KR100958581B1 - Photosensitive resin composition - Google Patents

Abstract

The present invention relates to a photosensitive cured resin composition, and more particularly, to a pattern spacer of a transparent material having excellent storage stability, heat resistance, chemical resistance, and resolution capable of buffering according to temperature change while maintaining a uniform cell gap stably. In photoresist composition and negative resist composition for TFT-LCD which can form transparent cured resin pattern with excellent storage stability and chemical resistance, uniform height of formed pattern, excellent elastic recovery and buffering effect and high transmittance to visible light. It is about.

To this end, the present invention provides a polymerized unit of maleimide or di (meth) acrylamide structure, an oxetane polymerized unit, a lauryl polymerized unit, and a polymerized unit derived from unsaturated carboxylic acid, which form a cyclic structure in a polymer main chain. 3 to 40% by weight of the alkali-soluble binder resin, 2 to 40% by weight of the polyvalent acrylic photopolymerizable compound having a polyvalent acrylic group, 0.01 to 10% by weight of the photopolymerization initiator, and 10 to 94.99% by weight of the residual solvent .

Pattern spacer, elastic recovery rate, crimp amount, chemical resistance

Description

Photosensitive cured resin composition {PHOTOSENSITIVE RESIN COMPOSITION}

The present invention relates to a photosensitive cured resin composition.

The photosensitive curable resin composition is, for example, used in a thin film transistor (hereinafter, referred to as TFT) type liquid crystal display device to form a pattern for maintaining a constant film thickness so that a liquid crystal can be driven between a color filter plate and a thin film transistor (TFT) plate. Column spacers, insulating films, TFT insulating films used in organic EL display devices, diffusion reflecting plates used in reflective TFT substrates, organic EL insulating films, TFT-LCDs, protective films of organic EL and charge transfer devices (CCD), and the like. It is useful as a material for forming cured resin patterns, including.

Since the liquid crystal display device is an electro-optical device that drives by applying a voltage to the liquid crystal molecules injected at regular intervals between the transparent substrates, it is very important to maintain the two substrates at regular intervals. Spacers are used to regulate the two substrate gaps and to maintain the proper thickness of the liquid crystal layer. If the cell spacing is not constant, the voltage applied to the part and the transmittance of light passing through are different, resulting in a defect that shows spatially uneven brightness. This problem is more important as the size of the liquid crystal panel is gradually increased. It is becoming.

In general, in order to maintain a constant cell spacing of the panel, a method of spraying a plastic ball or silica sphere having a desired aperture on the substrate by spraying the spacer evenly on the front surface of the panel is used. come. However, it is not only difficult to disperse and apply the spacer particles at a desired position, but there are also problems such as change in the position of the particles due to agglomeration, vibration, or external impact of the particles.

Recently, the method of manufacturing the patterned column spacer using the photosensitive resin composition is applied. This method is applied by applying a photosensitive resin composition to a substrate and then exposing the substrate to which the photosensitive resin composition is applied to ultraviolet rays using a mask having a predetermined pattern corresponding to the column spacer pattern to remove the unexposed portion of the resin composition. To form.

The uniformity of the spacers has become increasingly important with the increase in size of liquid crystal display devices (LCDs). The use of LCDs is being extended to a wide range from the consumer sectors such as TV and e-paper to the industrial sectors such as PDA, notebook, monitor and mobile phone. In small LCDs, only hard spacers are required to maintain a stable cell gap. However, as in the recent popularization of large LCD TVs, spacers are not only stable in large-sized or high-precision LCDs but also optical characteristics due to temperature changes in the liquid crystal layer. It is required to have a constant elasticity in consideration of the fluctuation of the cell and the fluctuation of the cell spacing.

As examples of negative photosensitive curable resins, those containing a binder resin (A), a photopolymerizable compound (B) and a photopolymerization initiator (C) are known. As the binder resin, an acrylic copolymer of epoxy structure is generally used. The pattern formed by the negative photosensitive resin is preferably uniform in height, excellent in strength, good in elastic recovery, and suitable for liquid crystals or organic solvents so as to be suitable for the TFT-LCD bonding process.

However, in a conventional photosensitive composition containing a binder resin (A) having a conventional epoxy structure, increasing the ratio of epoxy groups in order to enhance the above characteristics has a problem that storage stability tends to be poor.

An object of the present invention is to provide a photosensitive resin composition for a pattern spacer of a transparent material having excellent storage stability, heat resistance, chemical resistance, and resolution capable of buffering with temperature changes while maintaining a uniform cell gap.

An object of the present invention is to provide a negative resist composition for TFT-LCD, which is capable of forming a transparent cured resin pattern having excellent storage stability and chemical resistance, uniform height of formed patterns, excellent elastic recovery and buffering effect, and high transmittance to visible light. Is to provide.

In order to solve the above technical problem, the negative register composition according to the present invention includes a polymerized unit (a) having a maleimide or di (meth) acrylamide structure and a polymerized unit (b) having an oxetane structure, forming a cyclic structure in a polymer main chain, 3 to 40% by weight of an alkali-soluble binder resin (A) consisting of a polymerized unit (c) having a lauryl structure, a polymerized unit (d) derived from an unsaturated carboxylic acid, and a polyvalent acrylic photopolymerizable compound (B) having a polyvalent acrylic group (B) 2 to 40 weight%, 0.01-10 weight% of photoinitiators (C), and 10-94.99 weight% of solvent are contained.

In order to achieve the above object, the present invention provides one polymerized unit (a) selected from polymerized units having a dimethacrylate structure of Formula 1 or a maleimide structure of Formula 2, Formula 3 It includes a polymerized unit of oxetane structure (b), a mixture of copolymerizable polymerized units (c) including a laurylmethacrylate structure of formula (4) and a polymerized unit (d) derived from unsaturated carboxylic acid 3 to 40% by weight of the alkali-soluble binder resin (A), 2 to 40% by weight of the polyvalent acrylic photopolymerizable compound (B) having a polyvalent acrylic group, 0.01 to 10% by weight of the photopolymerization initiator (C), and 10 to 94.99 % by weight of the residual solvent . It provides the photosensitive resin composition for pattern spacers containing.

The binder polymer (A) is a monomer having an amide or imide structure that forms a cyclic structure in the polymer backbone as represented by Formula 1 or 2, a monomer having an oxetane structure as represented by Formula 3, and Formula 4 It is preferred that it is a copolymer of other monomer (s) that can be copolymerized.

<일반식 1>

<Formula 1>

In Formula 1, R is each independently H or a methyl group, R 1, R 2 are each independently H or an alkyl group, cycloalkyl group or aromatic compound having 1 to 14 carbon atoms, R 3 is 1 to It is a compound of 14, and X is a compound which is a methylene group or ethylene group.

Examples of R 1 in general formula 1 include methyl, ethyl, propyl, isopropyl, butyl, t-butyl, isobutyl, pentyl, hexyl, cyclohexyl, phenyl, benzyl, naphthyl, adamantyl, 4-hydroxyphenyl , Decyl, dodecyl, and examples of R 3 are allyloxycarbonyl, methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, glycidyloxycarbonyl, butoxycarbonyl, t-butoxycarbonyl, isobutoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, cyclohexyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, naphthyloxycarbonyl, isobonyloxycarbon Carbonyl, 2-oxooxapentyloxycarbonyl, adamantyloxycarbonyl, dicyclopentanyloxycarbonyl, dicyclopentenyloxycarbonyl, dicyclopentanylethyloxycarbonyl, dicyclopentenylethyloxycarbonyl, Hydroxyethyloxycarbonyl, dimethyl Mino ethyl-butyloxycarbonyl, dodecyloxy Brassica Viterbo carbonyl, methoxy, ethoxy City, phenyloxy, phenyl, naphthyl, hydroxyphenyl, a nitrile may be used as the one or two or more.

The binder resin of the general formula (1) may be a random copolymer that is not restricted by the sequence of the polymerization units.

       In Formula 1, a is 0.01 to 0.70, b is 0.05 to 0.70, c is 0.03 to 0.50, d is 0.01 to 0.50, a is 0.1 to 0.5, b is 0.1 to 0.6, c is 0.1 to 0.4, d is 0.01 -0.4 is more preferable.

The average molecular weight of the binder resin represented by the general formula (1) is preferably 2,000 to 300,000, the dispersion degree is 1.0 to 10.0, the acid value is 10 to 400 KOH mg / g, the average molecular weight is 4,000 to 50,000, the dispersion degree is 1.5 It is more preferable to use those which are -3.0 and an acid value are 20-200 KOH mg / g.

Examples of the compound that forms a cyclic structure in the polymer backbone include a compound comprising a monomer represented by Formula 1 or Formula 2:

<Formula 1>

<Formula 2>

(Wherein R 1 and R 2 represent a hydrogen atom or a methyl group and R 3 represents a hydrogen atom or an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group or an aromatic group)

Can be mentioned.

Maleimide and dimethacrylamide derivatives have a high glass transition temperature (Tg) and are excellent in heat resistance and optical properties. As their content increases, they become hard spacers.

Examples of monomers include N, N'-dimethacrylamide, N, N'-diacrylamide, methyl-N, N'-dimethacrylamide, methyl-N, N'-diacrylamide, ethyl-N, N'-dimethacrylamide, ethyl-N, N'-diacrylamide, isopropyl-N, N'-dimethacrylamide, isopropyl-N, N'- diacrylamide, butyl-N, N ' Dimethacrylamide, butyl-N, N'-diacrylamide, dodecanyl-N, N'-dimethacrylamide, dodecanyltyl-N, N'-diacrylamide, t-butoxy-N, N'-dimethacrylamide, t-butoxy-N, N'-diacrylamide, ethoxyethyl-N, N'-dimethacrylamide, methoxypropyl-N, N'-dimethacrylamide, Pyranyl-N, N'-dimethacrylamide and maleimide, methylmaleimide, ethylmaleimide, isopropylmaleimide, butylmaleimide, dodecanylmaleimide, phenylmaleimide, t-butoxy-maleimide, Ethoxyethylmaleimide, methoxypropylmaleimide, pyranylmaleimide You can use one or more of them together.

Examples of the monomer having an oxetane structure include an oxetane structure represented by Formula 1a:

<Formula 3a>

및 화학식 3b로 표시되는 탄소 이중결합

And carbon double bonds represented by Formula 3b.

<Formula 3b>

(Wherein R 4 represents a hydrogen atom or a methyl group)

The compound which has a is mentioned.

More specifically, examples of the compound include a compound comprising a monomer represented by Formula 3:

<Formula 3>

(Wherein R 4 is as defined above, R 5 is a hydrogen atom or an alkyl group having 1 to 14 carbon atoms, a cycloalkyl group or an aromatic compound, and X represents a methylene or ethylene group).

Examples of the monomer include 3-methyl-3-methacryloxymethyl oxetane, 3-methyl-3-acryloxymethyl oxetane, 3-ethyl-3-methacryloxymethyl oxetane and 3-ethyl-3-acrylic. Oxymethyl oxetane, 3-methyl-3-methacryloxyethyl oxetane, 3-methyl-3-acryloxyethyl oxetane, 3-ethyl-3-methacryloxy ethyl oxetane and 3-ethyl-3-a Cryloxyethyl oxetane is mentioned.

The monomer unit having an oxetane structure in the binder polymer is derived from a monomer having an oxetane structure as in the above-mentioned monomers. The monomer unit having an oxetane structure may be one kind or a combination of two or more kinds.

<Formula 4>

In the above formula, R 6 is a hydrogen atom or a methyl group, and R 7 is a compound having 1 to 14 carbon atoms.

Examples of R 7 in formula 4 include allyloxycarbonyl, methoxycarbonyl, ethoxycarbonyl, propyloxycarbonyl, isopropyloxycarbonyl, glycidyloxycarbonyl, butoxycarbonyl, t-butoxy Carbonyl, isobutoxycarbonyl, pentyloxycarbonyl, nuxyloxycarbonyl, cyclonuxyloxycarbonyl, phenyloxycarbonyl, benzyloxycarbonyl, naphthyloxycarbonyl, isobonyloxycarbonyl, 2-oxooxa Pentyloxycarbonyl, adamantyloxycarbonyl, dicyclopentanyloxycarbonyl, dicyclopentenyloxycarbonyl, dicyclopentanylethyloxycarbonyl, dicyclopentenylethyloxycarbonyl, hydroxyethyloxy carbonyl , Dimethylaminoethyloxycarbonyl, dodecyloxycarbonyl, methoxy, ethoxy, phenyloxy, phenyl, naphthyl, hydroxyphenyl, nitrile, one or two or more of them can be used together. .

<Formula 5>

In particular, the lauryl methacrylate represented by the formula (5) has a low glass transition temperature, the higher the content of the spacer becomes softer and does not increase the elastic force of the photosensitive curable resin composition, but by changing the shape according to the force of the load portion of the cell gap It is stable in control.

The content of the mixture of one polymerized unit selected from the maleimide structure or the polymerized unit of dimethacrylate structure and the polymerized unit of laurylmethacrylate structure is 5 of the binder resin total content. It is preferable that it is to 70 parts by weight.

A mixture of one polymerized unit selected from maleimide or dimethacrylate polymerized units and a polymerized unit of laurylmethacrylate structure determines the hardness of the photosensitive composition of the present invention. do. Maleimide and dimethacrylamide enter selectively and the higher the content, the higher the hardness of the spacer and the stability of the cell gap is increased. On the other hand, lauryl methacrylate is a soft spacer and performs a buffer against the nonuniformity caused by the thickness variation of the sulf gap. Therefore, by appropriately adjusting the content of these two components it is possible to provide an optimal photosensitive composition for spacers suitable for the use of the liquid crystal panel. In small LCD products, the content of maleimide or dimethacrylamide is increased. In large LCD TV products, the content of lauryl acrylamide is increased. It is effective in preventing the gravity failure caused by.

 In addition, a separate photosensitive resin composition for a separate process should be prepared for each production of various liquid crystal panels. By simply adjusting the content of the composition, a photosensitive resin composition for a spacer can be manufactured, thereby increasing economic efficiency and rapidity of product manufacturing.

The polymerized unit (d) derived from unsaturated carboxylic acid may include a ball saturated carboxylic acid having one or more carboxyl groups such as unsaturated monocarboxylic acid or unsaturated dicarboxylic acid. Specific examples thereof include acrylic acid, methacrylic acid, crontonic acid, itaconic acid, maleic acid, and kumaric acid. These monomers with carboxyl are compounds with carbon carbon unsaturated double bonds and can be used alone or in combination of two or more.

The photopolymerizable compound (B) is a compound which can be polymerized by the action of an acid or an active radical generated from the photopolymerization initiator (C) by irradiating a light beam. In general, synthetic compounds in light have a polymerizable carbon-carbon unsaturated bond. It may be a monofunctional monomer as well as a bifunctional or polyfunctional monomer.

Examples of monofunctional monomers include nonylfeylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone Etc. can be mentioned.

Examples of difunctional monomers include 1,6-hexyldiol di (meth) acrylate, ethylene glycol (meth) acrylate, neopentylglycol di (meth) acrylate, triethylene glycol di (meth) acrylate, bisphenol A Bis (acryloyloxyethyl) ether, 3-methylenediol di (meth) acrylate, and the like. Examples of other polyfunctional monomers include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate etc. are mentioned.

These photopolymerizable monomers may be used alone or in combination of two or more. It is preferred that one or more difunctional or other multifunctional monomers are used. It is preferable that the quantity of a photopolymerizable compound (B) is 2-40 weight part generally with respect to the whole photosensitive resin composition. When the content of the photopolymerizable compound exceeds 40% by weight, the degree of crosslinking of the film is increased, thereby deteriorating physical properties of the film and deteriorating thermal stability. The polyvalent acryl monomer which is a polymeric compound which has such a polyvalent acryl group can manufacture the photosensitive cured resin composition which can maintain heat resistance and pattern stability by suitably adjusting a composition ratio with binder resin according to this invention.

Examples of the photopolymerizable initiator (C) include an active radical generator that generates active radicals by irradiation of light beams and an acid generator that generates acid by irradiation of light beams. Examples of active radical generators include acetophenone-based polymerization initiators, benzoin-based synthesis initiators, benzophenone-based polymerization initiators, thioxanthone-based polymerization initiators, triazine-based polymerization initiators, and other initiators.

Specific examples of the acetophenone-based polymerization initiators include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-2- monopolyno-1- (4-methylthiophenyl) propan-1-one, 2 -Benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1- Oligomers, such as on.

Specific examples of benzoin-based polymerization initiators include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.

Specific examples of the benzophenone-based polymerization initiators include benzophenone, methyl o- benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4, 4'-tetra ( Tert-butylperoxycarbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.

Specific examples of thioxanthone type polymerization initiators include 2-isopropyl thioxanthone, 4-isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4 Propoxy city oxanthone etc. are mentioned.

Specific examples of the triazine polymerization initiator include 2,4, -bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 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 (trichloro Romethyl) -6- [2- (3,4 [dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.

Examples of active radical generators include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2'-bis ( o -chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1, 2'-biimidazole, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, titanocene compound and the like Can be mentioned.

Commercially available active radical generators can also be used. Examples thereof include "Irgacure-907" (acetophenone-based polymerization initiator, manufactured by CIBA-GEIGY).

Examples of acid generators include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluenesulfonate, 4-acetoxyphenyl Onium salts such as methylbenzylsulfonium hexafluoroantimonate and triphenyl iodonium hexafluoroantimonate, nitrobenzyl tosylate, benzointosylate and the like.

Some of the active radical generators are also acid generators. For example, the triazine-based polymerization initiator may act as an acid generator as well as an active radical generator.

The photopolymerization initiators may be used alone or in combination of two or more.

The content of the photopolymerization initiator is preferably 0.01 to 10 parts by weight based on the total content of the photosensitive composition.

In addition, the photosensitive curable resin composition of the present invention may be used by adding a silicone compound having an epoxy group, a hydrogen sulfide group or an amine group as an adhesive aid, if necessary, such a silicone compound improves the adhesion of the resist composition, heat resistance after curing Increase the properties. Examples of the silicone-based compound having such an epoxy group or an amine group include (3-glycidoxypropyl) trimethoxysilane, (3-glycidoxypropyl) triethoxysilane, and (3-glycidoxypropyl) methyldimethoxysilane Phosphorus, (3-glycidoxypropyl) methyldiethoxysilane, (3-glycidoxypropyl) dimethylmethoxysilane, (3-glycidoxypropyl) dimethylethoxysilane, 3,4-epoxybutyl Trimethoxysilane, 3,4-epoxybutyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrie Methoxysilane, aminopropyltrimethoxy silane, and the like, and these may be used alone or in combination.

Moreover, compatible additives, such as a photosensitizer, a thermal polymerization inhibitor, an antifoamer, and a leveling agent, can be added as needed.

The photosensitive cured resin composition of the present invention forms a pattern through spin coating on a substrate by adding a solvent, and then irradiating ultraviolet rays using a mask to develop with an alkaline developer. It is preferable to add. These solvents are used to add and dissolve binder resins, photosensitizers and other additives, as well as to obtain excellent coating properties and transparent thin films. In consideration of compatibility with binder resins, photosensitizers and other compounds, ethyl acetate, Butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy propionate, ethyl ethoxy propionate (EEP), ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol methyl ether, propylene Glycolpropyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexanone, dimethyl formumamide (DMF), N, N- Dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-part Rolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl A solvent selected from ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane and octane alone or in mixture of one or more thereof may be used.

This invention apply | coats the photosensitive cured resin composition obtained above to the surface of a board | substrate by the spray method, the roll coater method, the rotary coating method, and the slit coater method, and forms a coating film. After coating, the coating film is completed by prebaking or ultraviolet irradiation, and then irradiated with visible light, ultraviolet light, far ultraviolet rays, electron beams, X-rays, etc. onto the coating film, and then developed with a developer to remove a predetermined portion.

As the developing solution, an aqueous alkali solution is used. For example, secondary alkalis, such as inorganic alkali ethylamines, such as sodium hydroxide, potassium hydroxide, and sodium carbonate, and diethylamine, such as primary amines, such as n-propylamine, trimethylamine, methyldiethylamine, dimethylethylamine, and triethylamine Aqueous amines, such as tertiary amines, such as diethylethanolamine, methyl diethanolamine, and triethanolamine, can be used for aqueous solutions of quaternary ammonium salts, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. The developer is used by dissolving the alkaline compound at a concentration of 0.1 to 10%, and a suitable amount of water-soluble organic organic solvents and surfactants such as methanol, ethanol, isopropanol and the like may be added.

After the development, washing with ultrapure water for 30 to 90 seconds to remove unnecessary parts and dry to form a pattern. After irradiating the formed pattern with light such as ultraviolet rays, the final pattern may be obtained by heating the pattern at 140 to 250 ° C. for 30 to 90 minutes using a heating apparatus such as an oven.

In addition to the pattern forming method, a pattern region may be designated by a direct transfer method such as an inkjet method or a printing method, and then a pattern having the same purpose may be obtained by treatment such as ultraviolet irradiation or heating.

Hereinafter, the present invention will be described in detail by the following examples, but the present invention is not limited to the following examples.

<Examples>

Synthesis Example 1

In a four-necked flask equipped with a stirrer, a coolant and a thermometer with a internal volume of 500 ml, 24.5 g of maleide, 64.5 g of 3-ethyl-3-methacryloxymethyl oxetane, 23 g of methacrylic acid, 7.5 g of lauryl methacrylate, benzyl 17.5 g of methacrylate was added and 250 g of diethylene glycol methylethyl ether and 1.5 g of azobisisobutyronitrile were charged. The temperature of the reaction mixture was maintained at 70 ° C. while stirring for 5 hours to obtain binder resin A1. The resulting binder resin A1 is a copolymer polymerized at the ratio of monomer loading.

Synthesis Example 2

Except having used the dimethacrylamide 38.3g instead of the maleimide of the synthesis example 1, it was made to react similarly to the synthesis example 1, and the binder resin A2 which is a copolymer was obtained.

Synthesis Example 3

A binder resin A3 as a copolymer was obtained in the same manner as in Synthesis example 1 except that the amount of benzyl methacrylate was changed to 23 g and lauryl methacrylate was not used.

(Production of Photosensitive Composition)

The components were mixed in the proportions shown in Table 1 to obtain a photosensitive transparent cured resin composition.

Example 1 Example 2 Example 3 Binder resin A1 A2 A3  15.0 parts by mass Photopolymerizable compound Dipentaerythritol hexaacrylate ("KAYARAD DPHA" Nihon Kayaku Kogyou K.K.)  15.0 parts by mass Photopolymerization initiator "Irgacure-907" (CIBA SPECIALTY CHEMICAL)  1.5 parts by mass Adhesion Aid (3-aminopropyl) trimethoxysilane  Amount Leveling agent FC-430 (3M)  Amount menstruum Propylene Glycol Monomethyl Ether Acetate  68.5 parts by mass

Table 1

 In Table 1, the binder resins had an average molecular weight of 20,000, a dispersity of 2.1, and an acid value of 95.

<Comparative Examples 1 and 2>

Synthesis Example 4

The reaction was carried out in the same manner as in Synthesis Example 1, except that 50 g of glycidyl methacrylate was used instead of 3-ethyl-3-methacryloxymethyl oxetane of Synthesis Example 1 to obtain a binder resin B1 which is a copolymer.

Synthesis Example 5

A binder resin B2 was obtained by polymerization in the same manner as in Synthesis Example 4 except that the amount of benzyl methacrylate was changed to 67 g and maleimide was not used. Binder resin B2 is a copolymer of benzyl methacrylate, glycidyl methacrylate and methacrylic acid, and copolymerized according to the proportion of the loading.

(Production of Photosensitive Composition)

A photosensitive transparent cured composition was prepared in the same manner as in Example 1 except that 15 parts by mass of binder resin B1 or B2 was used instead of the binder resin A1.

Comparative Example 1 Comparative Example 2 Binder resin B1 B2  15.0 parts by mass Photopolymerizable compound Dipentaerythritol hexaacrylate ("KAYARAD DPHA" Nihon Kayaku Kogyou K.K.)  15.0 parts by mass Photopolymerization initiator "Irgacure-907" (CIBA SPECIALTY CHEMICAL)  1.5 parts by mass Adhesion Aid (3-aminopropyl) trimethoxysilane  Amount Leveling agent FC-430 (3M)  Amount menstruum Diethylene glycol methylethyl ether  68.5 parts by mass

TABLE 2

 The binder resins in Table 2 have an average molecular weight of 20,000, a dispersity of 2.1 and an acid value of 100.

Experimental Example

(evaluation)

In the above Examples and Comparative Examples, the evaluation of the photosensitive resin composition for the pattern spacer was carried out on a substrate such as a silicon wafer or a glass plate, and the performances such as compression recovery rate and compression amount, heat resistance, pattern formation, chemical resistance, and storage stability of the resist composition Evaluation was performed and the results are shown in Table 3 below.

(1) Compression recovery rate and compression amount measurement

In order to evaluate the compression recovery rate of the resist composition for the column spacer, a nanoindentation experiment was conducted with a Nanoindenter manufactured by Shimatsu, Japan. When the indenter was used with a flat punch tip, loaded for 20 mN and stopped for 3 seconds, the load was removed to 2 mN, the measured distance and the amount of compression were compared, the compression was sufficient, and the pattern was soft enough not to break. ○ If the pattern is easily broken or too hard, the amount of crimp is insufficient.

(2) heat resistance

The negative resist composition was applied onto the substrate using a spin coater, then prebaked at 100 ° C. for 1 minute, exposed at 365 nm for 15 seconds, and post-baked at 240 ° C. for 30 minutes. After forming, it is subjected to postbake once again at 240 ° C. for 30 minutes to measure the decrease in film thickness. If the film thickness is less than 5%, 'good' or not is considered 'bad'.

(3) pattern formation

The silicon wafer in which the negative resist pattern was formed was cut from the vertical direction of a dot pattern, and the result observed with the electron microscope in the cross-sectional direction of the pattern was shown. The pattern side wall was erected at an angle of 55 degrees or more with respect to the substrate, the film was not reduced, and it was determined as 'good', and the reduction of the film was judged as 'film'.

(4) chemical resistance

After the negative resist composition was applied onto the substrate using a spin coater, a resist film formed through a process such as prebake and postbake was applied to a stripper or etchant solution at 40 ° C. at 10 ° C. After soaking for minutes, the change in the transmittance and thickness of the resist membrane was examined. When there was no change in transmittance and thickness, it was set as 'good', and when there was a change in transmittance and thickness, it was determined as 'poor'.

(5) storage stability

The resist composition was stored for one week in a clean room where far ultraviolet rays were blocked and the temperature was adjusted to 23 ° C., and then the viscosity was measured.

TABLE 3

Compression Restoration Rate (%) Crimp Heat resistance Pattern formation Chemical resistance Storage stability Example 1 92 ○ Good Good Good ○ Example 2 93 ○ Good Good Good ○ Example 3 93 X Good Good Good ○ Comparative Example 1 90 X Good Good Good X Comparative Example 2 77 X Bad Bad Good X

As can be seen from the above results, the negative resist composition for a liquid crystal display device of the present invention, unlike the conventional resist composition, not only has excellent compression recovery rate, but also has a suitable spacer pattern according to the bonding process by adjusting the hardness according to the composition. It can be seen that it is easy to implement, has excellent pattern forming ability, and has excellent heat resistance, chemical resistance, and storage stability.

Industrial availability

As described above, the photosensitive transparent resist composition according to the present invention not only has excellent compression recovery rate, but also has excellent heat resistance and chemical resistance. In addition, according to the bonding force applied in the upper and lower plate bonding process of TFT-LCD, the compression rate can be adjusted by changing the composition, so that defects such as pattern spacer collapse can be eliminated, and the effects on color abnormality and color difference change are minimized. can do. Therefore, the photosensitive transparent resist composition of the present invention can be easily prepared as a resist having specific physical properties required by changing the structure and composition ratio of the binder resin within the range defined in the present invention.

Configurations shown in the embodiments and drawings described herein are only one of the most preferred embodiments of the present invention and do not represent all of the technical spirit of the present invention, various equivalents that may be substituted for them at the time of the present application It should be understood that there may be variations and variations.

As described above, the photosensitive resin composition for a pattern spacer of the present invention can easily adjust the hardness of the spacer to suit the use of various LCDs by adjusting the content of its components, chemical resistance, which is an essential requirement of the photosensitive resin composition, It is excellent in low stability, heat resistance, etc., thereby increasing the efficiency and economical efficiency of manufacturing the photosensitive resin composition for spacers.

Claims (5)

Alkali-soluble binder resin (A) 3-40 weight which is a random copolymer which has an average molecular weight of 2,000-300,000, a dispersity of 1.0-10.0, and an acid value of 10-400 KOH mg / g, and is a polymerization unit represented by following General formula (1). %, 2 to 40 weight% of a polyvalent acrylic photopolymerizable compound (B) which has a polyvalent acrylic group, 0.01 to 10 weight% of a photoinitiator (C), and 10 to 94.99 weight% of a residual solvent . <Formula 1>

(In Formula 1, R is each independently H or a methyl group, R ₁ , R ₂ are each independently H or an alkyl group, cycloalkyl group or aromatic compound having 1 to 14 carbon atoms, R ₃ is a dodecyloxycarbonyl group Or a benzyloxycarbonyl group, X is a methylene group or an ethylene group, a is 0.01-0.70, b is 0.05-0.70, c is 0.03-0.50, and d is 0.01-0.50.) delete The solvent of claim 1, wherein the solvent is ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethylethyl ether, methyl methoxy propionate, ethyl ethoxy propionate (EEP), ethyl lactate, propylene glycol Methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl isobutyl ketone, cyclohexa Paddy, dimethylformumamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, digle Lime (Diglyme), tetrahydrofuran (THF), methanol, ethanol, propanol, iso-propanol, methyl cellosolve, ethyl cellosolve, diethylene glycol methyl ether, di Ethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, photosensitive-setting resin composition characterized in that it comprises at least one selected from the group consisting of heptane and octane. delete delete