KR101030486B1 - Photoresist composition for column spacer - Google Patents

Abstract

The present invention relates to a photocurable composition used to manufacture a column spacer of a liquid crystal display device.

The photocurable composition of the present invention comprises an [A] alkali-soluble resin, [B] a polymerizable compound having an ethylenically unsaturated bond, [C] an epoxy oligomer comprising an alkyleneoxy group represented by the following formula (1), and a [D] photopolymerization initiator. It is characterized by containing.

The photocurable composition according to the present invention is not only excellent in heat resistance, but also capable of pattern formation at an appropriate thickness when forming column spacers of liquid crystal display devices, and has good recovery rate, flatness, resolution, solvent resistance, and pattern shape.

<Formula 1>

Column spacers, photocurable, epoxy bonds

Description

Photocurable resin composition for column spacers {PHOTORESIST COMPOSITION FOR COLUMN SPACER}             

1 is a view for showing the compression displacement and recovery rate when applying a force to the column spacer.

2 is a graph showing the relationship between the compression displacement and the recovery rate of the column spacer.

Explanation of symbols for main parts of the drawings

A: Pattern state before applying certain force

B: Pattern state when a certain force is applied

C: Restored pattern state when the pressed force is removed

T: pattern height (film thickness), 3 (± 0.3) ㎛

D ₁ : Compression displacement (μm) when a certain force is applied

D ₂ : Difference between initial film thickness and final restored state

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a photocurable composition for column spacers used in liquid crystal display devices, and more particularly, to forming a pattern with an appropriate thickness when forming a column spacer of a liquid crystal display device, and having a recovery rate, flatness, resolution, residual film rate, and pattern. It relates to a photocurable composition having excellent stability.

The liquid crystal display device is constituted by upper and lower panels having a constant interval and liquid crystal injected between the panels. The gap between the upper and lower panels is called a cell gap and is determined by the thickness of the injected liquid crystal. The cell gap of the liquid crystal display device should be kept constant throughout the panel. This is because whether or not the cell gap is kept constant, that is, whether the cell gap is uniform, affects the high-speed response characteristics, contrast, and wide-field angle of the liquid crystal.

Conventionally, the method of spraying spherical spacer particles, such as glass beads and plastic beads, in the middle of two board | substrates, and adjusting the thickness of a liquid crystal layer by these sizes has been used.

However, in this method, 1) these spacer particles are randomly sprayed, so that the spacers are reflected inside the effective pixels, or incident light is scattered to reduce the contrast and aperture ratio of the liquid crystal panel, or 2) spherical glass beads during liquid crystal injection. The spherical spacers of partially cross-linked polymethylmethacrylate beads may change position due to external impact, which may affect the image. 3) Since the particle size of the spacer has a distribution, it may cause unevenness of the gap. Indicates. In particular, as the panel becomes larger and higher in resolution, this problem becomes extreme.

In order to solve this problem, a method of forming a spacer by a photolithography method has been proposed. This method is a method of applying a photocurable composition to a substrate, irradiating ultraviolet rays through a predetermined mask, and then leaving only the exposed and exposed portions as spacers. In this way, column spacers can be formed. The advantage of this method is that 1) the space can be formed only on the portions other than the effective pixels, and 2) the sep gap can be controlled by adjusting the thickness of the film to be applied.

The present invention provides an excellent photocurable composition having a uniform thickness after patterning, high sensitivity, and no developable afterimage, solvent resistance, and high recovery rate when forming a column spacer of a liquid crystal display by photolithography. The purpose.

The technical problem and object,

[A] Alkali-soluble resin

[B] a polymerizable compound having an ethylenically unsaturated bond

[C] epoxy oligomers containing alkyleneoxy groups                     

[D] Photopolymerization Initiator

It is achieved by the photocurable resin composition characterized by containing.

Hereinafter, each component of the photocurable composition of this invention is explained in full detail.

[A] Alkali-soluble resin

[A] alkali-soluble resin used in the photocurable composition of the present invention

(a1) unsaturated carboxylic acids and / or unsaturated carboxylic anhydrides,

(a2) epoxy group-containing unsaturated compounds,

(a3) Olefinic unsaturated compounds other than said (a1) and (a2)

Obtained by radical polymerization.

Examples of the compound (a1) unsaturated carboxylic acid and / or unsaturated carboxylic anhydride include acrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, citraconic acid, mesaconic acid and anhydrides of these dicarboxylic acids. Among these, acrylic acid, methacrylic acid, maleic anhydride and the like are preferably used in view of copolymerization reactivity, heat resistance and easy availability. These compounds (a1) are used individually or in combination.

Epoxy group-containing unsaturated compounds of the compound (a2) include glycidyl acrylate, glycidyl methacrylate, α-ethyl acrylate glycidyl, α-n-propyl acrylate glycidyl, α-n-butyl acrylate glycidyl , Acrylic acid-3,4-epoxy butyl, methacrylic acid-3,4-epoxy butyl, acrylic acid-6,7-epoxy heptyl, methacrylic acid-6,7-epoxy heptyl, α-ethyl acrylic acid-6,7- Epoxy heptyl, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether and the like are preferably used in view of increasing copolymerization reactivity and heat resistance and hardness of the resulting protective film. These compounds (a2) are used individually or in combination.

Examples of the compound (a3) include methacrylic acid alkyl ester methyl acrylate and isopropyl acrylate such as methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, sec-butyl methacrylate and t-butyl methacrylate. Methacrylic acid, such as acrylic acid alkyl ester cyclohexyl methacrylate, 2-methyl cyclohexyl methacrylate, dicyclopentenyl methacrylate, dicyclopentenyloxyethyl methacrylate, isoboroyl methacrylate, etc. Cycloalkyl ester cyclohexyl acrylate, 2-methyl cyclohexyl acrylate, dicyclopentenyl acrylate, dicyclopentenyloxyethyl acrylate, isoboroyl acrylate, such as acrylic acid cycloalkyl ester petyl methacrylate, benzyl Methacrylic acid aryl ester phenyl acrylates such as methacrylate, Hydroxyalkyl esters such as dicarboxylic acid acrylate ester diethyl maleate, diethyl fumarate, diethyl itaconic acid, etc. And styrene, o-methyl styrene, m-methyl styrene, p-methyl styrene, vinyl toluene, p-methoxy styrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, Vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like. Among them, styrene, t-butyl methacrylate, dicyclopentenyl methacrylate, p-methoxy styrene, 2-methyl cyclohexyl acrylate, 1,3-butadiene, and the like are preferred from the viewpoint of copolymerization reactivity and heat resistance. These compounds (a3) are used alone or in combination.

The copolymer [A] used in the present invention preferably contains 10 to 70%, particularly preferably 20 to 50% of the structural unit derived from the compound (a3). When this structural unit is less than 10%, the storage stability of copolymer [A] tends to fall, and when it exceeds 70%, alkali solubility, heat resistance, and surface hardness of copolymer [A] will fall. .

The above-mentioned [A] copolymer used in the present invention has a carboxyl group and / or a carboxylic anhydride group and an epoxy group, and can be easily cured by heating without using a special curing agent and is soluble in an aqueous alkali solution.

The molecular weight of the copolymer [A] and its distribution are not limited to specific values as far as possible to apply the composition solution of the present invention uniformly.

As a solvent used for the synthesis of the copolymer [A], ethers such as alcohols such as methanol and ethanol, tetrahydrofuran, diethylene glycol dimethyl ether and diethylene glycol diethyl ether, propylene glycol methyl ether acetate, and propylene glycol ethyl ether Propylene glycol alkyl ether acetates such as acetate, propylene glycol propyl ether acetate and propylene glycol butyl ether acetate are preferred.

As a polymerization initiator used for the synthesis | combination of copolymer [A], what is generally known as a radical polymerization initiator can be used. For example, 2,2'-azobis isobutyronitrile, 2,2'-azobis- (2,4-dimethylvaleronitrile), 2,2'-azobis- (4-methoxy-2, Azo compounds, such as 4-dimethylvaleronitrile), organic peroxides, such as benzoyl peroxide, t-butyl peroxy pibarate, and 1,1'-bis- (t-butyl peroxy) cyclohexane, and hydrogen peroxide are mentioned. When a peroxide is used as a radical polymerization initiator, you may use as a redox initiator by using a peroxide together with a reducing agent.

[B] a polymerizable compound having an ethylenically unsaturated bond

As the polymerizable compound having an [B] ethylenically unsaturated bond used in the present invention, mono-, bi-, or tri- or higher (meth) acrylates have good polymerizability, and the heat resistance and surface hardness of the resulting protective film are improved. It is preferable from a viewpoint of being.

As monofunctional (meth) acrylate, 2-hydroxy ethyl (meth) acrylate, carbitol (meth) acrylate, isobornyl (meth) acrylate, 3-methoxy butyl (meth) acrylate, for example , 2- (meth) acryloyl oxyethyl 2-hydroxy propyl phthalate, and the like.

As a bifunctional (meth) acrylate, for example, ethylene glycol (meth) acrylate, 1,6-hexanediol (meth) acrylate, 1,9-nonanediol (meth) acrylate, propylene glycol (meth) ) Acrylate, tetraethylene glycol (meth) acrylate, bisphenoxy ethyl alcohol fluorene diacrylate, etc. are mentioned.                     

As (meth) acrylate more than trifunctional, for example, tris hydroxyethyl isocyanurate tri (meth) acrylate, trimethyl propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, etc. are mentioned.

Such mono-, bi-, or tri- or more (meth) acrylates are used alone or in combination.

Epoxy oligomers containing [C] alkyleneoxy groups

Epoxy oligomers containing [C] alkyleneoxy groups such as the structural formulas represented by the following general formula (1) used in the present invention are preferable from the viewpoint of good curing property and improving heat resistance and recovery rate of the resulting protective film, which is 100 wt% of the total photocurable composition. More preferably from 0.1 to 20% by weight. When included in less than 0.1% by weight does not show the effect of improving the recovery rate, when included in more than 20% by weight is restored to some extent, but the effect on heat resistance and pattern shape is less.                     

<Formula 1>

In particular, in the present invention, as the epoxy oligomer containing an alkyleneoxy group,

Alpha, omega-bis (3-glycidomethyl) polytetramethylene glycol,

Alpha, omega-bis (3-glycidomethyl) polypropylene glycol,

Alpha, omega-bis (3-glycidomethyl) polyethylene glycol,

More preferably, at least one of alpha, omega-bis (3-glycidomethyl) polymethylene glycol is included.

[D] Photopolymerization Initiator

[D] photopolymerization initiators used in the present invention include acyloin ethers such as acyl benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, such as a-diketones benzoin such as benzyl and diacetyl. Ryu thioxanthone, 2,4-diethyl thioxanthone, thioxanthone-4-sulfonic acid, benzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) Benzophenones such as benzophenone, acetophenone, p-dimethylaminoacetophenone, α, α'-dimethoxy acetoxybenzophenone, 2,2'-dimethoxy-2-phenylacetophenone, p-methoxyacetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propanone, 2-benzyl-2-diethylamino-1- (4-morpholinophenyl) -butan-1-one Halogen compounds, such as acetophenones anthraquinone and 1, 4- naphthoquinone, quinone phenacyl chloride, tribromomethylphenyl sulfone, and tris (trichloromethyl) -s-triazine, etc. Oksa Acyl phosphine, such as peroxide, 2,4,6-trimethylbenzoyl diphenyl phosphine oxide, such as DE may be mentioned oxides such as pins.

[E] solvent

The photocurable resin composition of this invention is normally melt | dissolved in a suitable solvent, and is used in a solution state. This solvent is capable of uniformly dissolving each component of the [A] copolymer, the [B] polymerizable compound, the epoxy oligomer containing the [C] alkyleneoxy group, and the [D] thermal radical polymerization initiator. What does not react is used. Specifically, for example, alcohols, such as methanol and ethanol, ethers, such as tetrahydrofuran, diethylene glycol dimethyl ether, and diethylene glycol diethyl ether, propylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether And propylene glycol alkyl ether acetates such as acetate and propylene glycol butyl ether acetate. Among these solvents, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol methyl ether acetate are preferably used in view of solubility, reactivity with each component, and convenience of coating film formation.                     

Moreover, it is also possible to use a high boiling point solvent together with the said solvent. As a high boiling point solvent which can be used together, it is N-methyl formamide, N, N-dimethyl formamide, N-methyl acetamide, N, N-dimethyl acetamide, N-methyl pyrrolidone, dimethyl sulfoxide, for example. And benzyl ethyl ether.

[F] Other surfactants and adhesive aids

The photocurable composition of this invention may contain other components other than the said component as needed in the range which does not impair the objective of this invention.

Here, as another component, surfactant for improving applicability | paintability is mentioned. Surfactants include fluorine and silicone-based surfactants, for example, 3M's FC-129, FC-170C, FC-430, DIC's F-172, F-173, F-183, F-470, F -KP322, KP323, KP340, KP341 by Shin-Etsu Silicone, etc. are mentioned. Such surfactant is used in an amount of preferably 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the surfactant exceeds 5 parts by weight, bubbles are likely to occur during application.

Moreover, in order to improve adhesiveness with gas, it is also possible to use an adhesion | attachment adjuvant. As such an adhesion aid, a functional silane coupling agent is preferably used. For example, trimethoxysilyl benzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ -Isocyanate propyl triethoxysilane, (gamma)-glycidoxy propyl trimethoxysilane, etc. are mentioned. Such adhesion aid is used in an amount of preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the copolymer [A]. When the amount of the adhesion assistant exceeds 20 parts by weight, the heat resistance tends to be lowered.

The concentration in the composition solution is not particularly limited. The concentration of solids is preferably 10 to 60% by weight. More preferably, it is 15-40 weight%. The composition solution prepared as described above is used after filtration using a filter having a pore diameter of about 0.1 to 5 μm.

The following synthesis examples and examples further illustrate the present invention, but the present invention is not limited to the following examples.

Synthesis Example 1

5 parts by weight of 2,2'-azobis isobutyronitrile was dissolved in 200 parts by weight of propylene glycol methyl ether acetate in a reaction vessel equipped with a cooling tube and a stirrer. Subsequently, 20 parts by weight of styrene, 30 parts by weight of methacrylic acid, 40 parts by weight of glycidyl methacrylate, and 10 parts by weight of dicyclopentenyloxyethyl methacrylate were added thereto, followed by nitrogen substitution, followed by gentle stirring. The temperature of the solution was raised to 80 ° C. and maintained at this temperature for 4 hours to obtain a polymer solution including a copolymer. Solid content concentration of the obtained polymer solution was 33 weight%. This polymer is named [A-1].

In the mixing tank with agitator, alkali-soluble resin [A], polymerizable compound [B], epoxy oligomer including alkyleneoxy group [C], photoinitiator, silane coupling agent and thermal polymerization inhibitor, and surfactant Sequential addition was made to prepare a photocurable composition for a column spacer, followed by stirring at 25 ° C.

&Lt; Example 1 >

60 weight part (solid content) of obtained copolymer [A-1], 30 weight part of trimethyl propane trimethacrylates as a polymeric compound [B], and alpha, omega-bis (3-glycido methyl) poly as [C] 5 parts by weight of tetramethylene glycol (n = 10) (4.95% by weight), 5 parts by weight of Igacure 907 and 1 part by weight of fluorine-based surfactant as a photopolymerization initiator [D] were dissolved in propylene glycol methyl ether acetate, and then the solid concentration Was 30% by weight. Then, it filtered by the filter of 0.45 micrometers of pore diameters, and prepared the photocurable resin composition solution (S-1).

<Examples 2-4>

The photocurable composition for the column spacer was prepared in the same manner as in Table 1, except that the content and type of the [C] alkyleneoxy group-containing epoxy oligomer were changed.

Alkali-soluble resin
[A] Polymerizable Compound [B] Epoxy oligomers containing alkyleneoxy group [C] Photoinitiator Other additives Example 1
[A-1]
60 parts by weight
DPHA
30 parts by weight
Alpha, Omega-Bis (3-Glycidomethyl) polytetramethylene glycol (n = 10)
5 parts by weight (4.95% by weight) Igacure
907 5
Parts by weight
1 part by weight of fluorine-based surfactant
Example 2
[A-1]
60 parts by weight
DPHA
30 parts by weight
Alpha, Omega-Bis (3-Glycidomethyl) polytetramethylene glycol (n = 10)
10 parts by weight (9.43% by weight) Igacure
907 5
Parts by weight
1 part by weight of fluorine-based surfactant
Example 3
[A-1]
60 parts by weight
DPHA
30 parts by weight
Alpha, Omega-Bis (3-Glycidomethyl) polytetramethylene glycol (n = 10)
20 parts by weight (17.2% by weight) Igacure
907 5
Parts by weight
1 part by weight of fluorine-based surfactant
Example 4
[A-1]
60 parts by weight
DPHA
30 parts by weight
Alpha, omega-bis (3-glycidomethyl) polypropylene glycol (n = 10)
10 parts by weight (9.43% by weight) Igacure
907 5
Parts by weight
1 part by weight of fluorine-based surfactant

<Comparative Examples 1 and 2>

As shown in Table 1 below, Comparative Example 1 did not include the [C] alkyleneoxy group-containing epoxy oligomer, Comparative Example Example 2 [C] alkyleneoxy group-containing epoxy oligomer content more than 20% by weight 23.8 weight A photocurable composition for a column spacer was prepared in the same manner as the composition and content of Example 1, except for including%.

Alkali-soluble resin
[A] Polymerizable Compound [B] Epoxy oligomers containing alkyleneoxy group [C] Photoinitiator Other additives compare
Example
One [A-1]
60 parts by weight DPHA
30 parts by weight - Igacure
907 5
Parts by weight 1 part by weight of fluorine-based surfactant compare
Example
2 [A-1]
60 parts by weight DPHA
30 parts by weight Alpha, Omega-Bis (3-Glycidomethyl)
Polytetramethylene glycol (n = 10)
30 parts by weight (23.8% by weight) Igacure
907 5
Parts by weight 1 part by weight of fluorine-based surfactant

<Formation of column spacer>

Using a spin coater, the glass film was coated on the glass substrate such that the final film thickness of the photosensitive resin composition was 3 μm. After drying at 80 ° C. for 2 minutes, ultraviolet rays of 365 nm were irradiated with 150 mJ / cm ² in a state where a mask of a predetermined form was placed on the obtained coating film. The aqueous solution was used as a developer to dissolve and remove unnecessary portions, leaving only the exposed portions to form a pattern, which was then baked at 220 ° C. for 30 minutes in a clean oven to form a protective film on the glass substrate.

<Evaluation Method>

Evaluation methods for the aforementioned examples and comparative examples are as follows.

(1) adhesion

According to the checkered tape method, 100 checkers were formed on the protective film with a cutter knife, and the adhesion test was carried out to measure the number of peeled checkered patterns and to evaluate the adhesion of the protective film according to the following criteria.

Good: No more than 5 peeled checkerboard patterns

Shortage: 6 ~ 49 number of checkerboard

Poor: More than 50 peeled checkerboard

(2) pattern shape

After forming the pattern on the glass substrate on which ITO was spattered, cut it in the vertical direction of the lie pattern, and observe the cross-sectional direction of the pattern with an electron microscope. Mark as

(3) flatness

After the pattern of the composition was formed on the glass substrate on which the ITO was spattered, the difference between the maximum thickness and the minimum thickness was determined by using α step for the surface irregularities of the 25 coating layers, respectively.

Good: Below 400Å

Shortage: less than 1000Å

Poor: More than 1000Å

(4) heat resistance

The protective film was heated in a clean oven at 240 ° C. for 60 minutes, and the transmission spectrum was measured before and after heating, and the heat resistance of the protective film was evaluated according to the following criteria.

Good: Change in transmission spectrum is within 1%

Poor: Change of transmission spectrum is over 1%

(5) Compression displacement and recovery rate                     

In the present invention, a dot pattern having a thickness (T) of 3 μm and a width (W) of 20 (± 2) μm formed from a photocurable composition is a basic condition for measuring mechanical properties of the pattern, that is, compression displacement and elastic recovery rate. It was set as the shape of. SHIMADZU's ultra-compact hardness tester (model name: DHU-W201S) was used for measuring the compression displacement and elastic recovery rate. A flat indenter with a diameter of 50㎛ was used as the indenter for pressing the pattern. The measurement principle was carried out by a load-unload method. The test loading standard was 5gf / ㎠, the load speed was 0.45 gf / sec, and the maintenance time ( holding time) was constant at 2 seconds.

Hereinafter, the compression displacement and the recovery rate of the column spacer formed of the photosensitive resin of the present invention will be described with reference to FIG. 1.

The spacer 20 formed by the pattern process has a constant thickness T (state S ₀ ). Although only one spacer 20 is shown in FIG. 2, the thickness T of each spacer 20 formed on the substrate has a certain range of variation.

When another substrate, such as an array substrate, is bonded to the spacer, the thickness of the spacer is reduced by pressing (state S ₁ ). At this time, the compression displacement refers to the length (D ₁ ) in which the pattern enters when a given force is applied as shown in FIG. In addition, when the pressing force F is removed, the thickness of the spacer is increased by the restoring force (state S ₂ ). At this time, the difference between the thickness of the spacer and the initial thickness of the non-compressed spacer is indicated by D ₂ .

Recovery rates can be expressed in two ways.

First, as shown in FIG. 1, the ratio of the recovered distance (D ₁ -D ₂ ) to the length (D ₁ ) entered when given a constant force (recovery rate A).

Second, the ratio of the pattern height (T-D2) after the final deformation to the height (T) of the original pattern can mean (recovery rate B).

This is summarized as follows.

Compression displacement = D ₁ (㎛)

Recovery rate

In the Example of this invention, it evaluates comparatively as said recovery rate A.

Evaluation properties of the Examples and Comparative Examples are shown in Table 3 below.

Adhesion Pattern shape flatness Heat resistance Compression displacement
(D ₁ ) (㎛) D ₂
(Μm) Recovery rate A (%) Example 1 Good Good Good Good 1.14 0.54 53% Example 2 Good Good Good Good 1.25 0.59 53% Example 3 Good Good Good Good 1.38 0.65 53% Example 4 Good Good Good Good 1.12 0.56 50% Comparative Example 1 Good Good Good Good 0.71 0.46 35% Comparative Example 2 Good usually Good usually 1.49 0.88 41%

As can be seen from the above results, it can be seen that the photocurable composition for a column spacer of the present invention is superior in compression displacement, adhesion, heat resistance, flatness, and pattern shape as compared with the conventional resist composition. It can be seen that the photosensitive composition of the present invention can prevent excessive erosion of the pattern as it secures uniform physical properties to the thickness, that is, increases the compression displacement and improves the recovery rate, and can easily control the thickness by compression. have.

Claims (4)

In the photocurable composition for column spacers containing [A] alkali-soluble resin, the polymeric compound which has [B] ethylenically unsaturated bond, and the [D] photoinitiator, [C] 0.1 to 20% by weight of an epoxy oligomer containing an alkyleneoxy group based on the total composition, the photocurable composition for a column spacer. According to claim 1, wherein the epoxy oligomer containing the alkyleneoxy group Photocurable composition for a liquid crystal display device column spacer comprising any one or more of the compounds represented by the formula (1) <Formula 1>

According to claim 1, wherein the epoxy oligomer containing an alkyleneoxy group Alpha, omega-bis (3-glycidomethyl) polytetramethylene glycol, alpha, omega-bis (3-glycidomethyl) polypropylene glycol, alpha, omega-bis (3-glycidomethyl) polyethylene Photocurable composition for a liquid crystal display device column spacer comprising at least one of glycol, alpha, omega-bis (3-glycidomethyl) polymethylene glycol The method of claim 1 wherein the alkali-soluble resin (a1) Unsaturated carboxylic acid and / or unsaturated carboxylic acid, (a2) Epoxy-group-containing unsaturated compound, (a3) The photocurable composition for column spacers characterized by radical polymerization of olefinic unsaturated compounds other than said a1 and a2.

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