spacer.

Description

Composition for Forming Column Spacer with Excellent Elasticity Restoration Ratio {Composition for Forming Column-spacer With High Recovery Ratio}

The present invention relates to a composition for forming a column spacer having an excellent elastic recovery rate, and more particularly, to a column which exhibits excellent mechanical strength and elastic modulus and can control and maintain a constant interval of the planar body of the liquid crystal part for a long time in a large liquid crystal display device. The present invention relates to a photopolymerizable resin composition capable of providing a spacer.

The color display of the TFT-LCD is achieved through the operation of the TFT and the liquid crystal cell, which control the transmittance of white light of the backlight (B / L), and the additive mixing of the three primary colors transmitted through the red, green, and blue color filters. In the conventional liquid crystal panel, spherical spacers such as glass beads or plastic beads having a desired particle size are used to maintain two substrate gaps into which liquid crystals are injected. However, the use of spherical spacers makes it difficult to distribute them evenly on a substrate, allowing them to exist on effective pixels of red, green and blue cells. In this case, there may be a problem that there is a non-invasion of the spacer or the incident light is scattered and the contrast of the liquid crystal panel is lowered. In particular, there is a problem in that the alignment of the liquid crystal around the spacer is misaligned or the alignment control is not possible due to the voltage on and off.

In order to solve this problem, a method of installing a column spacer capable of installing a spacer on a desired site has been proposed. This method is the same as the pattern formation method using the existing red, green, and blue color resist. The photosensitive column spacer resin is applied to a substrate, and selectively irradiated with ultraviolet rays using a desired mask. By passing through a developing solution and applying heat, a dot or stripe spacer can be formed. In this way, a spacer capable of maintaining a gap at a place other than the effective pixel portion can be formed and the problems raised above can be solved. Conventionally, the cell gap (gap distance between the display side substrate and the liquid crystal drive side substrate) is limited, but this method enables a highly accurate gap control by adjusting the film thickness during coating. . The cell gap is the thickness of the liquid crystal layer itself, which prevents display irregularities such as color unevenness and contrast unevenness, and exhibits good display performance in uniform display, high-speed response, and high contrast ratio. In order to impart color liquid crystal display, precision and uniformity of height are required.

Generally, resins used in negative photo lithography consist of monomers, binder polymers, initiators, and solvents. However, plastic spacers formed in this way have plastic deformation under high temperature and high pressure when assembling and squeezing a color filter, which is an upper substrate, and a TFT array substrate, which is a lower substrate. Cell gap) can not be maintained, causing a problem of stain formation. In order to solve this problem, the hardness is increased, so that the liquid crystal layer cannot be squeezed or expanded in the practical temperature range (-30 ° C to 40 ° C), foaming occurs in the liquid crystal layer, and deterioration of quality display such as staining. There was a problem. Therefore, it is necessary to develop a column spacer having high elasticity. Highly elastic column spacers are necessary for minimizing deformation due to external forces as well as processes, and are the main characteristics that can overcome the cell gap due to pressure difference.

The present invention is to solve the problems of the prior art as described above, in the large liquid crystal display column spacer showing excellent mechanical strength and elastic modulus to maintain a constant liquid crystal cell gap for a long time, and exhibits good film uniformity and developability It is an object to provide a composition for formation.

That is, the present invention (1) a cardo-based copolymer resin prepared by mixing and copolymerizing a fluorene compound represented by the following formula (1), an epoxy compound represented by the following formula (2) and an acrylic acid compound represented by the following formula (3),

[Formula 1]

[Formula 2]

(Wherein R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, a phenyl group, or an ethoxy group having 1 to 8 carbon atoms, and X represents a halogen atom)

[Formula 3]

CH ₂ = CRCOOH

(Wherein R represents an alkyl or aryl group having 1 to 10 carbon atoms, a phenyl group, or an alkoxy group having 1 to 8 carbon atoms, and X represents a halogen atom)

(2) an acrylic copolymer resin containing a carboxyl group,

(3) acrylic photopolymerizable monomer,

(4) photopolymerization initiator,

(5) an epoxy resin, and

(6) It relates to the photopolymerizable resin composition for column spacer formation containing a solvent.

The present invention will be described in more detail below.

In the composition of the present invention, the binder resin may be a mixture of (A) a fluorene compound represented by the following Chemical Formula 1, (B) an epoxy compound represented by the following Chemical Formula 2, and (C) an acrylic acid compound represented by the following Chemical Formula 3, A cardo copolymer resin prepared by copolymerization is used.

In the formula, R represents an alkyl group having 1 to 10 carbon atoms or an aryl group, a phenyl group, or an alkoxy group having 1 to 8 carbon atoms, and X represents a halogen atom.

CH ₂ = CRCOOH

In the formula, R represents an alkyl group having 1 to 10 carbon atoms or an aryl group, a phenyl group, or an alkoxy group having 1 to 8 carbon atoms, and X represents a halogen atom.

At this time, the mixing ratio of the materials is preferably in the range of (A) :( B) :( C) = 1mol: 2-4mol: 2-8mol. The weight average molecular weight of the produced copolymer resin is in the range of 1000 to 20000.

In order to make the produced resin into an alkali soluble resin, it can be used by treating with an acid anhydride represented by the following formula (4).

In the above formula, R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, a phenyl group, or an alkoxy group having 1 to 8 carbon atoms.

The content of the cardo-based copolymer resin in the total composition is 0.5 to 20% by weight. If the content is more than 20% by weight, there is a problem that the phenomenon is torn when developing, and when used less than 0.5% by weight there is a problem that the pattern is not formed and development.

As the acrylic copolymer resin containing a carboxyl group included in the composition of the present invention, a copolymer of an ethylenically unsaturated monomer having one or more carboxyl groups with another copolymerizable ethylenically unsaturated monomer is used. Specifically as a carboxyl group-containing unsaturated monomer, acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, etc. are illustrated, These can be used individually or in mixture of 2 or more types. Examples of other unsaturated monomers include styrene, α-methyl styrene, vinyltoluene, vinyl benzyl methyl ether, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2 -Hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy butyl acrylate, 2-hydroxy butyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl meta Unsaturated carboxylic acid esters such as acrylate, phenyl acrylate and phenyl methacrylate; Unsaturated carboxylic acid amino alkyl esters such as 2-amino ethyl acrylate, 2-amino ethyl methacrylate, 2-dimethyl amino ethyl acrylate and 2-dimethyl amino ethyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; Unsaturated amides, such as acryl amide and methacryl amide, are illustrated, and these can be used individually or in mixture of 2 or more types.

As an acrylic copolymer resin containing such a carboxyl group, specifically, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl Methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxy ethyl methacrylate copolymer, and the like.

In the acrylic copolymer resin containing the carboxyl group, the weight ratio of the carboxyl group-containing unsaturated monomer is 5 to 50% by weight, preferably 10 to 40% by weight. If the content exceeds 50% by weight there is a problem in the initial initiator solubility problem and development characteristics, there is a problem that does not develop when less than 5% by weight.

The weight average molecular weight (Mw) of the carboxyl group-containing copolymer is in the range of 3,000 to 150,000, preferably 5,000 to 50,000.

The content of the carboxyl group-containing copolymer in the total composition is 0.5 to 20% by weight. If the content is more than 20% by weight there is a problem that is developed by a method that is not soluble during development, there is a problem that does not develop when used in less than 0.5% by weight.

As the acrylic photopolymerizable monomer included in the composition of the present invention, materials generally used may be used. Specifically, ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol penta Acrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, noblock epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate , Propylene glycol dimethacrylate, 1,4-butanediol dimeth Etc. dimethacrylate, 1,6-hexanediol dimethacrylate and the like.

In order to easily dissolve such a photopolymerizable monomer in an aqueous alkali solution, it is preferable to use it by treating with an acid anhydride of Formula 4 as shown above.

The content of the photopolymerizable monomer in the total composition is 1 to 20% by weight.

As the photopolymerization initiator included in the composition of the present invention, a photopolymerization initiator generally used may be used. Specifically, 2,2'- diethoxy acetophenone, 2,2'- dibutoxy acetophenone, 2-hydroxy-2-methylproriophenone, pt- butyl trichloro acetophenone, pt- butyl dichloro acetophenone, Benzophenone, 4-chloroacetophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, 2,2'-dichloro-4 -Phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholino Acetophenone compounds such as phenyl) -butan-1-one; Benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4'-bis (diethyl amino) benzo Benzophenone compounds such as phenone; Thioxanthone, 2-Chrol Thioxanthone, 2-Methyl Thioxanthone, Isopropyl Thioxanthone, 2,4-Diethyl Thioxanthone, 2,4-Diisopropyl Thioxanthone, 2-Chloro Thioxide Thioxanthone type compounds, such as Santon; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal; 2,4,6, -trichloro s-triazine, 2-phenyl 4,6-bis (trichloro methyl) -s-tria, 2- (3 ', 4'-dimethoxy styryl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tril) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl 4,6-bis ( Trichloro methyl) -s-triazine, bis (trichloro methyl) -6-styryl s-triazine, 2- (naphtho 1-yl) -4,6-bis (trichloro methyl) -s-tri Azine, 2- (4-methoxy naphtho 1-yl) -4,6-bis (trichloro methyl) -s-triazine, 2-4-trichloro methyl (piperonyl) -6-triazine, Triazine type compounds, such as 2-4- trichloro methyl (4'-methoxy styryl) -6-triazine, are illustrated. In addition, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, biimidazole compounds, and the like can be used.

The content of the photopolymerization initiator in the total composition is 0.1 to 10% by weight.

Specific examples of the epoxy resin included in the composition of the present invention include phenol noblock epoxy resins, tetramethyl bi-phenyl epoxy resins, bisphenol A type epoxy resins, and alicyclic epoxy resins.

In order to easily dissolve such an epoxy resin in an aqueous alkali solution, it is preferable to use it by treating with an acid anhydride of Formula 4 as described above.

The content of the epoxy resin in the total composition is 0.1 to 20% by weight.

Specific examples of the solvent included in the composition of the present invention include ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and the like. It may be used by mixing two or more kinds.

The content of the solvent in the total composition is 20 to 90% by weight.

In the composition of the present invention, a surfactant may be further used as necessary. As such a surfactant, a fluorine system is generally illustrated and these can be used individually or in mixture of 2 or more types.

When surfactant is added, its content in the total composition is 0.1 to 5% by weight.

In order to manufacture the column spacer using the photosensitive resin composition of the present invention as described above, the photosensitive resin composition is formed to a thickness of 0.5 to 10 μm using a suitable method such as spin coating, roller coating, and spray coating on the glass substrate for color filters. After application, the active line is irradiated to form a pattern necessary for the color filter. As a light source used for irradiation, UV of 190-450 nm, Preferably 200-400 nm area is used, and an electron beam and X-ray irradiation are also possible. After the irradiation, when the coating layer is treated with a developer, the unilluminated portion of the coating layer is dissolved to form a pattern necessary for the color filter. By repeating this process in accordance with the required number of colors, a color filter having a desired pattern can be obtained. In addition, the image pattern obtained by the development in the above step can be heated again or cured by active ray irradiation to improve crack resistance, solvent resistance and the like.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples are for the purpose of explanation and are not intended to limit the present invention.

Example 1

The photopolymerization initiator and the epoxy resin (YX-4000HK, Nippon Kayaku Co., Ltd.) were dissolved in a solvent, and then stirred at room temperature for 2 hours. Then, the photopolymerizable monomer, the cardo-based copolymer resin and the acrylate-based copolymer resin were added and stirred at room temperature for 2 hours, and then the surfactant was added and stirred at room temperature for 1 hour. Next, filtration was performed three times to obtain the photosensitive resin composition of the present invention. Specific contents of the composition components used in the present embodiment are as follows.

menstruum

62 g of propylene glycol monomethyl ether acetate

16 g of cyclohexanone

Photopolymerizable monomer

4 g of dipentaerythritol hexaacrylate

1 g of 1,6-hexanediol diacrylate

Photopolymerization Initiator

TAZ-110 (MIDORI KAGAKU) 0.3 g

Igacure 369 (Shiba-Gaigi Co., Ltd.) 0.3g

4,4'-bis (diethylamino) benzophenone (made by Hodogaya Corporation) 0.1 g

Epoxy resin

YX-4000HK (Japanese gunpowder product) 2g

Cardo Copolymer Resin 5 g

(A) :( B) :( C) = Cardo-based resin consisting of 1: 2: 2 molar ratio (Mw = 8000)

(A) 9,9 'bis (4-hydroxyphenyl) fluorene

(B) epichlorohydrin

(C) acrylic acid

Acrylic Copolymer 3 g

(A ') :( B') = acrylic resin consisting of a weight ratio of 30:70 (Mw = 25,000)

(A ') methacrylic acid

(B ') benzyl methacrylate

Surfactants

Fluorinated Surfactant (FC-430, 3M) 0.05g

Example 2

It carried out similarly to Example 1 except having used the acrylic copolymer resin as follows.

Acrylic Copolymer 3 g

(A ') :( B') :( C ') = acrylic resin consisting of a weight ratio of 30: 65: 5 (Mw = 25,000)

(A ') methacrylic acid

(B ') benzyl methacrylate

(C ') 2-hydroxy methyl acrylate

Comparative Example 1

It carried out similarly to Example 1 except not using cardo copolymer resin and only 8g of acrylic copolymer resins of Example 1 were used.

Comparative Example 2

The same procedure as in Example 1 was carried out except that only 8 g of cardo-based copolymer resin was used without using an acrylic copolymer resin.

Comparative Example 3

It carried out similarly to Example 1 except not having used acrylic copolymer resin, but using 2 g of epoxy resins (YX-4000HK, Nippon Kayaku Co., Ltd. product), and 6 g of cardo system copolymer resin.

The pattern formation evaluation of the photosensitive colored resin composition thus produced was performed as follows.

Developability

A photosensitive resin composition was applied on a 1 mm thick chromium coated glass substrate with a thickness of 2 to 6 μm, and dried on a hot plate at a predetermined time (1 minute) and at a constant temperature (80 ° C). Obtained. Subsequently, a photomask was placed on the coating film and exposed using a high pressure mercury lamp having a wavelength of 365 nm, followed by development for 30 seconds at 30 ° C. and atmospheric pressure using a 1% KOH-based aqueous solution. After development, a pattern was obtained by drying at a constant time (40 minutes) and a constant temperature (220 ° C.) in a hot air circulation drying furnace to evaluate the patternability by an optical microscope.

○ Excellent fairness: no residual film on pattern and non-exposed glass substrate

Good processability: When there is a residual film on the pattern, but there is no residual film on the unexposed glass substrate.

× Poor processability: When there is residual film on pattern and unexposed glass substrate

-Heat resistance

A photosensitive resin composition was applied on a chromium-coated glass substrate having a thickness of 1 mm, washed with a thickness of 2 to 6 μm, and dried on a hot plate at a predetermined time (1 minute) and at a constant temperature (80 ° C) to obtain a coating film. It was. Subsequently, a photomask was placed on the coating film and exposed using a high pressure mercury lamp having a wavelength of 365 nm, and then developed for 30 seconds at 30 ° C. and atmospheric pressure using a 1% KOH-based aqueous solution. After development, a pattern was obtained by drying at a constant time (40 minutes) and a constant temperature (220 ° C.) in a hot air circulation drying furnace to evaluate the patternability by an optical microscope. After heat-treatment of this pattern for 3 hours at 220 degreeC, the change of a pattern and color difference were observed.

○: No change in pattern, color difference (ΔE) is 3.0 or less

(Triangle | delta): A little change of a pattern or color difference ((DELTA) E) is 3.0-5.0

X: many pattern changes or color difference ((DELTA) E) is 5.0 or more

※ Pattern change: pattern swelling, recrystallization phenomenon on the pattern surface

Light resistance

A photosensitive resin composition was applied on a chromium-coated glass substrate having a thickness of 1 mm, washed with a thickness of 2 to 6 μm, and dried on a hot plate at a predetermined time (1 minute) and at a constant temperature (80 ° C) to obtain a coating film. It was. Subsequently, a photomask was placed on the coating film and exposed using a high pressure mercury lamp having a wavelength of 365 nm, and then developed for 30 seconds at 30 ° C. and atmospheric pressure using a 1% KOH-based aqueous solution. After development, a pattern was obtained by drying at a constant time (40 minutes) and a constant temperature (220 ° C.) in a hot air circulation drying furnace. After patterning the pattern for 500 hours in a xenon arc lamp (AT65 Ci65), the pattern change and color difference Was observed.

○: No change in pattern, color difference (ΔE) is 3.0 or less

(Triangle | delta): A little change of a pattern or color difference ((DELTA) E) is 3.0-5.0

X: many pattern changes or color difference ((DELTA) E) is 5.0 or more

※ Change of pattern: Inflation or cracking of pattern

Uniformity

A photosensitive resin composition was applied on a chromium-coated glass substrate having a thickness of 1 mm, washed with a thickness of 2 to 6 μm, and dried on a hot plate at a predetermined time (1 minute) and at a constant temperature (80 ° C) to obtain a coating film. It was. Subsequently, a photomask was placed on the coating film and exposed using a high pressure mercury lamp having a wavelength of 365 nm, and then developed for 30 seconds at 30 ° C. and atmospheric pressure using a 1% KOH-based aqueous solution. After development, a pattern was obtained by drying at a constant time (40 minutes) and a constant temperature (220 ° C.) in a hot air circulation drying furnace, and measuring the presence or absence of irregularities in the pattern height.

(Circle): Height difference ((DELTA) H) of a pattern on the same board | substrate is ± 0.2 or less

(Triangle | delta): The height difference ((DELTA) H) of a pattern on the same board | substrate is ± 0.2- ± 0.3

X: The height difference (ΔH) of the pattern on the same substrate is ± 0.3 or more

-Film modulus

A photosensitive resin composition was applied on a chromium-coated glass substrate having a thickness of 1 mm, washed with a thickness of 2 to 6 μm, and dried on a hot plate at a predetermined time (1 minute) and at a constant temperature (80 ° C) to obtain a coating film. It was. Subsequently, a photomask was placed on the coating film and exposed using a high pressure mercury lamp having a wavelength of 365 nm, and then developed for 30 seconds at 30 ° C. and atmospheric pressure using a 1% KOH-based aqueous solution. After development, a pattern was obtained by drying at a constant time (40 minutes) and a constant temperature (220 ° C.) in a hot air circulation drying furnace. The film elastic modulus of the pattern was measured by a Fischer membrane elasticity meter using a beaker type needle.

○: When the elastic recovery rate for penetration depth is 50% or more

○: When elastic recovery rate is 40 ~ 50% of penetration depth

×: elastic recovery rate against penetration depth is 40% or less

The results according to the above evaluation method are shown in Table 1 below.

Developability Heat resistance Light resistance Uniformity Film modulus Example 1 ○ ○ ○ ○ ○ Example 2 ○ ○ ○ ○ ○ Comparative Example 1 ○ × △ ○ ○ Comparative Example 2 × ○ ○ ○ ○ Comparative Example 3 × ○ ○ × ×

The photopolymerizable resin composition of the present invention can provide a column spacer exhibiting excellent film uniformity, high modulus of elasticity and good developability.

1 is a diagram illustrating a structure of a general color filter to which a column spacer is applied.

[Description of Signs of Major Parts of Drawings]

1: liquid crystal

2: polyimide

3: overcoat

4: column spacer

5: ITO electrode

6: glass

7: color resist

8: Black Matrix

Claims (11)

(1) a cardo-based copolymer resin prepared by mixing and copolymerizing a fluorene compound represented by Formula 1 below, an epoxy compound represented by Formula 2 below, and an acrylic acid compound represented by Formula 3 below, [Formula 1] [Formula 2] (Wherein R represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, a phenyl group, or an ethoxy group having 1 to 8 carbon atoms, and X represents a halogen atom) [Formula 3] CH ₂ = CRCOOH (Wherein R represents an alkyl or aryl group having 1 to 10 carbon atoms, a phenyl group, or an alkoxy group having 1 to 8 carbon atoms, and X represents a halogen atom) (2) an acrylic copolymer resin containing a carboxyl group, (3) acrylic photopolymerizable monomer, (4) photopolymerization initiator, (5) an epoxy resin, and (6) The photopolymerizable resin composition for column spacer formation containing a solvent. The content of the cardo-based copolymer resin is 0.5 to 20% by weight, the total amount of the acrylic copolymer resin is 0.5 to 20% by weight, the content of the photopolymerizable monomer is 1 to 20% by weight, The photopolymerization initiator composition is 0.1 to 10% by weight, the content of the epoxy resin is 0.1 to 20% by weight, and the content of the solvent is 20 to 90% by weight. The method of claim 1, wherein the ratio of the material represented by the formula (1), the material represented by the formula (2), and the material represented by the formula (3) is in the range of 1 mol: 2-4 mol: 2-8 mol. Photopolymerizable resin composition. The photopolymerizable resin composition according to claim 1, wherein the cardo-based copolymer resin, the photopolymerizable monomer, and / or the epoxy resin are treated with an acid anhydride represented by the following formula (4). [Formula 4] Wherein R ₁ and R ₂ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group, a phenyl group, or an alkoxy group having 1 to 8 carbon atoms) According to claim 1, The acrylic copolymer resin containing a carboxyl group is an ethylenically unsaturated monomer having at least one carboxyl group selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, itaconic acid, and fumaric acid, styrene, α-methyl Styrene, vinyltoluene, vinyl benzyl methyl ether, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxy ethyl acrylate, 2-hydroxy ethyl Methacrylate, 2-hydroxy butyl acrylate, 2-hydroxy butyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, and phenyl methacrylate Unsaturated carboxylic acid esters including; Unsaturated carboxylic acid amino alkyl esters including 2-amino ethyl acrylate, 2-amino ethyl methacrylate, 2-dimethyl amino ethyl acrylate, and 2-dimethyl amino ethyl methacrylate; Carboxylic acid vinyl esters including vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl esters including glycidyl acrylate and glycidyl methacrylate; Vinyl cyanide compounds including acrylonitrile, and methacrylonitrile; And acryl amide, and unsaturated amides including methacrylic amide. The photopolymerizable resin composition according to claim 5, wherein in the acrylic copolymer resin, the ratio of the ethylenically unsaturated monomer having a carboxyl group is 5 to 50% by weight. The method of claim 1, wherein the acrylic photopolymerizable monomer is ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate , Pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate Latex, trimethylolpropane triacrylate, noblock epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanedioldi Methacrylate, and 1,6-hexanedioldimethacrylate selected from the group consisting of It is 1 or more types, The photopolymerizable resin composition characterized by the above-mentioned. The method of claim 1, wherein the photopolymerization initiator is 2,2'- diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylproriophenone, pt-butyltrichloroacetophenone, pt-butyldichloroacetophenone, benzophenone, 4-chloroacetophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, 2 , 2'-dichloro-4-phenoxycetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1-one and 2-benzyl-2-dimethylamino-1 An acetophenone type compound containing-(4-morpholinophenyl) -butan-1-one; Benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone and 4,4'-bis (diethyl amino) benzo Benzophenone type compound containing a phenone; Thioxanthone, 2-Chrol Thioxanthone, 2-Methyl Thioxanthone, Isopropyl Thioxanthone, 2,4-Diethyl Thioxanthone, 2,4-Diisopropyl Thioxanthone and 2-Chloro Thioxide Thioxanthone type compound containing a santon; Benzoin compounds including benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether and benzyl dimethyl ketal; 2,4,6, -trichloro s-triazine, 2-phenyl 4,6-bis (trichloro methyl) -s-tria, 2- (3 ', 4'-dimethoxy styryl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxy phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tril) -4,6-bis (trichloromethyl) -s-triazine, 2-phenyl 4,6-bis ( Trichloro methyl) -s-triazine, bis (trichloro methyl) -6-styryl s-triazine, 2- (naphtho 1-yl) -4,6-bis (trichloro methyl) -s-tri Azine, 2- (4-methoxy naphtho 1-yl) -4,6-bis (trichloro methyl) -s-triazine, 2-4-trichloro methyl (piperonyl) -6-triazine and Triazine-based compounds including 2-4-trichloro methyl (4'-methoxy styryl) -6-triazine; Carbazole compounds; Diketone compounds; Sulfonium borate compounds; Diazo compounds; And a non-imidazole-based compound. The photopolymerizable resin composition according to claim 1, wherein the epoxy resin is at least one selected from the group consisting of a phenol noblock epoxy resin, a tetramethyl bi-phenyl epoxy resin, a bisphenol A epoxy resin, and an alicyclic epoxy resin. . The photopolymerizable resin composition according to claim 1, further comprising a fluorine-based surfactant alone or in mixture of two or more thereof in an amount of 0.5 to 5% by weight. A column spacer prepared using the photopolymerizable resin composition according to any one of claims 1 to 10.