KR100398746B1 - Photoresist composition for color filter containing low molecular silicon compound and manufacturing method thereof - Google Patents

Abstract

The present invention comprises a silicone compound represented by the general formula (I), (II) or (III) below, which can improve the uniformity of the coating, minimize the uniformity of the surface of the film, and control the process margin during development. Provided are new pigment dispersion photoresist (PDPR) compositions.

<Formula I>

<Formula II>

<Formula III>

Description

Photoresist composition for color filters containing low molecular weight silicone compound and method for producing same

The present invention relates to a photoresist composition. The present invention relates in particular to a photoresist composition for color filters comprising a low molecular weight silicone compound and a method for producing the same.

The materials of the color filter for liquid crystal display (LCD) should have high photosensitivity, excellent heat resistance and light resistance when forming fine patterns, high transmittance and good color reproducibility. Accordingly, it is important for pigment dispersed photoresist (PDPR) materials to have more excellent dispersibility and coating property, and in particular, the uniformity of the film during coating is a large part of the overall color filter manufacturing process. Efforts have been made to change the composition of photoresist materials currently used to achieve uniformity of the film. Moreover, when actually manufacturing color filters, it has been pointed out that it is very important to control the process development margin within a range that does not change the properties of the basic photoresist. Up to now, when manufacturing a color filter using a constant photoresist composition, in order to control the development time in the manufacturing process, the photoresist composition itself had to be newly formulated in order to obtain a pattern of the same characteristics. However, changing the proportion of the total composition to control process margins is not easy and requires considerable time and experimentation.

In the present invention, a low molecular weight material containing silicon is added to adjust the process margin and to increase the uniformity of the coated film within the range of maintaining the composition ratio of the photoresist used in the prior art to meet this requirement. The composition of the novel pigment dispersed photoresist (PDPR) will be described.

In general, when the surface tension of the film during coating in the coating is large, color defects, orange peel, Bernard cell, etc., surface defects are brought about, the silicone additive has been used as an antifoaming agent to reduce the surface defect by reducing the surface tension of the paint. In particular, it has been used to improve the properties of the surface because it is compatible with the composition in which a small molecular weight silicone additive is introduced. It is known to use the following silicone additives as adhesion enhancers with substrates in compositions of pigment dispersed color filter resists (US Pat. No. 5,368,976, EP 0645678A1).

Vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) 3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) 3 -Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) Ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane.

However, the above silicone additives were used for the purpose of improving adhesion to the substrate, and did not function to improve the stability during pattern formation by chemical reaction with the resin or the multifunctional monomer in the color resist composition.

The present invention comprises a silicone compound represented by the general formula (I), (II) or (III) below, which can improve the uniformity of the coating, minimize the uniformity of the surface of the film, and control the process margin during development. Provided are new pigment dispersion photoresist (PDPR) compositions.

<Formula I>

<Formula II>

<Formula III>

New composition using low molecular weight silicone additives directly bonded to hydrogen to disperse copolymers, multifunctional acrylic monomers, photoinitiators, and red, green and blue pigments to improve film uniformity and control process margins during development It provides a photosensitive color resist of.

The silicone additive of the present invention can improve the stability of the pattern through chemical reaction with the multifunctional monomer active by the photoinitiator to sufficiently increase the margin of the development process, and at the same time can significantly improve the nonuniformity of the pattern surface.

Details of the invention are as follows.

A. Synthesis of Binder Resin

1.Benzyl methacrylate (BzMA: benzyl methacrylate), methacrylic acid (MAA: methacrylic acid), and hydroxyethyl methacrylate (hydroxyethyl methacrylate) as monomers in PGMEA (propylene glycol methyl ether acetate) at 20% concentration It is dissolved and degassed with nitrogen gas.

2. The monomer solution was polymerized at 100 DEG C for 5 hours using 0.5 g of AIBN.

In the above monomer composition, the proportion of BzMA is 50% to 80%, the ratio of MAA is 5% to 40%, and the proportion of hydroxyethyl methacrylate is 5% to 40%. The molecular weight of the binder copolymer is 15,000 to 60,000, and the polydispersity index is preferably 2.4 or less.

Monomers used in the manufacture of binders are unsaturated ethylene carboxylic (sulphonic) acids based on acrylic acid, MAA, crotonic acid, itaconic acid, maleic acid, fumaric acid, monomethylmaleate, monomethyl fumarate, isoprensulphonic acid, styrenesulphonic acid Monomers copolymerizable therewith, such as α -methylstyrene, vinyltoluene, MMA, MA, EMA, EA, BuMA, BuA, HEMA, BzMA, BzA, and carboxylic acid vinyl esters (vinyl acetate, vinyl propionate). ), Vinyl cyanide (methacrylonitrile, α -chloroacrylonitrile) unsaturated ethylenecarboxylic acid and aminoalkyl ester (aminoethyl-acrylate), unsaturated fatty glycidyl ester (glycidyl methacrylate), and the like. And macromonomers having a terminal (meth) acryloyl group include polystyrenes having a terminal (meth) acrylate group and a terminal (meth) acryloyl group. Polymethyl (meth) acrylate, polybutyl (meth) acrylate having a terminal (meth) acryloyl group, and polysilicon having a terminal (meth) acryloyl group. Specific examples include MMA / MAA, MMA / sty / glycidyl MA, BzA / MAA / macromer, MMA / styy, BzMA / MAA / styy (65/25/10), BzMA / MAA / polymethylmacromer, etc. have.

Examples of the multifunctional monomers commonly used include functional (meth) acrylates such as polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, phenoxyethyl (meth) acrylate, and the like. As the acrylate, polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylol ethane triacrylate, trimethylol propane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, Pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate (PENA), hexanediol di (meth) acrylate, trimethylpropane tri (acryloyloxypropyl) ether, tri (acryloyloxy Ethyl) isocyanurate, tri (acryloyloxyethyl) -cyanurate, glycerin tri (meth) acrylic A.

Examples of the photopolymerization initiator include diacetyl, benzyl, benzoin, 2-hydroxy-2-methyl-1-phenylpropan-1-one, and 1- (4-isopropylphenyl) -2-hydroxy-2 based on carbonium compounds. -Methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl-2- (hydroxy-2-propyl) ketone, 1-hydroxychlorohexyl ketone, 2,2-dimethoxy-2-phenyl Acetophenone, 2-methyl [4- (methylthio) phenyl] -2-morpholino-1-propan-1-one, 4,4'-bis (dimethylamino) benzo-phenone, 4,4'-bis (Diethylamino) benzophenone, 2,4-diethyl thioxanthone, 3,3-dimethyl-4-methoxybenzophenone, and azo and azide compounds include azobisbutyronitrile, diazonium, 4- Azidobenzalacetophenone, 4-azidobenzalacetone, azidopyrene, 4-azidophenylamine, 4-diazido-4'-methoxydiphenylamine, 4-diazo-3'-methoxydi-phenylamine Examples of the organosulfur compound include mercaptan disulfide and diethyl eta peroxide as a peroxide. Trichloromethane compounds include trichloromethyl-s-triazine, 2- (2'-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine and 2- (p-meth Methoxyphenyl) -4,6, -bis (trichloromethyl) -s-triazine, 2-phenyl-4,6-bis (chloromethyl) -s-triazine, 2- (p-chlorophenyl) -4 , 6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy-1-naphthyl) -4,6-bis (trichloromethyl) -s-triazine, and imidazole series Examples thereof include 2- (2,3-dichlorophenyl) -4,5-diphenylimidazole dimer.

As the pigment, red pigment 97, 122, 149, 168, 177, 180, 192, 215, yellow pigment 83, 139, green pigment 7,36, blue pigment 15: 1, 15: 3, 15: 4, 15: 6, 22, 60, 64, purple pigment 23 and the like.

Solvents used include alcohols such as methanol, ethyl alcohol, n-propanol, iso-propanol, and cellosolves such as methyl cellosolve, ethyl cellosolve, and carbitol diethylene glycol methyl ether and diethylene glycol. Ethyl ether and ether type include ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, ethyl acetate, propylene glycol methyl ether acetate and the like. Ketones include acetone, methyl isobutyl ketone, cyclohexanone, and the like. Cellosolve acetates include methyl cellosolve acetate, ethyl cellosolve acetate, and carbitol acetate-based diethylene glycol methyl (or ethyl) acetate. Ether types include diethyl ether, ethylene glycol dimethyl ether, diglyme, THF, aprotic amides as DMF, N, N-dimethylacetamide, NMP, lactone as t-butyro Lactones and aromatic hydrocarbons include benzene, toluene, silane and naphthalene, and saturated hydrocarbons include hexane, heptane, n-octane and the like.

Among the silicone additives that may be used for the purposes of the present invention are silicon compounds 1,1,3,3-tetraalkyl disiloxane (R = C1-C3), 1,1,4,4-tetraalkyl disilethylene (R = C1 -C3), 1,1,3,3,5,5,7,7-octaalkyl tetrasiloxane (R = C1-C3), molecular weight having a structure in which a hydrogen group is directly connected to silicon, between 100 and 1,000 Of things.

B. Photoresist Composition Preparation

A color resist material was prepared using the binder resin synthesized in Example 1. About 10 to 40% by weight of the solid content except the solvent in the total resist composition, about 5 to 35% of the organic pigment, and about 5 to 30% of the resin are suitable. About 1 to 10% of photocrosslinkable multifunctional acrylic monomer and about 0.1 to 5% of photoinitiator are suitable. The above components are placed in a bead mill or triple roll mill and the pigment is dispersed while mixing for about 3 to 20 hours. Bead size was 0.3 to 3 mm in diameter, and after filtering, the solution was filtered with a 10 micron filter and stored in a UV-blocked room for about 10 days.

In the experiment which adds a silicon compound, it adds and stirred to a stable solution. The solution is spin coated onto glass and heated to about 70-100 ° C. for 2-10 minutes to form a homogeneous film about 2 mm thick. After exposing the film to a high pressure mercury lamp using a photomask with an energy of 100 to 300 mJ / cm 2, the pattern is developed with an alkaline solution, washed with deionized water, and then heated at 150 to 200 ° C. for about 40 to 60 minutes. . The thickness of the final formed film was measured with Alpha-Step 500, and the state of the surface was observed with an optical microscope.

Comparative Example 1

Photosensitive material

In the above case, the proper development time during pattern formation took an average of about 30 seconds for an alkaline solution of pH 12.0. The thickness of the film averaged 2.3 mm and the planar thickness change showed a value of about 3.0% (0.16 mm). The uniformity of the surface was about 0.03 mm. When the over develop time exceeded 20 seconds, the size of the formed pattern itself changed, and the uniformity of the surface rapidly increased, and defects began to occur.

<Example 2>

Photosensitive material

In the above formula, a silicon compound was added to form a film in the same manner as in Comparative Example 1. The film formed a stripe-free film with an average coating thickness of 2.24 mm, a planar thickness change of 0.5% (0.022 mm), and uniformity of about 0.01 mm, showing very improved properties. The development time in pattern formation showed an average of 45 seconds at pH 12.0. Even after 90 seconds of over developing time, the shape of the pattern was stable and the uniformity of the surface was not significantly different.

<Example 3>

Photosensitive material

In the same manner, the film obtained after coating had an average thickness of 2.23 mm, a planar thickness change of about 0.5% (0.023 mm), and a uniformity of surface showing a value of about 0.01 mm. The developing time was about 57 seconds for the developer at pH 12.0. No streaks could be observed on the surface. Even after the over developing time was over 110 seconds, the shape of the pattern was stable and the uniformity of the surface was not significantly different.

<Example 4>

Photosensitive material

In the same manner, the film obtained after coating had an average thickness of 2.24 mm, a planar thickness change of about 0.55% (0.024 mm), and a uniformity of the surface showing a value of about 0.011 mm. The developing time was about 62 seconds for the developer at pH 12.0. No streaks could be observed on the surface. Even when the over developing time was over 105 seconds, the pattern was stable and the uniformity of the surface was not significantly different.

Example 5

Photosensitive material

In the same manner, the film obtained after coating had an average thickness of 2.16 mm, a planar thickness change of about 0.47% (0.022 mm), and a stripe on the surface showing a value of about 0.012 mm. The development time of the developer at pH 12.0 was about 51 seconds, but the development time was slightly reduced. No streaks could be observed on the surface. The overdeveloping time was stable until 80 seconds, and the uniformity of the surface was not significantly different.

<Example 6>

Photosensitive material

In the same manner, the film obtained after coating had an average coating thickness of 2.23 mm, a planar thickness change of 0.5% (0.023 mm), and uniformity of about 0.011 mm. The development margin at the time of pattern formation was an average of 43 seconds at pH 12.0. Even after the over developing time of 87 seconds, the shape of the pattern was stable, and the uniformity of the surface was not significantly different.

<Example 7>

Photosensitive material

In the same manner, the film obtained after coating had an average thickness of 2.23 mm, a planar thickness change of about 0.5% (0.023 mm), and a uniformity of surface showing a value of about 0.009 mm. The developing time was about 55 seconds for the developer at pH 12.0. No streaks could be observed on the surface. Even after the over developing time of 114 seconds, the shape of the pattern was stable, and the uniformity of the surface was not significantly different.

<Example 8>

Photosensitive material

In the same manner, the film obtained after coating had an average thickness of 2.22 mm, a planar thickness change of about 0.5% (0.022 mm), and a uniformity of surface showing a value of about 0.01 mm. The developing time of the developer at pH 12.0 was about 61 seconds. No streaks could be observed on the surface. Even after the over developing time of 125 seconds, the shape of the pattern was stable, and the uniformity of the surface was not significantly different.

Example 9

Photosensitive material

In the same manner, the film obtained after coating had an average thickness of 2.23 mm, a planar thickness change of about 0.4% (0.02 mm), and a flatness of the surface showing a value of about 0.01 mm. The developing time was about 50 seconds for the developer of pH 12.0. No strips could be observed on the surface. The overdeveloping time was stable until the pattern passed 86 seconds, and there was no significant difference in the uniformity of the surface.

<Example 10>

Photosensitive material

The average coating thickness of the film obtained by the same method was 2.2 mm, the change in plane thickness was 0.45% (0.02 mm), and the uniformity showed a value of about 0.01 mm. The development margin at the time of pattern formation was an average of 43 seconds at pH 12.0. Even after 85 seconds of over developing time, the shape of the pattern was stable and the uniformity of the surface was not significantly different.

<Example 11>

Photosensitive material

In the same manner, the film obtained after coating had an average thickness of 2.23 mm, a planar thickness change of about 0.45% (0.022 mm), and a uniformity of surface showing a value of about 0.01 mm. The developing time was about 56 seconds for the developer at pH 12.0. No streaks could be observed on the surface. Even after the over developing time was over 110 seconds, the shape of the pattern was stable and the uniformity of the surface was not significantly different.

<Example 12>

Photosensitive material

In the same manner, the film obtained after coating had an average thickness of 2.2 mm, a planar thickness change of about 0.5% (0.022 mm), and a uniformity of the surface showing a value of about 0.01 mm. The developing time was about 60 seconds for the developer at pH 12.0. No streaks could be observed on the surface. Even after the over developing time of 124 seconds, the shape of the pattern was stable, and the uniformity of the surface was not significantly different.

Example 13

Photosensitive material

In the same manner, the film obtained after coating had an average thickness of 2.18 mm, a planar thickness change of about 0.46% (0.022 mm), and a uniformity of the surface showing a value of about 0.01 mm. The developing time was about 49 seconds for the developer of pH 12.0. No streaks could be observed on the surface. The pattern was stable until the over developing time passed 90 seconds, and the uniformity of the surface was not significantly different.

Comparative Example 2

In the same manner, the film obtained after coating had an average thickness of 2.4 mm, a planar thickness change of about 5% (0.24 mm), and a uniformity of surface showing a value of about 0.04 mm. The developing time was about 44 seconds for the developer at pH 12.0. No streaks could be observed on the surface. When the over develop time exceeded 24 seconds, the size of the formed pattern itself changed and the uniformity of the surface rapidly increased, and defects began to occur.

<Example 14>

Photosensitive material

In the same manner, the film obtained after coating had an average thickness of 2.38 mm, a planar thickness change of about 0.42% (0.024 mm), and a uniformity of surface showing a value of about 0.014 mm. The developing time was about 64 seconds for the developer at pH 12.0. No streaks could be observed on the surface. The pattern was stable until the over developing time passed 120 seconds, and the uniformity of the surface was not significantly different.

Comparative Example 3

Photosensitive material

In the same manner, the film obtained after coating had an average thickness of 2.0 mm, a planar thickness change of about 3.75% (0.15 mm), and a uniformity of surface showing a value of about 0.035 mm. The developing time was about 22 seconds for the developer at pH 12.0. No streaks could be observed on the surface. When the excess developing time exceeded 14 seconds, the size of the formed pattern itself changed, and the uniformity of the surface rapidly increased, and defects began to occur.

<Example 15>

Photosensitive material

In the same manner, the film obtained after coating had an average thickness of 2.0 mm, a planar thickness change of about 0.5% (0.02 mm), and a flatness of the surface showing a value of about 0.01 mm. The development time was about 46 seconds for the developer at pH 12.0. No streaks could be observed on the surface. The pattern was stable until the over developing time of 96 seconds and the surface uniformity was not significantly different.

Use of the photoresist composition for the photosensitive color filter of the present invention can improve the stability of the pattern and improve the uniformity of the pattern surface.

Claims (12)

In a photoresist composition, a) a silicone compound represented by formula I below; b) binder copolymers; c) multifunctional monomers; d) photoinitiators; And e) pigments of red, rust and blue Photoresist composition for a photosensitive color filter comprising: <Formula I> here, n is an integer from 0 to 12, R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon substituent having 1 to 6 carbon atoms. The method of claim 1, The binder copolymer has a molecular weight of 15,000 to 60,000 and a polydispersity index of 2.4 or less. The method of claim 1, Wherein said photoinitiator is a carbonium compound, an azide compound, an organic sulfur compound, a peroxide, a trihalomethane compound, an imidazole compound, or a mixture thereof. The method of claim 1, Composition comprising propylene glycol methyl ether acetate (PGMEA) as a solvent. In a photoresist composition, a) a silicone compound represented by formula II below; b) binder copolymers; c) multifunctional monomers; d) photoinitiators; And c) pigments of red, rust and blue Photoresist composition for a photosensitive color filter comprising: <Formula II> here, n is an integer from 0 to 12, R ₁ and R ₂ each independently represent a hydrogen atom or a hydrocarbon substituent having 1 to 6 carbon atoms. The method of claim 5, The binder copolymer has a molecular weight of 15,000 to 60,000 and a polydispersity index of 2.4 or less. The method of claim 5, Wherein said photoinitiator is a carbonium compound, an azide compound, an organic sulfur compound, a peroxide, a trihalomethane compound, an imidazole compound, or a mixture thereof. The method of claim 5, Composition comprising propylene glycol methyl ether acetate (PGMEA) as a solvent. In a photoresist composition, a) a silicone compound represented by formula III below; b) binder copolymers; c) multifunctional monomers; d) photoinitiators; And e) pigments of red, rust and blue Photoresist composition for a photosensitive color filter prepared by dispersing; <Formula III> N is an integer of 4-7 here. The method of claim 9, The binder copolymer has a molecular weight of 15,000 to 60,000 and a polydispersity index of 2.4 or less. The method of claim 9, Wherein said photoinitiator is a carbonium compound, an azide compound, an organic sulfur compound, a peroxide, a trihalomethane compound, an imidazole compound, or a mixture thereof. The method of claim 9, Composition comprising propylene glycol methyl ether acetate (PGMEA) as a solvent.