KR101119818B1 - Photoresist composition for colour filter and preparation method of liquid crystal display colour filter using the same - Google Patents

Abstract

The present invention relates to a photosensitive resin composition for color filters and a method of manufacturing a liquid crystal display color filter using the same, and more particularly, to a polyalkylene oxide methylsilane polymer, a polyether modified dimethylpolysiloxane polymer solution, and a polyether modified. Including a silicon-based surface additive selected from the group consisting of dimethylpolysiloxane polymers to minimize the unnecessary portion generated at the edge portion of the resist film rotated on the substrate in the TFT and STN-type LCD manufacturing process and to improve the coating and leveling The manufacturing method of the color filter photosensitive resin composition and the liquid crystal display color filter using the said photosensitive resin composition for color filters.

Photosensitive resin composition, color filter

Description

Photosensitive resin composition for color filter and manufacturing method of liquid crystal display color filter using same {PHOTORESIST COMPOSITION FOR COLOR FILTER AND PREPARATION METHOD OF LIQUID CRYSTAL DISPLAY COLOUR FILTER USING THE SAME}

The present invention relates to a photosensitive resin composition for color filters and a method for manufacturing a liquid crystal display color filter using the same, and particularly, to minimize unnecessary edges (Edge Beads (EB)) generated at the edges of a resist film that is rotated and coated on a substrate in an LCD manufacturing process. And it relates to a photosensitive resin composition for color filters that can improve the coating properties and leveling of the resist and a method of manufacturing a transmissive, reflective or semi-transmissive liquid crystal display color filter using the same.

As a method of forming a color filter of a liquid crystal display, a printing method, an electrodeposition method, an ink-jet method, a pigment dispersion method, and the like have been conventionally used, but in recent years, a pigment for easy pattern resolution and a manufacturing method is easily used. A distributed method is adopted, and this method is applied to manufacturing LCDs of mobile phones, laptops, monitors, and TVs.

Recently, even in the pigment-dispersion type coloring composition having various advantages, not only the fineness of the pattern but also the improved performance are required. That is, a general pigment dispersion type coloring composition is applied to a substrate and exposed to develop to form a colored pixel. In this case, the pigment is not dissolved even in a developer by appropriate curing in the exposed pixel.

In this TFT-LCD process, color resists (R, G, B) are applied onto a glass substrate, and the exposure and development processes are sequentially performed. In general, equipment contamination during the movement of the applied substrate, and difficulty in ensuring alignment during the exposure process are performed. And, after the development process, problems such as the remaining of the EB portion due to the thick film thickness, which cannot be developed completely, can be solved. Edge Bead Remover process

Recently, however, in the STN or TFT-LCD process, a method of omitting the EBR process is preferred due to the simplification of the number of processes. If the EBR treatment step is omitted, at least three to four times the EBR treatment step may not be performed in the color filter manufacturing process, thereby simplifying the entire manufacturing process and saving manufacturing time, and the thinner composition used in the EBR treatment process. The cost savings associated with the non-use of this product and the environmentally friendly manufacturing process can be brought closer.

In order to omit the EBR treatment process, the unnecessary film portion generated at the edge portion of the resist film during rotation application should be minimized (width, thickness) to prevent the occurrence of unnecessary film within the general developing process time even without the EBR process. . In addition, as the size of the substrate is gradually increasing, it is required to minimize the coated film step and improve the coating property when coating the color resist, and to improve the color resist composition based thereon.

However, the conventional photosensitive resin composition has a problem that the width and thickness of the EB is considerable, so that the EB part may not be completely removed in the general developing process without the EBR process.

In order to solve the above-mentioned problems, the present invention improves and changes the rheological properties, thereby minimizing unnecessary EB portions generated at the edges of the resist film rotated on the substrate, and improving the coating property and the leveling of the photoresist. The purpose is to provide.

In addition, the present invention can improve the coating properties, minimize the unnecessary EB portion generated in the edge portion of the resist film rotated on the substrate to omit the EBR process when manufacturing the liquid crystal display color filter, thereby significantly reducing the manufacturing cost It is an object of the present invention to provide a method for manufacturing a liquid crystal display color filter.

In order to achieve the above object, the present invention, in the photosensitive resin composition for color filters, the polyalkylene oxide methyl silane polymer, polyether modified dimethylpolysiloxane polymer solution and polyether modified dimethylpolysiloxane polymer It provides a photosensitive resin composition for color filters, characterized in that it comprises at least one silicon-based surface additive selected.

The present invention also provides a method for producing a liquid crystal display color filter comprising the step of applying the photosensitive resin composition for color filters to a substrate.

Hereinafter, the present invention will be described in detail.

The photosensitive resin composition for color filters of the present invention may include at least one silicone surface additive selected from the group consisting of a polyalkylene oxide methylsilane polymer, a dimethylpolysiloxane polymer solution modified with polyether, and a dimethylpolysiloxane polymer modified with polyether. It is characterized by. The silicon-based surface additive induces a reduction in surface tension during rotational coating on a substrate to have good wettability and stain prevention on the substrate. The content of the silicon-based surface additive is preferably used 0.1 to 2% by weight based on the total composition. If the content of the additive is less than 0.1% by weight, uniform coating is not performed well on the entire substrate during coating, and when the content of the additive exceeds 2% by weight, the occurrence of stains during coating increases. Preferably the molecular weight of the polymer is preferably from 1,000 to 100,000, more preferably from 3,000 to 10,000. In addition, the solvent of the silicon-based surface additive is preferably in the form of a solvent or phenoxy ethanol / xylene.

Examples of preferred photosensitive resin compositions for color filters of the present invention include: a) alkali-soluble binders, b) crosslinkable monomers having at least two or more ethylenic double bonds, c) pigments, d) photopolymerization initiators, e) silicone-based Surface additives and, e) solvents.

In the photosensitive resin composition for color filters of the present invention, the a) alkali-soluble binder is preferably a copolymer of a monomer having an ethylene acidic group and a monomer having no ethylene acidic group in the polymer chain.

The monomer having an ethylenic acid group may be in the form of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl acetic acid or an acid anhydride thereof, or 2-acryloxyethyl hydrogen phthalate, 2-acryloxyoxypropyl hydrogen Phthalate, 2-acrylooxypropylhexahydrogen phthalate, and the like, and these may be used alone or in combination of two or more thereof. The content of the monomer having an ethylenic acid group is preferably 10 to 40% by weight of the alkali-soluble binder, more preferably 15 to 35% by weight. If the content of the monomer having an acidic group is less than 10% by weight, the solubility of the photosensitive resin composition in the alkaline developer tends to be lowered, and if it exceeds 40% by weight, the dropping and tearing of the pattern occurs during development by the alkaline developer. .

In addition, examples of the monomer having no acidic group include isobutyl acrylate, t-butyl acrylate, lauryl acrylate, alkyl acrylate, steacrylate, cyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, 2- Hydroxyacrylate, trimethoxybutyl acrylate, ethylcarbitol acrylate, phenoxyethyl acrylate, 4-hydroxybutyl acrylate, phenoxy polyethylene glycol acrylate, 2-hydroxyethyl acrylate, hydroxy Ethyl cinnamic acrylate, 2-hydroxypropyl acrylate, 2-acryloxyethyl 2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxy propyl acrylate and their methacrylates; Acrylates containing halogen compounds such as 3-fluoroethyl acrylate and 4-fluoropropyl acrylate and methacrylates thereof; Acrylates containing siloxane groups such as triethylsiloxane ethyl acrylate and methacrylates thereof; Olefins having aromatics such as styrene and 4-methoxystyrene, and the like, and these may be used alone or in combination of two or more thereof.

The content of the monomer having no acidic group is preferably from 60 to 90% by weight of the alkali-soluble binder, more preferably from 65 to 85% by weight. If the content of the monomer having no acidic groups is less than 60% by weight, the adhesion to the substrate is reduced during the development process, so that the pattern tearing is severe and the straightness of the formed pattern is deteriorated. The rate of dissolution is reduced, resulting in longer development time.

The content of the alkali-soluble binder is preferably used in 5 to 40% by weight based on the total photosensitive resin composition.

In the photosensitive resin composition of the present invention, b) 1,4-butadiol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol as a crosslinkable monomer having at least two or more ethylenic double bonds Diacrylate, pentaerythritol tetraacrylate, triethylene glycol diacrylate, polyethylene glycol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, trimethyl propane triacrylate, dipentaerythritol diacrylate, dipenta Erythritol hexaacrylate and these methacrylates. The content of the crosslinkable monomer having at least two or more ethylenic double bonds is preferably 5 to 30% by weight, more preferably 5 to 20% by weight based on the total photosensitive resin composition. When the content of the crosslinkable monomer is less than 5% by weight, it is difficult to realize a pattern due to low curing degree with the photosensitive resin. When the content of the crosslinkable monomer exceeds 30% by weight, the viscosity of the resist composition is excessively increased and the dissolution rate in the alkaline developer is increased. It becomes so fast that the resistance to the developer is significantly lowered even in the exposed portion.

In addition, in the photosensitive resin composition of the present invention, c) pigment may be used both organic pigments and inorganic pigments, specific examples of such organic pigments are C.I. Pigment Yellow 83, C.I. Pigment Yellow 150, C.I. Pigment Yellow 138, C.I. Pigment Yellow 128, C.I. Pigment Orange 43, C.I. Pigment Red 177, C.I. Pigment Red 202, C.I. Pigment Red 209, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Green 7, C.I. Pigment Green 36, C.I. Pigment Blue 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Violet 23, C.I. Pigment Black 1, C.I. Pigment black 7 and the like. Examples of the inorganic pigments include titanium oxide, titanium black and carbon black. These pigments can be used 1 type or in mixture of 2 or more types in order to make color tone sum. The content of the pigment is preferably used in 10 to 60% by weight based on the total photosensitive resin composition.

Moreover, in the photosensitive resin composition of this invention, d) a photoinitiator is a compound which can start superposition | polymerization of the said crosslinkable monomer by wavelengths, such as visible light, an ultraviolet-ray, and a far infrared ray. As the photopolymerization initiator, one or more selected from the group consisting of triazine compounds, acetophenone compounds, xanthone compounds, benzoin compounds and imidazole compounds may be used.

Specific examples of the triazine-based compound include 2,4-bistrichloromethyl-6-p-methoxystyryl-s-triazine and 2-p-methoxystyryl-4,6-bistrichloromethyl-s -Triazine, 2,4-trichloromethyl-6-triazine, 2- (2-bromo-4-methylphenyl) -4,6-bis (trichloromethyl) -s-triazine and the like. However, in the case of the triazine-based initiator, the sensitivity to light is high, and thus the sensitivity is excellent. However, a halogen gas may be generated during exposure to contaminate a device such as a mask and have a unique yellow color. Can be lowered. Therefore, the content of the triazine initiator is preferably used in less than 1% by weight of the total photosensitive resin composition.

In addition, specific examples of the acetophenone-based compound include benzophenone, p- (dimethylamino) benzophenone, 2,2-dichloro-4-phenoxycetophenone, 4,4-bisdiethylaminobenzophenone, 2,2- Diethoxyacetophenone, 2,2-dibutoxyacetophenone, 2-hydroxy-2-methylproriophenone, pt-butyltrichloroacetophenone, and the like. Specific examples of the xanthone-based compound include xanthone, thioxanthone, 2-methyl thioxanthone, 2-isobutyl thioxanthone, 2-dodecyl thioxanthone, and 2,4-dimethyl thioxanthone. In addition, specific examples of the benzoin-based compound include compounds such as benzoin, benzoin ethyl ether, benzoin methyl ether, benzoyl propyl ether, t-butyl benzoyl ether and the like. In addition, specific examples of the imidazole compound include 2,2-bis-2-chlorophenyl-4,5,4,5-tetraphenyl-2-1,2-biimidazole, 2,2-bis (2,4 And compounds such as 6-tricyanophenyl) -4,4,5,5-tetraphenyl-1,2-biimidazole.

The photopolymerization initiator may be mixed with a sensitizer, a curing accelerator, and the like as necessary, and specific examples thereof include 4-dimethylamino benzophenone, isopropyl thioxanthone, methyl-o-benzoylbenzoate, and 4- (methylphenylthio). Compounds, such as -phenyl- phenylmethane, 2, 4- diethyl thioxanthone, 2-chloro thioxanthone, benzophenone, and ethyl anthraquinone, can be used.

The content of the photopolymerization initiator is preferably 0.5 to 5% by weight, more preferably 1 to 2% by weight based on the photosensitive resin composition. If the content of the photopolymerization initiator is less than 0.5% by weight, it is difficult to implement a normal pattern due to the low sensitivity, and it is not good for the straightness of the pattern. If the content is more than 5% by weight, the embossing occurs on the surface of the pattern, or it is soluble in a solvent. And storage stability may cause problems

Moreover, in the photosensitive resin composition for color filters of this invention, e) The said silicone type surface additive is as having defined above. In addition, it may further include a dispersant for improving the dispersibility with the pigment or an additive for improving the coating property, the content of these additives may be used in 0.1 to 2% by weight based on the total photosensitive resin composition for color filters.

In addition, in the photosensitive resin composition for color filters of the present invention, the bar) solvent is selected by solubility, pigment dispersibility and coating properties, specifically, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol mono Methyl ether acetate, propylene glycol methyl monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclonucleanone, 3-methoxypropionate, methyl 3-ethoxypropionate, 3-ethoxypropionate ethyl Etc. are preferable, and these can be used individually or in mixture of 2 or more types. The amount of the solvent is included in the remaining amount excluding the above-described components, preferably 20 to 70% by weight based on the total photosensitive resin composition.

In another aspect, the present invention provides a method for producing a liquid crystal display color filter comprising the step of applying the photosensitive resin composition for color filters to a substrate, before and after the process of applying the photosensitive resin composition for color filters to the substrate Of course, the processes used in the conventional manufacturing method of the color filter can be applied. In particular, the manufacturing method of the liquid crystal display color filter of the present invention can improve the coating property, and minimize the unnecessary EB portion generated at the edge of the resist film rotated on the substrate to omit the EBR process when manufacturing the liquid crystal display color filter. As a result, manufacturing costs can be significantly reduced.

Hereinafter, the present invention will be described in detail based on the following examples, but the present invention is not limited to the following examples. In the following examples, unless stated otherwise, percentages and mixing ratios are by weight.

Example 1

A) Copolymer of benzyl methacrylate / methacrylic acid / hydroxyethyl cinnamic acrylate as an alkali-soluble binder (copolymerization ratio is 60/20/20 under the solution of propylene glycol methyl ether acetate and the solid content is 35% by weight Copolymer having a weight average molecular weight of 30,000) 25% by weight, b) 5% by weight of dipentaerythritol hexaacrylate as a crosslinkable monomer having at least two or more ethylenic double bonds, and c) Pigment Red 254 as a pigment. And CI Pigment Yellow 138 22% by weight, d) 1% by weight of Irgacure369 (manufactured by Ciba Specialty Chemical) as a photopolymerization initiator, 0.5% by weight of 4,4-bisdiethylaminobenzophenone and 0.5 of 2,4-diethylthioxanthone Wt%, e) dimethylpolysiloxane polymer solution and polyoxyalkylene thymethylenepolysiloxane polymer solution in which polyether is modified as a silicone-based surface additive (where the two types are The additive-containing component ratio is 1: 1) and, f) a solvent containing a mixed solvent in which propylene glycol methyl ether acetate and cyclohexanone are mixed 3: 1 as a residual amount, and then mixed to mix the photosensitive resin for liquid color filters. The composition was prepared.

[Example 2]

Prepared in the same composition and content as Example 1, e) 0.5 wt% of a dimethylpolysiloxane polymer solution in which polyether was modified as a silicone-based surface additive was mixed to prepare a photosensitive resin composition for a liquid color filter.

Example 3

Prepared in the same composition and content as in Example 1, e) 0.5 wt% of a polyoxyalkylene thymethylenepolysiloxane polymer was mixed as a silicone-based surface additive to prepare a photosensitive resin composition for a color filter in a liquid state.

Example 4                     

Prepared in the same composition and content as in Example 1, e) 0.2 wt% of a dimethylpolysiloxane polymer modified with polyether as a silicone-based surface additive was mixed to prepare a photosensitive resin composition for a color filter.

Comparative Example 1

Prepared in the same composition and content as in Example 1, e) A photosensitive resin composition was prepared using 0.5 wt% of BYK-340 (manufactured by BYK-Chemi), a fluorine-based additive, in place of the silicon-based surface additive.

Comparative Example 2

The photosensitive resin composition was manufactured by using the same composition and content as Example 1, but using 0.5 wt% of BYK-354 (manufactured by BYK-Chemi), an acrylate-based additive, in place of the silicone-based surface additive.

[Coating Characteristics Comparison]

The coating properties of Examples 1 to 4 and Comparative Examples 1 and 2 obtained by changing the type and content of the silicon-based and non-silicone-based additives were compared.

Experimental method was carried out by coating the photosensitive resin composition obtained in Examples 1 to 4 and Comparative Examples 1 and 2 by dropping 0.8 cc on a glass substrate and rotating the coating at 300 rpm, and then drying through a prebak on a 90 ° C. hot plate. A film was obtained and the thickness and width of the unnecessary EB portion of the edge of the spin coated substrate were measured. The measured results are shown in Table 1 below.

[Table 1]

EB width (mm) EB film thickness (um) Coating Stain condition after coating Example 1 2.5 to 3.0 2.6 ○  Good (no stain) Example 2 3.3 to 3.7 3.3 ○ Good (no stain) Example 3 3.0 to 3.5 3.0 ○ Good (no stain) Example 4 2.7 to 3.2 3.4 ○ Good (no stain) Comparative Example 1 4.5 to 5.2 5.2 △ Slight staining Comparative Example 2 5.5 to 6.0 4.6 △ Slight staining

    As shown in Table 1, in Examples 1 to 4, the width and thickness of the edge unnecessary film portion (EB) of the coated substrate were relatively reduced in comparison with Comparative Examples 1 and 2, and the overall film after coating The state was also in a good state in which most coating spots were not seen. On the contrary, in the case of Comparative Examples 1 and 2, the EB width and the film thickness were observed to be two times larger than those of Example 1, and some coating stains were observed during the coating. These comparative examples 1 and 2 have a thick thickness of the EB portion, which disadvantageously complete removal of the resist film in a general developing process. Therefore, it can be seen that the application performance at the time of rotational coating is superior in the case of Examples 1 to 4 compared with Comparative Examples 1 and 2.

As described above, the photosensitive resin composition for color filters of the present invention may improve and change the rheological properties, thereby minimizing unnecessary EB portions generated at the edge portions of the resist film rotated on the substrate, and improving coating property and leveling. The method for manufacturing a liquid crystal display color filter using the photosensitive resin composition for color filters improves coating properties and minimizes unnecessary EB portions generated at the edges of a resist film rotated on a substrate, thereby producing an EBR process in manufacturing a liquid crystal display color filter. Can be omitted, thereby significantly reducing the manufacturing cost.

Claims (11)

In the photosensitive resin composition for color filters, A) 5 to 40% by weight of an alkali-soluble binder which is a copolymer of 10 to 40% by weight of monomer having ethylene-based acidic groups and 90 to 60% by weight of monomer having no ethylene-based acidic groups; B) 5 to 30% by weight of a crosslinkable monomer having at least two ethylenic double bonds; C) 10 to 60% by weight of pigment; D) 0.5 to 5 wt% of a photopolymerization initiator; E) 0.1 to 2% by weight of at least one silicone-based surface additive from the group consisting of a polyalkylene oxide methylsilane polymer, a polyether modified dimethylpolysiloxane polymer solution and a polyether modified dimethylpolysiloxane polymer; And F) residual solvent Photosensitive resin composition for color filters comprising a. delete delete delete The method of claim 1, The monomer having an ethylenic acid group may be in the form of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, vinyl acetic acid or acid anhydrides thereof; 2-acrylooxyethylhydrogenphthalate; 2-acrylooxypropylhydrophthalphthalate; And 2-acrylooxypropylhexahydrophthalphthalate. The photosensitive resin composition for color filters, characterized in that at least one member is selected. The method of claim 1, Monomers having no ethylenic acid group are isobutyl acrylate, t-butyl acrylate, lauryl acrylate, alkyl acrylate, steacrylate, cyclohexyl acrylate, isobornyl acrylate, benzyl acrylate, 2-hydrate Hydroxyacrylate, trimethoxybutyl acrylate, ethylcarbidol acrylate, phenoxyethyl acrylate, 4-hydroxybutyl acrylate, phenoxy polyethylene glycol acrylate, 2-hydroxyethyl acrylate, hydroxyethyl Cinnamic acrylate, 2-hydroxypropyl acrylate, 2-acryloxyethyl 2-hydroxypropyl phthalate, 2-hydroxy-3-phenoxypropyl acrylate and methacrylates thereof; Acrylates containing halogen compounds and methacrylates thereof; And at least one member selected from the group consisting of acrylates and methacrylates thereof including siloxane groups. The method of claim 1, B) 1,4-butanediol diacrylate, 1,3-butylene glycol diacrylate, ethylene glycol diacrylate, pentaerythritol tetraacrylate, or tri-crosslinkable monomer having at least two ethylenic double bonds; Ethylene glycol diacrylate, polyethylene glycol diacrylate, dipentaerythritol diacrylate, sorbitol triacrylate, bisphenol A diacrylate derivative, trimethyl propane triacrylate, dipentaerythritol polyacrylate, and methacryl thereof At least 1 type is selected from the group which consists of a latex, The photosensitive resin composition for color filters characterized by the above-mentioned. The method of claim 1, (C) The photosensitive resin composition for color filters, wherein the pigment is an organic pigment or an inorganic pigment. The method of claim 1, (D) the photopolymerization initiator is at least one selected from the group consisting of triazine compounds, acetophenone compounds, xanthone compounds, benzoin compounds, and imidazole compounds. The method of claim 1, Bar) The solvent is ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 3- At least one selected from the group consisting of ethyl methoxy propionate, methyl 3-ethoxypropionate, and ethyl 3-ethoxypropionate is a photosensitive composition for color filters. A method for manufacturing a liquid crystal display color filter, comprising the step of applying the photosensitive resin composition for color filters according to any one of claims 1 and 5 to 10 to a substrate.