KR20140136729A - Photosensitive resin composition for spacer, spacer manufactured by the composition and display device including the spacer - Google Patents

Abstract

The present invention relates to (A) an alkali soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a solvent and (E) a calix derivative, Structure, which makes it possible to prepare a spacer having not only the improvement in the elastic recovery rate but also the hardness without the pixel strain due to the external pressure.
(Formula 1)

Description

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

The present invention relates to a photosensitive resin composition for forming a spacer, a spacer for a display device manufactured using the same, and a display device including the spacer. More particularly, the present invention relates to a spacer which is excellent in adhesion, A spacer for a liquid crystal display device manufactured using the same, and a liquid crystal display device including the spacer.

In general display devices, silica beads or plastic beads having a certain diameter have been used to maintain constant spacing of the upper and lower substrates. However, when such beads are randomly dispersed on the substrate and located inside the pixel, there is a problem that the aperture ratio is lowered and light leakage phenomenon occurs. In order to solve these problems, a spacer formed by photolithography has been used in a display device. Currently, a spacer used in most display devices is formed by photolithography. The formation of the spacer by photolithography is performed by applying a photosensitive resin composition on a substrate, irradiating ultraviolet rays through the mask, and forming a spacer at a desired position on the substrate in accordance with a pattern formed on the mask through a developing process.

On the other hand, as the demand for the touch panel is increased due to popularization of smartphones and tablet PCs, the elastic recovery rate, which is a basic characteristic of the spacer maintaining the interval between the color filter substrate and the array substrate constituting the display device, A hard property is required without deformation. However, although the conventional photosensitive resin composition for forming a spacer has a sufficient elastic recovery rate, hard properties without pixel deformation due to external pressure can not be achieved satisfactorily. Japanese Patent Laid-Open Publication No. 1998-115927 describes a positive chemically amplified photosensitive resin composition using a novel material, but the above-described novel material is not only excessively expensive but also has a problem that it can not be applied to a negative pattern.

Japanese Patent Application Laid-Open No. 1998-115927

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made keeping in mind the above problems occurring in the prior art, and it is an object of the present invention to provide a photosensitive resin composition having a hardness characteristic without a pixel deformation due to external pressure, And to provide a photosensitive resin composition applicable to a pattern.

The present invention for achieving the above object is to provide a photosensitive resin composition containing (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a solvent, and (E) The present invention provides a photosensitive resin composition for forming a spacer, which comprises a structure represented by the following formula (1).

(Formula 1)

(In the formula 1,

R 1 is independently a hydrogen atom, an epoxy group (having 2 to 12 carbon atoms), a vinyl group (having 2 to 12 carbon atoms), an alkyl group (having 1 to 12 carbon atoms), an allyl group, a phenyl group, a benzyl group, a halogen atom or an alkoxy group 1 to 8 carbon atoms); And R 2 is a hydrogen atom, a hydroxyl group, a carboxyl group, an alkyl group (having 1 to 12 carbon atoms) or an alkoxy group (having 1 to 8 carbon atoms).

Further, the present invention provides a liquid crystal display element spacer formed by forming the photosensitive resin composition in a predetermined pattern, followed by exposure and development.

Further, the present invention provides a liquid crystal display element including the liquid crystal display element spacer.

When a spacer is produced using the photosensitive resin composition according to the present invention, a spacer having excellent adhesiveness and excellent mechanical properties such as elastic recovery properties can be manufactured. In addition, a liquid crystal display device including a spacer Can be provided.

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition for forming spacers according to the present invention comprises (A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a solvent, and (E) a calixil derivative, The derivative is characterized in that it comprises a compound having the following formula (1).

(Formula 1)

The photosensitive resin composition for forming a spacer according to the present invention is excellent in adhesion to a substrate of a pattern when forming a negative pattern when a spacer is prepared by adding a (E) calix derivative, .

Hereinafter, the contents of the present invention will be described in detail according to the constitution.

(A) an alkali-soluble resin

The alkali-soluble resin (A) comprises structural units of the following formulas (A-1) to (A-4).

≪ Formula (A-1) >

≪ Formula (A-2) >

<A-3>

&Lt; Formula (A-4)

In the alkali-soluble resin, the reactants of the 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-soluble resin (A) . 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 (A) having the structural units represented by the above formulas (A-1) to (A-4) can be produced by polymerization of various polymerizable compounds.

Specific examples of the unsaturated bonds which can be copolymerized with the alkali-soluble resin (A) include a styrene-based resin such as styrene, vinyltoluene, -methylstyrene, p-chlorostyrene, o-methoxystyrene , m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o- vinyl benzyl glycidyl ether, m- Aromatic vinyl compounds such as ether and p-vinylbenzyl 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 (A) according to the present invention may be further mixed with various other alkali-soluble resins which are generally known in the art, if necessary.

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 and the photopolymerizable compound (B) The difference in molecular weight is very large, and thus the phenomenon that the boundary of the pattern is not smooth is observed.

The acid value of the alkali-soluble resin (A) 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 (A) is 30 to 250 (KOH mg / g), the solubility in the developer 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 (A) is in the range of 10 to 80% by weight, preferably 10 to 70% by weight, based on the total solid weight of the photosensitive resin composition for forming a spacer of the present invention. When the content of the alkali-soluble resin (B) is 10 to 80% by weight on the basis of the above-mentioned criteria, the solubility of the developer is sufficient and the pattern formation is easy. In the development, the film portion of the pixel portion of the exposed portion is prevented from being reduced, So that it is preferable.

(B) Photopolymerization  compound

The photopolymerizable compound (B) is not particularly limited as long as it is a compound capable of polymerizing under the action of the photopolymerization initiator (C) to be described later, but is preferably a monofunctional photopolymerizable compound, a bifunctional photopolymerizable compound, Functional photopolymerizable compounds, and the like.

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

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

The photopolymerizable compound (B) 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 the solid content of the photosensitive resin composition for forming a spacer of the present invention. When the photopolymerizable compound (B) 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 are preferably improved.

(C) Light curing Initiator

The photopolymerization initiator (C) can be used without any particular limitation as long as it can polymerize the photopolymerizable compound (B).

In particular, the photopolymerization initiator (C) is preferably selected from the group consisting of an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound, and an oxime 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 an oxalic acid compound and an oxalic acid compound.

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'-biimidazole is preferably used do.

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.

Other examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclyoxylic acid A methyl or a titanocene compound may be used in combination as a photopolymerization initiator.

The photopolymerization initiator (C) may further comprise a photopolymerization initiator (C-1) to improve the sensitivity of the photosensitive resin composition for forming a spacer of the present invention. The photosensitizing resin composition for forming a spacer according to the present invention contains a photopolymerization initiation auxiliary (C-1), whereby the sensitivity can be further increased and the productivity can be improved.

As the photopolymerization initiation auxiliary (C-1), 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 (C) is used in an amount of 0.1 to 40% by weight, preferably 1 to 40% by weight, based on the total solid weight of the photosensitive resin composition for forming a spacer of the present invention, To 30% by weight. When the photopolymerization initiator (C) is in the range of 0.1 to 40% by weight, the photosensitivity of the photosensitive resin composition for forming a spacer is improved and the exposure time is shortened, so that productivity is 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 (C-1) is further used, it is preferable to use the same content range as that of the photopolymerization initiator (C). When the photopolymerization initiator is used in the above-mentioned content, And the productivity of the color filter formed using the composition is improved.

(D) Solvent

When the solvent (D) is effective for dissolving other components contained in the photosensitive resin composition for forming a spacer, a solvent used in a usual photosensitive resin composition may be used without particular limitation, and in particular, an ether, an aromatic hydrocarbon, , Alcohols, esters or amides are preferred.

The solvent (D) specifically includes at least one of 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 Diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol di Ethers such as propyl 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 (D) is preferably an organic solvent having a boiling point of 100 ° C to 200 ° C in terms of coatability and drying property, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butylacetate, ethyl 3-ethoxypropionate or methyl 3-methoxypropionate can be used.

The above-exemplified solvents (D) may be used alone or in combination of two or more.

The solvent may include 60 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 solvent (D) is in the range of 60 to 90% by weight as described above, when it is coated with a coating device such as a roll coater, a spin coater, a slit and spin coater, a slit coater Thereby providing an effect of improving the property.

(E) Calix  derivative

The composition for forming a spacer of the present invention not only significantly improves the elastic recovery rate of the spacer by adding the Kalix derivative (E) but also improves the characteristics of the spacer so as not to deform the pixel due to external pressure.

The calixate derivative (E) of the present invention may have the structure of Formula (1).

(Formula 1)

(1 to 12), an alkyl group (having a carbon number of 1 to 12), an allyl group, a phenyl group, a benzyl group, a halogen An atom or an alkoxy group (having 1 to 8 carbon atoms). Also preferably, R 1 is a hydrogen atom or

Lt; / RTI &gt;

R2 may be a hydrogen atom, a hydroxyl group, an alkyl group (having 1 to 12 carbon atoms) or an alkoxy group (having 1 to 8 carbon atoms), preferably a hydrogen atom.

The (E) calixate derivative is added in an amount of 0.1 to 10% by weight, preferably 2 to 10% by weight, based on the total solid weight of the photosensitive resin composition for forming a spacer, based on the sum of the alkali- 6% by weight. It was experimentally confirmed that the effect of improving the physical properties of the spacer of the (E) calix derivative within the above range was remarkably excellent.

It is preferable that the (E) calixate derivative has an acid value of 100 mgKOH / g or more based on the equivalent of KOH. The acid value of not more than 100 mgKOH / g is not suitable because it slows the developability very slowly in the resist development process. And the acid value is preferably 500 mgKOH / g or less based on the equivalent of KOH. If the acid value is higher than 500 mgKOH / g, the structure of the calixate derivative is weak and it is not effective to improve the mechanical properties of the resist.

Meanwhile, the present invention provides a spacer formed by forming a photosensitive resin composition for forming a spacer in a predetermined pattern, followed by exposure and development, and a display device having the same. The display device spacer can be produced, for example, by coating a photosensitive resin composition for forming a spacer on a substrate as described below, and photo-curing and developing it to form a pattern.

First, a photosensitive resin composition for forming a spacer is coated on a substrate (usually glass) or a layer comprising a solid component of a photosensitive resin composition formed in advance, and then heated and dried to remove volatile components such as a solvent to obtain a smooth coating film.

The coating method can be carried out by, for example, a spin coating method, a flexible coating method, a roll coating method, a slit and spin coating method, a slit coating method or the like. After application, heating and drying (prebaking), or drying under reduced pressure to evaporate the volatile components such as solvent. Here, the heating temperature is usually 70 to 200 占 폚, preferably 80 to 130 占 폚. The thickness of the coated film after heat drying is usually about 1 to 8 mu m. Ultraviolet rays are applied to the thus obtained coating film through a mask for forming a desired pattern. At this time, it is preferable to use an apparatus such as a mask aligner or a stepper so as to uniformly irradiate a parallel light beam onto the entire exposed portion and accurately align the mask and the substrate. When ultraviolet light is irradiated, the site irradiated with ultraviolet light is cured.

The ultraviolet rays may be g-line (wavelength: 436 nm), h-line, i-line (wavelength: 365 nm), or the like. The dose of ultraviolet rays can be appropriately selected according to need, and the present invention is not limited thereto. When the coating film after curing is brought into contact with a developing solution to dissolve and develop the non-visible portion, a spacer having a desired pattern shape can be obtained.

The developing method may be any of a liquid addition method, a dipping method, and a spraying method. Further, the substrate may be inclined at an arbitrary angle during development. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or an organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, disodium hydrogenphosphate, sodium dihydrogenphosphate, ammonium dihydrogenphosphate, ammonium dihydrogenphosphate, potassium dihydrogenphosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate , Sodium hydrogencarbonate, potassium hydrogencarbonate, sodium borate, potassium borate, and ammonia. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine, and the like.

These inorganic and organic alkaline compounds may be used alone or in combination of two or more. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by mass, and more preferably 0.03 to 5% by mass.

The surfactant in the alkali developer may be at least one selected from the group consisting of a nonionic surfactant, an anionic surfactant, and a cationic surfactant.

Specific examples of the nonionic surfactants include polyoxyethylene alkyl ethers, polyoxyethylene aryl ethers, polyoxyethylene alkyl aryl ethers, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, glycerin fatty acid esters, polyoxyethylene fatty acid esters, and polyoxyethylene alkylamines.

Specific examples of the anionic surfactant include higher alcohol sulfuric acid ester salts such as sodium lauryl alcohol sulfate ester and sodium oleyl alcohol sulfate ester, alkylsulfates such as sodium laurylsulfate and ammonium laurylsulfate, sodium dodecylbenzenesulfonate And alkylarylsulfonic acid salts such as sodium dodecylnaphthalenesulfonate.

Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryltrimethylammonium chloride, and quaternary ammonium salts. Each of these surfactants may be used alone or in combination of two or more.

The concentration of the surfactant in the developer is usually 0.01 to 10% by mass, preferably 0.05 to 8% by mass, and more preferably 0.1 to 5% by mass. After development, it is washed with water, and post baking at 150 to 230 캜 for 10 to 60 minutes may be carried out if necessary.

By using the photosensitive resin composition for forming a spacer of the present invention, a pattern can be formed on a substrate or a color filter substrate through each of the steps described above. This pattern is useful as a photo spacer used in a display device.

Therefore, the spacer having such a pattern thus obtained can be effectively used in an image display apparatus such as a liquid crystal display apparatus, and is excellent in transparency and high in cross-linking density even at a low exposure dose, Solvent resistance) and has a high elastic recovery rate.

Hereinafter, the present invention will be described in more detail based on examples. However, the embodiments of the present invention described below are illustrative only, and the scope of the present invention is not limited to these embodiments. The scope of the present invention is indicated in the claims, and moreover, includes all changes within the meaning and range of equivalency of the claims. In the following Examples and Comparative Examples, "%" and "part" representing the content are based on weight unless otherwise specified.

< Synthetic example  1: Synthesis of alkali-soluble resin (A)

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 and mixed. 6 parts by weight of n-dodecanethiol and 24 parts by weight of PGMEA were added as a chain transfer agent dropping vessel And the mixture was stirred. 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 mixture was allowed to stand at 90 DEG C for 2 hours and then heated at 110 DEG C for 1 hour. The temperature was then maintained 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)

< Synthetic example  2: Calix  Preparation of derivative (E) &gt;

The Kalix derivatives used in this experiment were tested using the products of Mitsubishi Gas Chemical Company. The calixate derivatives used in this experiment were used with the following three different contents:

<MGR 108>

<MGR 108-A>

(At any 3 to 5 positions of the 8 positions of R3)

And the position of the remaining R3 is hydrogen.)

<MGR 108-B>

R ₄ : H or Vinyl group (Vinyl group is introduced at any 3 to 5 positions of R4, and remaining R4 is hydrogen).

On the other hand, the Kalix derivatives used in this experiment can be synthesized by the following method.

(1) Synthesis of MGR 108 (Tetra-C-methylcalix [4] resorcinarene)

Tetra-C-methylcalix [4] resorcinarene can be prepared by the following method.

A solution of 33.0 g (0.3 mol) resorcinol and 16.8 mL (0.3 mol) acetaldehyde in 300 mL methanol was heated at 75 ° C. To the solution, 75 mL of concentrated hydrochloric acid was added for 0.5 h. The solution was stirred at 75 &lt; 0 &gt; C for 1 h and a yellow solid precipitated from the homogeneous mixture. After further refluxing for 2 h, the mixture was cooled in an ice bath. The precipitate was collected with a glass filter and dried under reduced pressure. The product was recrystallized from methanol. Yield: 23.0 g (57%).

1 H-NMR (DMSO-d 6): d (ppm) 1.36 (d, CH 3, 12H), 4.52 (q, CH 4H), 6.18 (s, ArH, 4H), 6.83 (s, ArH, 4H); 13C-NMR (DMSO-d6): d (ppm) 20.3 (CH3), 28.7 (CH), 103.6 (ArC), 125.2, 126.1, 152.3.

(2) Synthesis of MGR 108-A and MGR 108-B

MGR 108-A to MGR 108-B were prepared by reacting Tetra-C-methylcalix [4] resorcinarene prepared in (1) above with glycidyl methacrylate.

In the case of MGR 108-A, an epoxy group was introduced by reacting vinyl group of glycidyl methacrylate with Tetra-C-methylcalix [4] resorcinarene.

In the case of MGR 108-B, MGR 108-B containing vinyl group was prepared by reacting epoxy group of glycidyl methacrylate with Tetra-C-methylcalix [4] resorcinarene.

Of the 8 reaction groups, about 3 to 5 reaction groups introduced from MGR 108-A and MGR 108-B were introduced through Nuclear magnetic resonance.

&Lt; Examples and Comparative Example : Spacer  &Lt; Preparation of photosensitive resin composition for forming &

Using the alkali-soluble resin (A) and the calixate derivative (E) synthesized or prepared in the above Synthesis Example, a photosensitive resin composition for forming a spacer was prepared with 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) Calix derivatives MGR 108 MGR 108-A MGR 108-B Example 1 55 45 C-1 + C-2 2.5 + 2.5 100 2 Example 2 60 40 C-1 + C-3 2.5 + 2.5 100 4 Example 3 40 60 C-2 + C-3 2.5 + 2.5 100 6 Example 4 55 45 C-1 + C-3 2.5 + 2.5 100 4 Example 5 55 45 C-1 + C-3 2.5 + 2.5 100 4 Comparative Example 1 55 45 C-1 + C-3 2.5 + 2.5 100 0 Comparative Example 2 55 45 C-2 + C-3 2.5 + 2.5 100 10

(B) Photopolymerizable compound: DIPENTAERYTHRITOL HEXAACRYLATE (HPHA, Japan Yaketsaku Co., Ltd., Japan)

(C) a photopolymerization initiator component

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

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

C-3: Irgacure (R) 369 (BASF), 1- (4-morpholinophenyl)

(D) Solvent

Propylene Glycol Methyl Ether Acetate, Propylene Glycol Monomethyl Ether Acetate (PGMEA, DOW chemical company, USA)

< Experimental Example  1: Fabrication of pattern &gt;

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, cross-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 amount (占 퐉)] / [total displacement amount (占 퐉)] 占 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 measurement of physical properties are shown in Table 2 below.

division pattern Mechanical properties Line width shape Total displacement (㎛) Recovery Rate (%) Example 1 9.0 Sun Taper 0.68 86 Example 2 8.9 Sun Taper 0.65 88 Example 3 9.1 Sun Taper 0.66 92 Example 4 8.9 Sun Taper 0.55 95 Example 5 9.1 Sun Taper 0.56 98 Comparative Example 1 9.6 Sun Taper 0.76 68 Comparative Example 2 9.3 Reverse taper 0.85 72

In the case of Comparative Example 1, which was a pattern prepared using a composition not containing a calcix derivative, the total displacement amount was 0.76, which was relatively high, and the recovery rate was also measured as 68%, indicating that the mechanical properties were inferior.

Thus, in Examples 1 to 5, which are patterns produced using a composition containing a Kalix derivative, not only the angle of the pattern with respect to the substrate was measured at less than 90 degrees (net taper), the total displacement amount was less than 0.7 , And recovery rate was more than 80%, indicating that the mechanical properties were remarkably improved.

On the other hand, in the case of Comparative Example 2 in which an excessive amount (10 parts by weight) of a Kalix derivative was contained, the total displacement amount was as high as 0.85, the recovery rate was also as low as 72%, and the reverse taper , And it was confirmed that the mechanical properties were not improved.

That is, from the above experimental results, when the photosensitive resin composition for forming a spacer contains 2 to 6% by weight of the sum of the alkali-soluble resin (A) and the photopolymerizable compound (B) in the alkali-soluble resin (A) Of the present invention is remarkably improved. In Examples 4 to 5 having an epoxy group and a vinyl group, it was found that even though a force of 49 mN was applied in the evaluation, the displacement was small and the physical properties of the pattern were excellent. Also, the recovery rate was 88% As shown in FIG.

Claims (7)

(A) an alkali-soluble resin, (B) a photopolymerizable compound, (C) a photopolymerization initiator, (D) a solvent and (E) a calixate derivative, Wherein the photosensitive resin composition is a photosensitive resin composition for forming a spacer.
(Formula 1)

(In the formula 1,
R 1 is independently a hydrogen atom, an epoxy group (having 2 to 12 carbon atoms), a vinyl group (having 2 to 12 carbon atoms), an alkyl group (having 1 to 12 carbon atoms), an allyl group, a phenyl group, a benzyl group, a halogen atom or an alkoxy group 1 to 8 carbon atoms); And
R2 is a hydrogen atom, a hydroxyl group, a carboxyl group, an alkyl group (having 1 to 12 carbon atoms) or an alkoxy group (having 1 to 8 carbon atoms).
The method according to claim 1,
Wherein R1 in the formula (1) is a hydrogen atom or an epoxy group (having 2 to 12 carbon atoms), and R2 is a hydrogen atom.
The method according to claim 1,
Wherein R1 in the formula (1) is a hydrogen atom or a vinyl group (having from 2 to 12 carbon atoms) and R2 is a hydrogen atom.
The method according to claim 1,
(E) 0.1 to 10% by weight, based on the total solid weight of the photosensitive resin composition for forming a spacer, of (E) an alkali-soluble resin and (B) a photopolymerizable compound. Sensitive resin composition for forming a spacer.
The method according to claim 1,
(A) 10 to 80% by weight of an alkali-soluble resin and (B) 10 to 85% by weight of a photopolymerizable compound based on the total solid weight of the photosensitive resin composition for forming a spacer,
(C) 0.1 to 40% by weight of a photopolymerization initiator and (E) 0.1 to 10% by weight of a calixate derivative relative to the sum of the alkali-soluble resin (A) and the photopolymerizable compound (B) Sensitive resin composition.
A spacer for a liquid crystal display element formed by forming the spacer resin-forming photosensitive resin composition according to any one of claims 1 to 5 in a predetermined pattern, followed by exposure and development.
A liquid crystal display element comprising a spacer for a liquid crystal display element according to claim 6.