KR20150011070A - A photosensitive resin composition for spacer and a spacer using the same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for forming a spacer comprising silicon acrylate, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent represented by the following formula (1) and a spacer made from the composition.
[Chemical Formula 1]

Description

TECHNICAL FIELD [0001] The present invention relates to a photosensitive resin composition for forming a spacer and a spacer using the same. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a photosensitive resin composition for a spacer comprising silicon acrylate and a spacer produced using the same.

In general, a spacer is used to uniformize the thickness of a liquid crystal layer of an LCD panel in a process of manufacturing a liquid crystal display (LCD), and is characterized in that the characteristics of a liquid crystal cell Since the response speed, contrast ratio, viewing angle, and luminance uniformity are closely related to the thickness of the liquid crystal layer, it is important to keep the cell gap constant. In the conventional liquid crystal display device technology, transparent spherical particles such as silica beads and plastic beads have been used as spacers in order to maintain an interval between the array substrate and the counter substrate. Korean Patent Publication No. 2007-0082973 discloses a photosensitive resin composition for forming a spacer containing silica particles into which a reactive functional group is introduced.

However, the prior art spacer has a problem that it is difficult to uniformly spread and uniformly maintain the spacing between the substrates while keeping the gap therebetween. Therefore, there is a need to develop a photosensitive resin composition for forming a spacer which uniformly spreads the spacer to form a spacer at a desired position at a constant height, and has improved mechanical properties and excellent elastic restoration.

Korea Patent Publication No. 2007-0082973

The present invention has been made to solve the above problems of the prior art, and it is an object of the present invention to provide a resin composition which is excellent in performances such as transmittance, insulation, chemical resistance, heat resistance, and sensitivity and has remarkably improved adhesion and high heat resistance, It is an object of the present invention to provide a photosensitive resin composition for forming a spacer.

In order to achieve the above object,

There is provided a photosensitive resin composition for forming a spacer, which comprises silicone acrylate, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent represented by the following formula (1).

[Chemical Formula 1]

In this formula,

R ₁ is independently hydrogen or an alkyl group having 1 to 5 carbon atoms,

R ₂ represents, independently of each other, an alkylene group having 2 to 20 carbon atoms containing an ester bond, 1 to 20 repeating units of an alkylene oxide group having 2 to 10 carbon atoms, an alkylene group having 1 to 20 carbon atoms, An arylene group or an epoxy group having 1 to 20 carbon atoms,

a and b are each independently an integer of 1 to 10,

Y may include a hetero atom as the aliphatic or aromatic hydrocarbon having 0 to 30 carbon atoms (excluding the number of carbon atoms of the (meth) acrylate group) and containing 1 to 10 (meth) acrylate groups reacting at the time of curing.

The present invention also provides a spacer made of the photosensitive resin composition for forming a spacer.

The photosensitive resin composition for forming a spacer of the present invention contains silicon acrylate represented by the formula (1) as an essential component, thereby reducing pixel strain due to the external pressure of the spacer. In addition, it has excellent transmittance, insulation, chemical resistance, heat resistance, sensitivity and adhesiveness, excellent elastic recovery ability, and can solve the problem of yellowing and viscosity increase.

Therefore, the photosensitive resin composition of the present invention can be more uniformly applied to the liquid crystal, thereby increasing the transparency and improving the stability.

The present invention

A photosensitive resin composition for forming a spacer containing silicon acrylate, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent, and may further comprise various additives commonly used in the art, if necessary.

Hereinafter, each component will be described in more detail.

1. Silicon Acrylate

The silicone acrylate of the present invention is represented by the following general formula (1).

[Chemical Formula 1]

In this formula,

R ₁ is independently hydrogen or an alkyl group having 1 to 5 carbon atoms,

R ₂ represents, independently of each other, an alkylene group having 2 to 20 carbon atoms containing an ester bond, 1 to 20 repeating units of an alkylene oxide group having 2 to 10 carbon atoms, an alkylene group having 1 to 20 carbon atoms, An arylene group or an epoxy group having 1 to 20 carbon atoms,

a and b are each independently an integer of 1 to 10,

Y may include a hetero atom as the aliphatic or aromatic hydrocarbon having 0 to 30 carbon atoms (excluding the number of carbon atoms of the (meth) acrylate group) and containing 1 to 10 (meth) acrylate groups reacting at the time of curing.

The silicone acrylate suppresses the penetration of the developer by R ₁ attached to the silicon main chain to suppress development unevenness, and improves the reactivity and adhesion by R ₂ . At the same time, the acrylate participates in the reaction by the initiator, so that the color separation phenomenon is suppressed and the reliability is excellent.

The silicone acrylate may be used without limitation as long as it has the structure of Formula 1. The amount of the silicone acrylate is preferably 0.1 to 20% by weight, more preferably 0.5 to 5% by weight based on the total amount of the photosensitive resin composition for forming a spacer. When the content of the silicone acrylate is less than 0.1% by weight, it is difficult to expect the occurrence of development unevenness and the adhesion improvement. If the content is more than 20% by weight, the viscosity of the composition is increased, There is a problem of bad sex.

2. Alkali-soluble resin

The alkali-soluble resin includes at least one structural unit selected from structural units represented by the following formulas (A-1) to (A-4).

[A-1]

[A-2]

[A-3]

[A-4]

In the alkali-soluble resin, the structural units of formulas (A-1) to (A-4) are preferably contained in an amount of 3 to 80 mol%, more preferably 5 to 70 mol%, based on the total molar amount of the alkali- . When the above-mentioned structural unit is contained within the above range, the photosensitive resin composition for forming a spacer exhibits excellent sensitivity and adhesion so that there is no peeling of the pattern during the development process and excellent solvent resistance.

The alkali-soluble resin comprising at least one of the structural units of the above formulas A-1 to A-4 may be prepared by polymerization of various polymerizable compounds.

The structural units of the formulas A-1 to A-4 of the alkali-soluble resin can be copolymerized with other types, and specific examples of the unsaturated bond capable of copolymerization include styrene, vinyltoluene,? -Methylstyrene, p- , o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m Aromatic vinyl compounds such as vinyl benzyl glycidyl ether and p-vinyl benzyl glycidyl ether; Propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, alkyl (meth) acrylates such as sec-butyl (meth) acrylate and t-butyl (meth) acrylate; (Meth) acrylate, cyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, tricyclo [5.2.1.0 2,6] decan- Alicyclic (meth) acrylates such as dicyclopentanyloxyethyl (meth) acrylate and isobornyl (meth) acrylate; 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, No-hydroxyphenylmaleimide, Nm-hydroxyphenylmaleimide, Np-hydroxyphenylmaleimide, No-methylphenylmaleimide, Nm N-substituted maleimide compounds such as methylphenylmaleimide, Np-methylphenylmaleimide, No-methoxyphenylmaleimide, Nm-methoxyphenylmaleimide and Np-methoxyphenylmaleimide; (meth) acrylamide, Unsaturated amide compounds such as N, N-dimethyl (meth) acrylamide; 3- (methacryloyloxymethyl) -2-trifluoromethyl oxetane, 3- (methacryloyloxymethyl) oxetane, 3- (methacryloyloxymethyl) 2- (methacryloyloxymethyl) oxetane, 2- (methacryloyloxymethyl) -4-trifluoromethyloxetane, and the like Unsaturated oxetane compounds, and the like.

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

The alkali-soluble resin according to the present invention can be used by further mixing various other alkali-soluble resins known in the art commonly used in the art.

Preferably, the alkali-soluble resin has a weight average molecular weight in terms of polystyrene of 3,000 to 100,000, more preferably 5,000 to 50,000. When the alkali-soluble resin has a weight-average molecular weight of less than 3,000, the resin has a too small molecular weight and a smooth surface. When the molecular weight is more than 100,000, the development speed is slow at the time of development and compared with the photopolymerizable compound Since the difference in molecular weight is very large, a phenomenon in which the boundary of the pattern is not smooth is observed.

The acid value of the alkali-soluble resin is 30 to 250 (KOH mg / g), preferably 50 to 200 (KOH mg / g), and more preferably 60 to 150 (KOH mg / g). When the acid value of the alkali-soluble resin is 30 to 250 (KOH mg / g), the solubility in a developing solution is improved and the residual film ratio is improved. When the acid value is 30 or less, it can be seen that development in alkaline developer does not proceed well. When the acid value is more than 250, it is difficult to use as an alkali-soluble resin for resists due to a decrease in other physical properties due to too many carboxyl groups.

Here, the acid value is a value measured as the amount (mg) of potassium hydroxide necessary for neutralizing 1 g of the acrylic polymer, and can be generally determined by titration using an aqueous solution of potassium hydroxide.

The alkali-soluble resin is in the range of 10 to 80% by weight, preferably 10 to 70% by weight, based on the total weight of the solid content in the photosensitive resin composition for forming a spacer of the present invention. When the content of the alkali-soluble resin is 10 to 80% by weight on the basis of the above-mentioned criteria, the solubility of the developer is sufficient and pattern formation is easy, and reduction of film in the pixel portion of the exposed portion is prevented during development, It is preferable.

3. Photopolymerization  compound

The photopolymerizable compound is not particularly limited as far as it is a compound capable of polymerizing under the action of a photopolymerization initiator described later, but preferably a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound or a trifunctional or higher functional polyfunctional photopolymerizable compound .

Specific examples of the monofunctional monomer include acrylate, methacrylate, nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl Acrylate, and N-vinyl pyrrolidone. Commercially available products include Aronix M-101 (Doagosei), KAYARAD TC-110S (Nippon Kayaku) or Biscoat 158 (Osaka Yuki Kagaku Kogyo) .

Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) (Acryloyloxyethyl) ether of bisphenol A and 3-methylpentanediol di (meth) acrylate. Commercially available products include Aronix M-210, M-1100, 1200 (Doagosei), KAYARAD HDDA (Nippon Kayaku), Viscoat 260 (Osaka Yuki Kagaku Kogyo), AH-600, AT-600 or UA-306H (Kyoeisha Chemical Co., Ltd.).

Specific examples of the polyfunctional photopolymerizable compound having three or more functional groups include trimethylolpropane tri (meth) acrylate, ethoxylated trimethylolpropane tri (meth) acrylate, propoxylated trimethylolpropane tri (meth) acrylate (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ethoxylated dipentaerythritol hexa (Meth) acrylate such as Aronix M-309, TO-1382 (Doagosei), KAYARAD TMPTA, KAYARAD DPHA or KAYARAD DPHA-40H (Nippon Kayaku).

Of the photopolymerizable compounds exemplified above, trifunctional or higher (meth) acrylate esters and urethane (meth) acrylates are particularly preferable because they have excellent polymerizability and can improve the strength.

The photopolymerizable compounds exemplified above may be used alone or in combination of two or more.

The photopolymerizable compound is preferably contained in an amount of 10 to 85% by weight, more preferably 20 to 70% by weight, based on the total weight of solid components in the photosensitive resin composition for forming a spacer of the present invention. When the photopolymerizable compound is contained in an amount of 10 to 85% by weight based on the above-mentioned criteria, the strength and smoothness of the pixel portion can be improved.

4. Light curing Initiator

The photopolymerization initiator can be used without particular limitation as long as it can polymerize the photopolymerizable compound.

In particular, the photopolymerization initiator is preferably selected from the group consisting of an acetophenone based compound, a benzophenone based compound, a triazine based compound, a nonimidazole based compound, an oxime compound, and a thioxanthone based compound from the viewpoints of polymerization characteristics, initiation efficiency, absorption wavelength, availability, It is preferable to use at least one compound selected from the group consisting of compounds. Further, ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime) (trade name Irgacure® Oxe02, BASF) have.

Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, 2-hydroxy- 1- [4- 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one, 2-methylcyclohexyl phenyl ketone, 2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1-one -On or 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one.

Examples of the benzophenone compound include benzophenone, methyl 0-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra tert-butylperoxycarbonyl) benzophenone or 2,4,6-trimethylbenzophenone.

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

Specific examples of the imidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbimidazole, 2,2'-bis (2,3- Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) , 2,2'-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) Imidazole compounds in which 4'5,5'-tetraphenyl-1,2'-biimidazole or phenyl groups at 4,4 ', 5,5' positions are substituted by carboalkoxy groups. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3- , 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- Is used.

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

Examples of the thioxanthone compound include 2-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone or 1-chloro-4-propanecioxanthone .

Further, other photopolymerization initiators and the like may be further used in combination within the range not impairing the effects of the present invention. Examples thereof include a benzoin compound and an anthracene compound. These compounds may be used alone or in combination of two or more.

Examples of the benzoin-based compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.

Examples of the anthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, have.

In addition, it is also possible to use 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10- phenanthrenequinone, camphorquinone, phenylclyoxyl An acid methyl or a titanocene compound can be used in combination as a photopolymerization initiator.

The photopolymerization initiator may further include a photopolymerization initiator to improve the sensitivity of the photosensitive resin composition for forming a spacer of the present invention. The photosensitivity resin composition for forming a spacer according to the present invention contains a photopolymerization initiation auxiliary agent, thereby further increasing the sensitivity and improving the productivity.

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

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

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

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

The photopolymerization initiator may be contained in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight based on the sum of the alkali-soluble resin and the photopolymerizable compound of the photosensitive resin composition for forming a spacer of the present invention. When the photopolymerization initiator is in the range of 0.1 to 40% by weight, the sensitivity of the photosensitive resin composition for forming a spacer is increased and the exposure time is shortened, which is preferable because productivity can be improved and high resolution can be maintained. Further, the strength of the pixel portion formed using the composition of the above-described conditions and the smoothness of the surface of the pixel portion can be improved.

When the photopolymerization initiator is further used, it is preferable to use the same content range as that of the photopolymerization initiator. When the photopolymerization initiator is used in the above-mentioned content, the sensitivity of the photosensitive resin composition for spacer formation becomes higher, The productivity of the color filter is improved.

5. Solvent

The solvent used in the photosensitive resin composition for forming a spacer is not particularly limited as long as it is effective in dissolving other components contained in the photosensitive resin composition for forming a spacer. In particular, the solvent can be selected from ethers, aromatic hydrocarbons, Alcohols, esters, amides and the like are preferable.

Specific examples of the solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, di Propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, Ethers such as propylene glycol dipropyl ether and dipropylene glycol dibutyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene, and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin; Methylcellosolve acetate, ethylcellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-methoxypropionate, methyl 3-methoxypropionate, Methoxybutyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate, Lactone, etc. And the like.

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

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

The solvent may contain 45 to 90% by weight, preferably 70 to 85% by weight, based on the total weight of the photosensitive resin composition for forming a spacer of the present invention. When the above-mentioned solvent is in the range of 45 to 90% by weight, when applied with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater (sometimes referred to as a die coater) Provides a resolution effect.

The present invention also provides a spacer made of the photosensitive resin composition for forming a spacer of the present invention.

The photosensitive resin composition is preferably a negative type in which the non-visible portion is developed. The negative photosensitive resin has very few portions that are unclearly removed at the time of development and can have excellent mechanical properties with very high photosensitivity. Thus, the negative photosensitive resin composition can minimize the defective rate, increase the processing efficiency and resolution, and can be easily applied to highly integrated and fine patterned electronic devices.

Hereinafter, the present invention will be described more specifically with reference to Examples. The following examples are illustrative of the present invention and are not intended to limit the scope of the present invention.

Manufacturing example

Manufacturing example  1: Preparation of an alkali-soluble resin containing a structural unit of the formula (A-1)

A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was prepared. On the other hand, 3,4-epoxytricyclodecan-8-yl (meth) 40 parts by weight of a mixture (50:50 mole ratio) of epoxy tricyclodecan-9-yl (meth) acrylate, 50 parts by weight of methyl methacrylate, 40 parts by weight of acrylic acid, 70 parts by weight of vinyltoluene, 4 parts by weight of 2-ethylhexanoate and 40 parts by weight of propylene glycol monomethyl ether acetate (PGMEA) were added and stirred to prepare a mixture. 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA And the mixture was stirred and prepared. Thereafter, 395 parts by weight of PGMEA was introduced into the flask, the atmosphere in the flask was changed to nitrogen in air, and the temperature of the flask was raised to 90 DEG C while stirring. Then, the monomer and the chain transfer agent were added dropwise from the dropping funnel. The temperature was elevated by 110 DEG C for 1 hour and maintained at that temperature for 5 hours to obtain a resin (A-1) having a solid acid value of 75 mgKOH / g. The weight average molecular weight measured by GPC in terms of polystyrene was 17,000 and the molecular weight distribution (Mw / Mn) was 2.3.

The weight average molecular weight (Mw) and the number average molecular weight (Mn) of the alkali-soluble resin were measured by the GPC method under the following conditions.

Apparatus: HLC-8120GPC (manufactured by TOSOH CORPORATION)

Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial connection)

Column temperature: 40 DEG C

Mobile phase solvent: tetrahydrofuran

Flow rate: 1.0 ml / min

Injection amount: 50 μl

Detector: RI

Measurement sample concentration: 0.6 mass% (solvent = tetrahydrofuran)

Standard materials for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by TOSOH CORPORATION)

The ratio of the weight average molecular weight to the number average molecular weight obtained above was defined as a molecular weight distribution (Mw / Mn).

Manufacturing example  2: Silicon epoxy Acrylate  Produce

[Compound 1]

A three-neck reactor was charged with 456 g of TEMOOMER LAG-876 (TEGO, polydimethylated hydroxide), 150 g of NaOH and 290 g of epichlorohydrin in a heating device connected to a mechanical stirrer, a temperature sensor and a temperature sensor, 2.5 parts by weight of Rad 2500 as a defoaming agent was added dropwise thereto and reacted at a reaction temperature of 95 캜 for 3 hours, followed by drying in a 150 캜 drying oven for 5 hours to prepare an epoxy resin from which moisture was removed. After the reaction was completed, the reaction temperature was cooled to room temperature, 20 g of quaternary ammonium triethylamine hydrochloride and 0.3 g of hydroquinone as a polymerization inhibitor were completely dissolved in 80 g (0.8 mol) of acrylic acid, added to the mixture, For 7 hours to prepare the silicone-based epoxy acrylate of the compound 1. [ Reaction confirmation showed an increase in the epoxy peak of IR (910 cm -1) and a decrease in the -OH peak of the diol. The reaction was terminated by measuring the acid value and proceeding to 2 mg KOH / g resin or less to terminate the reaction. The reaction formula is described below.

Scheme 1

Experimental Example

Using the alkali-soluble resins and silicone acrylates prepared in Preparation Examples 1 and 2, photosensitive resin compositions for spacers were prepared in the components and compositions shown in Table 1 below (parts by weight).

(A) an alkali-soluble resin (B) a photopolymerizable compound (C) a photopolymerization initiator (D) Solvent (E) Silicone acrylate Example 1 55 35 C-1 + C-2 2.5 + 2.5 100 10 Example 2 60 25 C-1 + C-3 2.5 + 2.5 100 15 Example 3 40 40 C-2 + C-3 2.5 + 2.5 100 20 Example 4 55 20 C-1 + C-3 2.5 + 2.5 100 25 Example 5 55 15 C-1 + C-3 2.5 + 2.5 100 30 Comparative Example 1 55 45 C-1 + C-3 2.5 + 2.5 100 0 Comparative Example 2 55 0 C-2 + C-3 2.5 + 2.5 100 45

- Alkali-soluble resin: The alkali-soluble resin prepared in Preparation Example 1

- Photopolymerizable compound: DIPENTAERYTHRITOL HEXAACRYLATE (DPHA, Nippon Yakushin Co., Ltd., Japan)

- Photopolymerization initiator

C-1: Ethanone-1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (O- acetyloxime) (trade name Irgacure.RTM. Oxe02, BASF)

C-2: 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1-one (trade name Irgacure 907, BASF)

C-3: 2- (4-Methylbenzyl) -2- (dimethylamino) -1 - ((4-morpholinophenyl)

- Solvent

Propylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate (PGMEA, DOW chemical company, USA)

- Silicone acrylate: The silicone-based epoxy acrylate prepared in Preparation Example 2

Experimental Example

Experimental Example  One: Spacer  Preparation of pattern using photosensitive resin composition for forming

A pattern was prepared using the photosensitive resin composition for forming spacers prepared in Examples 1 to 5 and Comparative Examples 1 and 2. Specifically, each of the spacer-forming photosensitive resin compositions for spacer formation was coated on a glass substrate at a specific speed by a spin coating method, and then placed on a heating plate and held at a temperature of 100 캜 for 3 minutes to form a thin film. Subsequently, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% to a step-like pattern and a line / space pattern of 1 to 50 m was placed on the thin film and the distance between the test photomask and the test photomask was set to 100 m. Respectively. At this time, the ultraviolet light source was irradiated at a light intensity of 100 mJ / cm 2 using a 1 kW high pressure mercury lamp containing g, h and i lines. The thin film irradiated with ultraviolet rays was immersed in a KOH aqueous solution of pH 10.5 for 2 minutes to develop. The glass plate coated with the thin film was washed with distilled water, dried by blowing nitrogen gas, and heated in a heating oven at 230 ° C for 20 minutes to prepare a pattern. The thickness of the pattern prepared above was 3.5 mu m. The film thickness was measured using a film thickness measuring apparatus (DEKTAK 6M; Veeco).

Experimental Example  2: Measurement of physical properties of pattern

The pattern (linewidth, sectional shape) and mechanical properties (total displacement and recovery rate) of the pattern produced in Experimental Example 1 were measured as follows.

(1) Pattern (line width, sectional shape)

The line width of the cured film obtained above was measured using a scanning electron microscope (S-4200, manufactured by Hitachi, Ltd.), and the sectional shape was evaluated as follows. The cross section shape indicates the bottom length (um) of the pattern generated in the 10um pattern. When the angle of the pattern with respect to the substrate was less than 90 degrees, it was determined to be a reverse taper. If it is a reverse taper, ITO wiring is easily short-circuited at the time of formation of a display device, and if it is a pure taper, disconnection of the ITO wiring is unlikely to occur.

(2) Mechanical properties (total displacement and recovery rate)

The total amount of displacement (占 퐉) and the amount of elastic displacement (占 퐉) were measured under the following measurement conditions using a dynamic ultra-microhardness tester (DUH-W201; manufactured by Shimadzu Corporation) The recovery rate (%) was calculated as follows. When the total displacement was small and the recovery rate was high, it was judged to be rigid.

Recovery rate (%) = [Elastic displacement (占 퐉)] / [Total displacement (占 퐉)] X 100

The measurement conditions are as follows.

Test mode: load - unloading test

Test force: 5 gf [SI unit conversion value; 49.0 mN]

Load speed: 0.45 gf / sec [SI unit conversion value; 4.41 mN / sec]

Holding time: 5sec

Indenter: conical indenter (diameter 50 탆)

The results of measuring the physical properties of the pattern prepared in Experimental Example 1 are shown in Table 2 below.

division pattern Mechanical properties Line width shape Total displacement (㎛) Recovery Rate (%) Example 1 9.3 Sun Taper 0.68 78 Example 2 9.1 Sun Taper 0.65 87 Example 3 9.2 Sun Taper 0.66 92 Example 4 9.1 Sun Taper 0.55 88 Example 5 9.3 Sun Taper 0.56 82 Comparative Example 1 9.7 Sun Taper 0.76 68 Comparative Example 2 9.3 Reverse taper 0.55 73

As shown in Table 2, in Comparative Example 1 prepared using the composition containing no silicon acrylate of the present invention, the total displacement amount was 0.76, which was relatively high, and the recovery rate was also 68% .

On the other hand, in Examples 1 to 5 prepared using the composition containing silicon acrylate of the present invention, not only the angle of the pattern with respect to the substrate was measured at less than 90 degrees (net taper), but the total displacement amount was less than 0.7 And the recovery rate was 78% or more, indicating that the mechanical properties were remarkably improved.

In Comparative Example 2 in which silicon acrylate was contained in an excessive amount (45 parts by weight), the total displacement amount was as low as 0.55, but the recovery rate was also as low as 73%, and the pattern angle with respect to the substrate was 90 degrees or more Taper, showing no improvement in mechanical properties.

That is, when the photosensitive resin composition for forming a spacer contains 5 to 50% by weight of silicon acrylate based on the sum of the alkali-soluble resin and the photopolymerizable compound from the experimental results, the effect of improving the pattern mechanical properties is improved Respectively. In Examples 1 to 5 having an epoxy group, although the force of 49 mN was applied in the evaluation, it was found that the physical properties of the pattern were excellent due to the small amount of displacement, and the recovery rate was large compared with the recovery rate of Comparative Example 1 And improved.

Claims (4)

A photosensitive resin composition for forming a spacer, which comprises a silicone acrylate represented by the following formula (1), an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator and a solvent.
[Chemical Formula 1]

In the above formula
R ₁ is independently hydrogen or an alkyl group having 1 to 5 carbon atoms,
R ₂ represents, independently of each other, an alkylene group having 2 to 20 carbon atoms containing an ester bond, 1 to 20 repeating units of an alkylene oxide group having 2 to 10 carbon atoms, an alkylene group having 1 to 20 carbon atoms, An arylene group or an epoxy group having 1 to 20 carbon atoms,
a and b are each independently an integer of 1 to 10,
Y may include a hetero atom as the aliphatic or aromatic hydrocarbon having 0 to 30 carbon atoms (excluding the number of carbon atoms of the (meth) acrylate group) and containing 1 to 10 (meth) acrylate groups reacting at the time of curing. The composition according to claim 1, which comprises 0.1 to 20% by weight of silicon acrylate and 45 to 90% by weight of a solvent based on the total weight of the composition, wherein 10 to 80% by weight of the alkali-soluble resin is added to the total weight of the solid content in the composition, 10 to 85% by weight of the photosensitive resin composition, and 0.1 to 40% by weight of a photopolymerization initiator based on the sum of the alkali-soluble resin and the photopolymerizable compound. The photosensitive resin composition for forming a spacer according to claim 1, wherein the silicone acrylate is contained in an amount of 5 to 50% by weight based on the sum of the alkali-soluble resin and the photopolymerizable compound. The spacer according to claim 1, wherein the spacer is made from the photosensitive resin composition for forming a spacer.