KR20120057677A - Photosensitive resin composition for spacer, spacer using the same and liquid crystal display device including the spacer - Google Patents

Abstract

PURPOSE: A photo-sensitive resin composition, a spacer for a liquid display device manufactured by the same, and the liquid display device including the same are provided to prevent the exfoliation of patterns during a developing process. CONSTITUTION: A photo-sensitive resin composition includes an alkali soluble resin, a photo-polymerizable compound, a photo-polymerization initiator, and a solvent. The alkali soluble resin includes a structural unit represented by chemical formula 1. In chemical formula 1, R2 is R3 which is represented by chemical formula 2, -R1-R3, or chemical formula 3; and R1 is -CH_2, ethylene, (iso)propylene, butylenes, (poly)ethyleneglycol, or (poly)propyleneglycol. In chemical formula 2, R4 is -CH_2, ethylene, (iso)propylene, butylene, (poly)ethylene glycol, or (poly)propylene glycol; and R5 is hydrogen or methyl. In chemical formula 3, R3 is represented by chemical formula 2; R6 is -CH_2, ethylene, (iso)propylene, butylene, (poly)ethylene glycol, or (poly)propylene glycol; R7 is hydrogen, methyl, ethyl, propyl, butyl, or -R1-R3; and R1 is -CH_2, ethylene, (iso)propylene, butylene, (poly)ethylene glycol, or (poly)propylene glycol.

Description

Photosensitive resin composition, a spacer for a liquid crystal display device manufactured using the same, and a liquid crystal display device including the same {PHOTOSENSITIVE RESIN COMPOSITION FOR SPACER, SPACER USING THE SAME AND LIQUID CRYSTAL DISPLAY DEVICE INCLUDING THE SPACER}

The present invention relates to a photosensitive resin composition, a spacer for a liquid crystal display device manufactured using the same, and a liquid crystal display device including the same.

Conventional liquid crystal display devices have used silica beads or plastic beads having a constant diameter in order to maintain a constant distance between the upper and lower substrates. However, when such beads are randomly dispersed on the substrate and positioned inside the pixel, the aperture ratio is lowered and light leakage occurs. In order to solve these problems, liquid crystal display devices have started to use spacers formed by photolithography therein, and most of the spacers used in liquid crystal display devices are formed by photolithography.

The method of forming a spacer by photolithography is to apply a photosensitive resin composition on a substrate, irradiate ultraviolet rays through a mask, and then form the spacer at a desired position on the substrate according to a pattern formed on the mask through a developing process. In recent years, research has been continuously conducted to shorten the process time in order to improve the productivity and reduce the cost of liquid crystal display devices, and research for shortening the irradiation time or shortening the development time of the photolithography process for forming spacers is continued. It is becoming.

However, in the conventional photosensitive resin composition, when the spacer pattern is formed by using a low exposure amount light irradiation process in which the irradiation time is shortened, the sensitivity is low, so that crosslinking by light irradiation is not sufficient. The resulting pattern may be poor in thermal stability, or may be defective in peeling off part of the pattern during development. In addition, after the formation of the spacer, the size of the pattern becomes smaller than the required value, so that the desired pattern size is not obtained, which causes a problem of defects.

An object of the present invention is to provide a photosensitive resin composition having excellent sensitivity and adhesion to light when forming a spacer for a liquid crystal display device, no peeling of a pattern during a developing step, and excellent solvent resistance.

Moreover, another object of this invention is to provide the spacer for liquid crystal display elements excellent in adhesiveness with a board | substrate.

Another object of the present invention is to provide a high quality liquid crystal display device.

In order to achieve the above object, the photosensitive resin composition according to the present invention contains an alkali-soluble resin (A), a photopolymerizable compound (B), a photopolymerization initiator (C) and a solvent (D), and the alkali-soluble resin (A). Is characterized in that it comprises a structural unit represented by the formula (1).

<Formula 1>

(In Formula 1, R ₂ is represented by R ₃ , -R ₁ -R ₃ or represented by the following formula (3), R ₁ is -CH _2- , ethylene, (iso) propylene, butylene , (Poly) ethylene glycol or (poly) propylene glycol.)

<Formula 2>

(In Formula 2, R ₄ is -CH _2- , ethylene, (iso) propylene, butylene, (poly) ethylene glycol or (poly) propylene glycol, R ₅ is hydrogen or methyl.)

<Formula 3>

(In Formula 3, R ₃ is represented by Formula 2, R ₆ is -CH _2- , ethylene, (iso) propylene, butylene, (poly) ethylene glycol or (poly) propylene glycol, R ₇ is Hydrogen, methyl, ethyl, propyl, butyl or -R ₁ -R ₃ , and R ₁ is -CH _2- , ethylene, (iso) propylene, butylene, (poly) ethylene glycol or (poly) propylene glycol.)

Moreover, this invention provides the spacer for liquid crystal display elements formed by forming the said photosensitive resin composition in a predetermined pattern, and exposing and developing.

Moreover, this invention provides the liquid crystal display element provided with the said liquid crystal display element spacer.

By using the photosensitive resin composition which concerns on this invention mentioned above, the effect which becomes excellent in the sensitivity, adhesiveness, and solvent resistance of the spacer for liquid crystal display elements can be acquired.

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

The photosensitive resin composition which concerns on this invention contains alkali-soluble resin (A), a photopolymerizable compound (B), a photoinitiator (C), and a solvent (D).

Alkali-soluble resin (A)

The alkali-soluble resin (A) comprises a structural unit represented by the following formula (1).

<Formula 1>

(In Formula 1, R ₂ is represented by R ₃ , -R ₁ -R ₃ or represented by the following formula (3), R ₁ is -CH _2- , ethylene, (iso) propylene, butylene , (Poly) ethylene glycol or (poly) propylene glycol.)

<Formula 2>

(In Formula 2, R ₄ is -CH _2- , ethylene, (iso) propylene, butylene, (poly) ethylene glycol or (poly) propylene glycol, R ₅ is hydrogen or methyl.)

<Formula 3>

(In Formula 3, R ₃ is represented by Formula 2, R ₆ is -CH _2- , ethylene, (iso) propylene, butylene, (poly) ethylene glycol or (poly) propylene glycol, R ₇ is Hydrogen, methyl, ethyl, propyl, butyl or -R ₁ -R ₃ , and R ₁ is -CH _2- , ethylene, (iso) propylene, butylene, (poly) ethylene glycol or (poly) propylene glycol.)

In the alkali-soluble resin (A), the structural unit represented by the formula (1) is preferably contained in a mole fraction of 3 to 80 mol%, more preferably 5 to 70 mol%. When the structural unit represented by Chemical Formula 1 is included in the above range, the photosensitive resin composition is excellent in sensitivity and adhesiveness, and thus there is no peeling of the pattern during the developing process, and exhibits excellent solvent resistance.

Alkali-soluble resin having a structural unit represented by the formula (1) can be prepared by polymerization of various polymerizable compounds. Preferably, the polymer may be a polymer obtained by further reacting an isocyanate compound (a2) having an unsaturated bond with a copolymer of monomers including the compound (a1) having an unsaturated bond and a hydroxyl group.

The compound (a1) having an unsaturated bond and a hydroxy group may be selected from a vinyl ether compound or an allyl ether compound having at least one hydroxy group in a molecule, and more specifically, 2-allyloxyethanol and 3-allyloxy-1. And 2-propanediol, 1,4-butanediol vinyl ether, ethylene glycol monovinyl ether, di (ethylene glycol) vinyl ether, and the like. Said (a1) can be used individually or in combination of 2 or more types.

Among the monomers used to prepare a copolymer of monomers including (a1), other monomers than (a1) may include monomers (a3) having a carboxyl group and unsaturated bonds, and monomers (a4) polymerizable with (a1). ) And the like, but are not necessarily limited thereto.

Specific examples of the polymerization monomer (a3) having the carboxyl group and an unsaturated bond include unsaturated monocarboxylic acids such as (meth) acrylic acid and crotonic acid, and examples thereof include maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid. Unsaturated dicarboxylic acids and anhydrides of these unsaturated dicarboxylic acids. The polymerization monomers exemplified in the above (a3) may be used alone or in combination of two or more thereof.

Specific examples of the polymerization monomer (a4) having an unsaturated bond copolymerizable with (a1) include styrene, vinyltoluene, α-methylstyrene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, and p- Methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl Aromatic vinyl compounds such as ethers; Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; Cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 ^2,6 ] decane-8-yl (meth) acrylate, 2- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; Aryl (meth) acrylates such as phenyl (meth) acrylate and benzyl (meth) acrylate; Hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; N-cyclohexylmaleimide, N-benzylmaleimide, N-phenylmaleimide, N-phenylmaleimide, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No N-substituted maleimide compounds such as -methylphenylmaleimide, Nm-methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide; Unsaturated amide compounds such as (meth) acrylamide and N, N-dimethyl (meth) acrylamide; 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) -3-ethyloxetane, 3- (methacryloyloxymethyl) -2-trifluoromethyloxetane, 3- (methacryloyloxymethyl) -2-phenyloxetane, 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, etc. And unsaturated oxetane compounds. The monomers illustrated by said (a4) can be used individually or in combination of 2 types or more, respectively.

(Meth) acryloyloxyethyl isocyanate etc. are mentioned as a specific example of the isocyanate compound (a2) which has an unsaturated bond further reacted with the copolymer of the monomer containing said (a1).

The method for producing a copolymer of monomers including the above (a1) is not particularly limited, and various known polymerization methods can be used, and a solution polymerization method is more preferable among known polymerization methods. The polymerization temperature and the polymerization time vary depending on the type and ratio of the monomer to be introduced, the target binder resin molecular weight and the acid value, but are preferably polymerized at 60 ° C to 130 ° C for 1 to 10 hours.

According to the present invention, the alkali-soluble resin (A) preferably has a weight average molecular weight in terms of polystyrene in the range of 3,000 to 100,000, more preferably in the range of 5,000 to 50,000. When the weight average molecular weight of the said alkali-soluble resin (A) exists in the range of 3,000-100,000, since film reduction is prevented at the time of image development, the omission property of a pattern part becomes favorable, and it is preferable.

The acid value of the said alkali-soluble resin (A) is 50-150 (KOHmg / g), Preferably it is 60-140 (KOHmg / g), More preferably, it is 80-135 (KOHmg / g), Most preferably 80 to 130 (KOH mg / g). When the acid value of the said alkali-soluble resin (A) is 50-150 (KOHmg / g), since the solubility to a developing solution improves and a residual film rate improves, it is preferable. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be determined by titration using an aqueous potassium hydroxide solution.

Content of the said alkali-soluble resin (A) is 5-85 weight% with respect to solid content in the photosensitive resin composition, Preferably it is the range of 10-70 weight%. When the content of the alkali-soluble resin (A) is 5 to 85% by weight based on the above criteria, the solubility in the developing solution is sufficient, so that pattern formation is easy. It is preferable because omission becomes good.

Photopolymerization  Compound (B)

Although the said photopolymerizable compound (B) is a compound which can superpose | polymerize by the action of the photoinitiator mentioned later, it will not specifically limit, Preferably it is a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, or trifunctional or more than polyfunctional photopolymerizable. Compounds and the like.

Specific examples of the monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-vinyl py. And commercially available products include Aronix M-101 (Toagosei), KAYARAD TC-110S (Nipbon Kayaku), and Biscotti 158 (Osaka Yuki Kagaku High School).

Specific examples of the bifunctional monomers include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like; commercially available products such as Aronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA Nippon Kayaku, Biscot 260 (Osaka Yuki Kagaku High School), AH-600, AT-600, and UA-306H (Kyoeisha Kagakusa).

Specific examples of the trifunctional or higher polyfunctional photopolymerizable compound include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, and propoxylated trimethylolpropane tri (meth) acryl. Latex, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, tipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (meth) acrylate, propoxyl Graded dipentaerythritol hexa (meth) acrylate and dipentaerythritol hexa (meth) acrylate are available, and commercially available products include Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA, KAYARAD DPHA-40H (Nippon Kayaku).

Among the photopolymerizable compounds (B) exemplified above, trifunctional or more than trifunctional (meth) acrylic acid esters and urethane (meth) acrylates are particularly preferable in terms of excellent polymerizability and improving strength.

The photopolymerizable compound (B) illustrated above can be used individually or in combination of 2 types or more, respectively.

The content of the photopolymerizable compound (B) is usually used in the range of 5 to 50% by weight, preferably 10 to 40% by weight with respect to the solid content in the photosensitive resin composition. When the photopolymerizable compound (B) is in the range of 5 to 50% by weight based on the above criteria, the strength and smoothness of the spacer pattern become good, which is preferable.

Light curing Initiator (C)

The photopolymerization initiator (C) can be used without particular limitation as long as it can polymerize the photopolymerizable compound (B). In particular, the group consisting of acetophenone-based compounds, benzophenone-based compounds, triazine-based compounds, biimidazole-based compounds, oxime compounds, and thioxanthone-based compounds in terms of polymerization properties, starting efficiency, absorption wavelength, availability, and price. Preference is given to using at least one compound selected from.

Specific examples of the acetophenone compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Ethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2 Benzyl-2-dimethyla

Mino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one, 2- (4 -Methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, etc. are mentioned.

As a benzophenone type compound, for example, benzophenone, methyl 0- benzoyl benzoate, 4-phenyl benzophenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3, 3 ', 4, 4'- tetra (tert) -Butyl peroxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 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-triazine, 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine, etc. are mentioned.

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

Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and OXE01 and OXE02 manufactured by BASF Corporation are typical examples of commercial products.

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

Moreover, as long as it does not impair the effect of this invention, another photoinitiator etc. can also be used together. As another photoinitiator, a benzoin type compound, an anthracene type compound, etc. are mentioned, for example, These can be used individually or in combination of 2 or more types, respectively.

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

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. .

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.

You may use combining a photoinitiator (C-1) with a photoinitiator (C). When using a photoinitiator adjuvant (C-1) together with a photoinitiator (C), since the photosensitive resin composition containing these becomes more sensitive and improves productivity, it is preferable.

As the photopolymerization start adjuvant (C-1), for example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds and organic sulfur compounds having thiol groups can be preferably used.

Specific examples of the amine compound include aliphatic amine compounds such as triethanolamine, methyldiethanolamine and triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-amylaminobenzoic acid isoamyl and 4-dimethylamino 2-ethylhexyl benzoic acid, 2-dimethylaminoethyl benzoic acid, N, N-dimethyl paratoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone), 4,4'-bis (diethyl Aromatic amine compounds, such as amino) benzophenone, are mentioned. As an amine compound, an aromatic amine compound is used preferably.

Specific examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid and dichloro And aromatic heteroacetic acids such as phenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

Specific examples of the organic sulfur compound having the thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropanetris (3-mergaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl Late), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. are mentioned. Can be.

The amount of the photopolymerization initiator (C) used is 0.1 to 40% by weight, preferably 1 to 30% by weight, based on the solid content, based on the total amount of the alkali-soluble resin (A) and the photopolymerizable compound (B), and photopolymerization. The usage-amount of a starting adjuvant (C-1) is 0.1-50 weight% normally on the said reference | standard, Preferably it is 1-40 weight%. When the usage-amount of a photoinitiator (C) exists in the said range, since the photosensitive resin composition becomes highly sensitive and the intensity | strength and the smoothness on the surface of the spacer formed using this composition become favorable, it is preferable. Moreover, since the sensitivity of the photosensitive resin composition becomes high and the productivity of the spacer formed using this composition improves, when the usage-amount of a photoinitiator adjuvant (C-1) exists in the said range, it is preferable.

Solvent (D)

The solvent (D) contained in the photosensitive resin composition of this invention is not specifically limited, Various organic solvents used in the field of the photosensitive resin composition can be used.

Specific examples of the solvent (D) 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 glycol di. Diethylene glycol dialkyl ethers such as ethyl 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 monomethyl Alkylene glycol alkyl ether acetates such as ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, 3-methoxy-1-butyl acetate and methoxypentyl acetate, benzene, toluene, xylene, mesitylene, etc. Aromatic hydrocarbons, Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin, 3-methoxybutanol, Esters such as ethyl 3-ethoxypropionate and methyl 3-methoxypropionate, and cyclic esters such as γ-butyrolactone.

Among the solvents described above, organic solvents having a boiling point of from 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 methyl 3-methoxy propionate, is mentioned, More preferably, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, 3-ethoxy propionate, 3-methoxy Methyl oxypropionate, 3-methoxy-1- butyl acetate, 3-methoxy butanol, etc. are mentioned.

The solvent (D) mentioned above can be used individually or in mixture of 2 or more types, respectively.

The content of the solvent (D) in the photosensitive resin composition of the present invention is usually 60 to 90% by weight, preferably 70 to 85% by weight, based on the total amount of the photosensitive resin composition including the same. When the content of the solvent (D) is in the range of 60 to 90% by weight based on the above criteria, it is applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater), inkjet, or the like. Since applicability | paintability becomes favorable at the time, it is preferable.

Additive (E)

The photosensitive resin composition of this invention can also add additives (E), such as a filler, another high molecular compound, a hardening | curing agent, surfactant, an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, as needed.

Specific examples of the filler include glass, silica, alumina and the like.

Specific examples of the other high molecular compound include curable 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.

The curing agent is used to increase the core hardening and mechanical strength, and specific examples of the curing agent include epoxy compounds, polyfunctional isocyanate compounds, melamine compounds, oxetane compounds and the like.

Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, noblock type epoxy resin, other aromatic epoxy resin, 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 their brominated derivatives, butadiene (co) polymer epoxides, isoprene A polymer epoxide, glycidyl (meth) acrylate (co) polymer, a triglycidyl isocyanurate, etc. are mentioned.

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 epoxy resin hardening | curing agent, a brand name (Adekahadona EH-700) (made by Adeka Industrial Co., Ltd.), a brand name (Rikaditdo HH) (made by Nippon Ewha Co., Ltd.), a brand name (MH-700) ( New Nippon Ewha Co., Ltd.) etc. are mentioned. The hardeners illustrated above can be used individually or in mixture of 2 or more types.

The surfactant may be used to further improve the film formability of the photosensitive resin composition, and there are usually fluorine-based surfactants and silicone-based surfactants.

Commercially available silicone-based surfactants include DC3PA, DC7PA, SH11PA, SH21PA, SH8400, etc. of Dow Corning Toray Silicone Co., Ltd. And commercially available products of the fluorine-based surfactants include Megapieces F-470, F-471, F-475, F-482, and F-489 manufactured by Dainippon Ink & Chemicals. Surfactant illustrated above can be used individually or in combination of 2 types or more, respectively.

Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (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-mercaptopropyltrimeth And oxysilane, 3-isocyanatepropyltrimethoxysilane, and 3-isocyanatepropyltriethoxysilane.

The adhesion promoter exemplified above can be used individually or in combination of 2 or more types, respectively.

The adhesion promoter usually contains 0.01 to 10% by weight, preferably 0.05 to 2% by weight, based on the weight of solids of the photosensitive resin composition.

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

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

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

The photosensitive resin composition of this invention adds and mixes alkali-soluble resin (A), a photopolymerizable compound (B), a photoinitiator (C), and other additives used as needed to a solvent (D), for example. It can be prepared by. However, the present invention does not limit this method.

The present invention provides a liquid crystal display device spacer having the same and a liquid crystal display device spacer formed by exposing and developing the photosensitive resin composition according to the present invention in a predetermined pattern. Since the spacer and the liquid crystal display device can be easily formed by applying a known technology, a detailed description thereof will be omitted.

As follows, the present invention will be described in more detail based on Examples. However, 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 changes within the meaning and range equivalent to the scope of the claims.

Synthesis of Alkali-Soluble Resin (A)

&Lt; Synthesis Example 1 &

120 parts by weight of propylene glycol monomethyl ether acetate, 80 parts by weight of propylene glycol monomethyl ether, 2 parts by weight of azobisisobutyronitrile (AIBN) in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. 13 parts by weight of acrylic acid, 10 parts by weight of benzyl methacrylate, 65.2 parts by weight of vinyltoluene, 5.1 parts by weight of 2-allyloxyethanol, and 3 parts by weight of n-dodecyl mercapto were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 110 ° C and reacted for 8 hours.

Subsequently, after lowering the temperature of the reaction solution to room temperature and replacing the flask atmosphere with nitrogen from air, 0.2 parts by weight of methylhydroquinone and 6.7 parts by weight of methacryloyloxyethyl isocyanate were added and the flask temperature was raised to 70 ° C for 10 hours. Proceeded. The solid acid value of the alkali-soluble resin thus synthesized was 116 mgKOH / g and the weight average molecular weight measured by GPC was about 9800.

&Lt; Synthesis Example 2 &

Synthesis was carried out in the same manner as in Synthesis Example 1 except that 2-allyloxyethanol was changed to 3-allyloxy-1,2-propanediol, and the solid acid value of the synthesized alkali-soluble resin was 121 mgKOH / g. And the weight average molecular weight measured by GPC was about 12500.

&Lt; Synthesis Example 3 &

Synthesis was carried out in the same manner as in Synthesis Example 1 except that 2-allyloxyethanol was changed to 1,4-butanediol vinyl ether, and the solid acid value of the synthesized alkali-soluble resin was 118 mgKOH / g and was obtained by GPC. The weight average molecular weight measured was about 11000.

Synthesis Example 4

108 parts of propylene glycol mono methyl ether acetate, 72 parts of propylene glycol mono methyl ether, 2 parts AIBN, 18 parts acrylic acid, 22 parts benzyl methacrylate, styrene in a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot and a nitrogen introduction tube. 40 parts, 10 parts of methyl methacrylate, and 3 parts of n-dodecyl mercapto were added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 110 ° C. and reacted for 3 hours. The solid acid value of the alkali-soluble resin thus synthesized was 147 mgKOH / g and the weight average molecular weight Mw measured by GPC was about 21200.

Synthesis Example 5

120 parts of propylene glycol mono methyl ether acetate, 80 parts of propylene glycol mono methyl ether, 2 parts AIBN, 18 parts acrylic acid, 82 parts benzyl methacrylate, n -3 parts of dodecyl mercapto was added and nitrogen-substituted. After stirring, the temperature of the reaction solution was raised to 110 ° C. and reacted for 3 hours. The solid acid value of the alkali-soluble resin thus synthesized was 120 mgKOH / g, and the weight average molecular weight Mw measured by GPC was about 22100.

<Examples 1-3 and Comparative Examples 1-2>: Preparation of the photosensitive resin composition

&Lt; Example 1 >

41.90 parts of resin of Synthesis Example 1, 13.95 parts of KAYARAD DPHA (manufactured by Nippon Kayaku), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one (Irgacure 369; BASF Corporation 0.56 parts, 2,2 ', 4-tris (2-chlorophenyl) -5- (3,4-dimethoxyphenyl) -4', 5'-diphenyl-1,1'-biimidazole ( 0.56 parts of 4,4'-bis (diethylamino) benzophenone (EAB-F; the product made by Hodogaya Kagaku Co., Ltd.), 0.56 parts of trimethylol propane tris (3-mercaptopropionate) (TMMP Sakai Chemical Co., Ltd.) 0.28 parts, 3-glycidoxy propyltrimethoxysilane (KBM-403; Shin-Etsu Silicone) 0.14 parts, diethylene glycol methyl ethyl ether 28.05 parts, propylene glycol monomethyl ether acetate, a photosensitive mixture A resin composition was prepared.

<Example 2>

The photosensitive resin composition was produced similarly except having changed the resin of Example 1 into the resin of the synthesis example 2.

<Example 3>

Except having changed the resin of Example 1 into the resin of the synthesis example 3, the photosensitive resin composition was produced similarly.

Comparative Example 1

Except having changed the resin of Example 1 into the resin of the synthesis example 4, the photosensitive resin composition was produced similarly.

Comparative Example 2

The photosensitive resin composition was produced similarly except having changed the resin of <Example 1> into the resin of <Synthesis example 5>.

<Experimental Example>

The physical properties of the photosensitive resin compositions of Examples 1 to 3 and Comparative Examples 1 and 2 were measured by the following methods, and the results are shown in Table 1 below.

(1) Development speed evaluation

After coating the composition solution on a glass substrate, it was pretreated by baking for 3 minutes on a hot plate at 90 ° C. Ultraviolet was irradiated at a micrometer. At this time, the ultraviolet light source was irradiated at 100mJ / cm 2 using a 1kw high-pressure mercury lamp containing all g, h, and i rays, and no special optical filter was used. The development was carried out by changing the development time of the thin film irradiated with ultraviolet rays with a KOH aqueous solution development solution of pH10.5. The development speed was defined as the minimum development time possible for pattern formation and no residue in the unexposed areas.

(2) adhesion evaluation

The pattern formation was carried out in the same manner as in (1) except that the exposure amount was 40mJ / cm 2, and if the pattern could be formed without tearing the circular pattern of 10 μm in diameter, the adhesiveness was evaluated as good (○). It evaluated as bad.

(3) sensitivity evaluation

The same procedure as in (1) was carried out except that a pattern mask was used in which the transmittance was changed in a step shape in the range of 1 to 100%. Indicated by sensitivity.

 (4) elastic recovery rate measurement

The substrate subjected to the exposure process in the same manner as in (1) was developed for 60 seconds with a KOH aqueous solution developing solution of pH10.5, and then washed for 60 seconds with distilled water. The cleaned substrate was baked in an oven at 220 ° C. for 60 minutes to form a spacer pattern. Then, using a microhardness tester (FISC HERSCOPE H100 manufactured by Fischer Installation Co., Ltd.), the maximum and final displacement were measured under the following conditions, and then calculated by Equation 1 to measure the elastic recovery rate.

Measurement condition: Using a planar indenter with a temperature of 23 ° C. and a diameter of 50 μm, the spacer was loaded at a constant speed (2 mN / sec), held at the point where the maximum load of 80 (mN) was reached for 5 seconds, and then loaded at the same speed. Measure the maximum displacement and final displacement by removing it.

[Equation 1]

Elastic recovery rate R (%) = (maximum displacement-final displacement) / maximum displacement x 100

　 Example Comparative example One 2 3 One 2 Developing speed (s) 32 45 40 67 54 Sensitivity (mJ / cm2) 30 30 30 60 60 Adhesion O O O O X Elasticity Restoration Rate (%) 88 91 86 73 74

As shown in Table 1, in the case of the composition examples 1 to 3 according to the present invention, it can be confirmed that the development speed is very excellent as compared to the comparative examples 1 to 2, and it can be confirmed that the elastic recovery rate and adhesion are also good.

Claims (12)

In the photosensitive resin composition containing alkali-soluble resin (A), a photopolymerizable compound (B), a photoinitiator (C), and a solvent (D),
Said alkali-soluble resin (A) contains the structural unit represented by following formula (1), The photosensitive resin composition characterized by the above-mentioned.
<Formula 1>

(In Formula 1, R ₂ is represented by R ₃ , -R ₁ -R ₃ or represented by the following formula (3), R ₁ is -CH _2- , ethylene, (iso) propylene, butylene , (Poly) ethylene glycol or (poly) propylene glycol.)
<Formula 2>

(In Formula 2, R ₄ is -CH _2- , ethylene, (iso) propylene, butylene, (poly) ethylene glycol or (poly) propylene glycol, R ₅ is hydrogen or methyl.)
<Formula 3>

(In Formula 3, R ₃ is represented by Formula 2, R ₆ is -CH _2- , ethylene, (iso) propylene, butylene, (poly) ethylene glycol or (poly) propylene glycol, R ₇ is Hydrogen, methyl, ethyl, propyl, butyl or -R ₁ -R ₃ , and R ₁ is -CH _2- , ethylene, (iso) propylene, butylene, (poly) ethylene glycol or (poly) propylene glycol.) The photosensitive resin composition according to claim 1, wherein the structural unit represented by Chemical Formula 1 in the alkali-soluble resin (A) is contained in a molar fraction of 3 to 80 mol%. The polymer according to claim 1, wherein the alkali-soluble resin (A) further comprises a polymer obtained by further reacting an isocyanate compound (a2) having an unsaturated bond with a copolymer of monomers including the compound (a1) having an unsaturated bond and a hydroxyl group. The photosensitive resin composition characterized by the above-mentioned. The compound (a1) having a bond with a hydroxy group and a hydroxy group is at least one compound selected from the group consisting of a vinyl ether compound and an allyl ether compound having at least one hydroxy group in a molecule. Photosensitive resin composition. The compound (a1) according to claim 3, wherein the compound (a1) having a bond and a hydroxyl group is selected from the group consisting of a monomer (a3) having a carboxyl group and an unsaturated bond and a monomer (a4) polymerizable with the compound (a1). The photosensitive resin composition characterized by copolymerizing with a monomer of at least one species. The monomer (a3) according to claim 5, wherein the monomer (a3) having an unsaturated bond with a carboxyl group is at least one compound selected from the group consisting of unsaturated monocarboxylic acids, unsaturated dicarboxylic acids and anhydrides of unsaturated dicarboxylic acids. Photosensitive resin composition characterized by the above-mentioned. The monomer (a4) is an aromatic vinyl compound, alicyclic (meth) acrylates, aryl (meth) acrylates, N-substituted maleimide compounds, unsaturated amide compounds, and unsaturated oxetane compounds. At least one compound selected from the group consisting of the photosensitive resin composition characterized by the above-mentioned. The photosensitive resin composition according to claim 3, wherein the isocyanate compound (a2) is (meth) acryloyloxyethyl isocyanate. The said photoinitiator (D) is 1 type chosen from the group which consists of an acetophenone type compound, a benzophenone type compound, a triazine type compound, a biimidazole type compound, an oxime compound, and a thioxanthone type compound. It is the above compound, The photosensitive resin composition characterized by the above-mentioned. The photosensitive resin composition according to claim 1, wherein the photosensitive resin composition contains 5 to 85% by weight of the alkali-soluble resin (A) and 5 to 50% by weight of the photopolymerizable compound (B). The photosensitive resin composition of any one of Claims 1-10 was formed in a predetermined pattern, and then exposed and developed, The spacer for liquid crystal display elements characterized by the above-mentioned. The liquid crystal display element of Claim 11 is provided with the spacer for liquid crystal display elements.