KR20040053964A - Radiation curing resin composition for color filter - Google Patents

Abstract

PURPOSE: A radiation curing resin composition for a color filter is provided to improve heat resistance, sensitivity, transparency and coating drying property, thereby preventing the discoloration and deformation of a resin even at a high temperature and the deterioration of light transmitting property. CONSTITUTION: The radiation curing resin composition comprises a polymer binder comprising a photopolymerizable prepolymer represented by the formula 1; a photopolymerizable compound; a photopolymerization initiator; a pigment; and an organic solvent, wherein R1, R2, R3, R4 and R5 are H or an alkyl group of C1-C10; and n is an integer of 0-100. Preferably the content of the photopolymerizable prepolymer of the formula 1 is 0.1-50 wt% based on the weight of the total resin composition. Also the polymer binder comprises a mixture of the photopolymerizable prepolymer and an acid monomer; a copolymer of the photopolymerizable prepolymer and an acid monomer; or a mixture of a homopolymer of the photopolymerizable prepolymer and a homopolymer of an acid monomer.

Description

Photocurable resin composition for color filters {RADIATION CURING RESIN COMPOSITION FOR COLOR FILTER}

The present invention relates to a photocurable colored resin composition used in the production of color filters for fine color separation such as color developing elements, color sensors, color displays, and the like.

Color filters are widely used in flat panel display devices, liquid crystal displays (LCDs), field emission displays (FELs), and electroluminescent displays (ELDs). Among them, LCD (liquid crystal displays), which are technology-intensive items in which liquid crystal and semiconductor technologies are combined, in particular, As a component of Liquid Crystal Display), the application range of the monitor of the notebook PC, the medical apparatus such as the X-ray measuring instrument, the LCD-TV, the automobile navigator, etc. is rapidly expanding. In this situation, to achieve the development of the TFT-LCD (Thin Film Transistor-LCD) industry and the generalization of its applications, many other components that make up the LCD, namely liquid crystal materials, backlights, polarizer films, compensation As with films, transparent substrates, alignment films, and spacers, there is a need for high quality and high functionalization of polymers that are frequently used as materials in the fabrication of components.

The color of the LCD is to pass the white light from the backlight through the liquid crystal cell to adjust the transmittance, and then the light from the adjacent red (R), green (G) and blue (B) color filters. It is made up of mixed colors. The substrate of the color filter is composed of a color filter that implements color and a black matrix that distinguishes between R, G, and B cells and serves to block light, and a transparent electrode for applying a voltage to the liquid crystal cell. . The color filter is divided into a dye method and a pigment method according to the material of the organic filter used in the manufacture, and may be classified into a dyeing method, a pigment dispersion method, a printing method, an electrodeposition method, and the like according to a manufacturing method.

The dyeing method is applied to a glass substrate by adding a photosensitive agent such as dichromate to a soluble aqueous polymer material such as gelatin, casein, polyacrylamide, polyvinylalcohol, polyvinylpyrrolidone, and the like. A pattern is formed by exposure to ultraviolet rays using a type photomask, followed by coloring using an acidic dye or a reactive dye (Japanese Patent Laid-Open Nos. Hei 6-51301 and Hei 5-19113). This method is excellent in terms of transmittance, chromaticity, etc., but lack of uniformity of pigment in large-area coating due to the increase in size of liquid crystal display (LCD), high price due to complicated process, lack of heat resistance and weather resistance due to dye use. Do. In addition, there is a problem of yield deterioration and high price due to a long time of the manufacturing process according to the dyeing process after the pattern formation, and the degradation of reliability due to the heat resistance and weakness of the resins and dyes has been pointed out as a problem.

The printing method is a method in which an ink is mounted on a metal having a printed pattern, which is transferred to an elastic body called a blanket made of rubber material and then transferred to a glass substrate again (Japanese Patent Laid-Open Nos. Hei 6-109918 and Hei 6-214 106). Since this method compresses by applying pressure to the viscous ink, the precision of the pattern end portion should be excellent. The ink used in the printing method is a ground resin (Matrix Resin) such as epoxy resin is used as a colorant pulverized high transparency pigment of 0.1㎛ or less. In this method, the production process is relatively simple, and the cost of material and equipment is low, so that a low-cost color filter can be produced, but the low accuracy is the biggest problem.

Pigment dispersion method is a method of apply | coating photosensitive resin which disperse | distributed the pigment uniformly to a glass substrate, and forming a coloring pattern by ultraviolet exposure. Usually, an oxygen barrier film is applied in order to prevent the penetration of oxygen which weakens photosensitivity before ultraviolet irradiation. For example, photosensitive acrylic resins (Japanese Patent Laid-Open Nos. Hei 2-144502, Hei 2-199404) and stylbazole groups incorporating photosensitivity to a colored base resin (Japanese Laid-Open Patent Application) Photocurable using # 60-129707 and # 60-129738 and a photosensitive polyimide-based resin (JP-A-60-237403) can be divided into an etching method using a base resin. The method mainly used is a photocuring type (Japanese Patent Laid-Open No. Hei 6-331814, Japanese Patent Laid-Open No. Hei 6-289601) using an acrylic resin. As the pigment, organic pigments or inorganic pigments having excellent stability and light resistance are used. With the advancement of color filters, the demand for reliability of precision, heat resistance, light resistance, chemical resistance, etc. is increasing, and thus the use of this method is mainly used for improving accuracy by photolithography and heat resistance using pigments. However, in the manufacture of liquid crystal color display devices, heat treatment processes such as transparent conductive film and alignment film formation are carried out at around 200 ° C, so that discoloration and deformation of resins occur frequently due to high process temperature, and that the decrease in light transmission characteristics is the biggest problem. It is becoming.

The electrodeposition method is a method of dissolving or dispersing a pigment-dispersed polymer resin in a solvent and depositing it on an electrode. The polymer resin to be used uses a polyester having excellent transparency and safety as a base resin and an anion in an aqueous solution. A carboxyl group to be introduced is introduced (Japanese Patent Laid-Open Nos. Hei 4-104102 and Hei 4-172303). The pigment is dispersed in such a polymer in an aqueous solution. When a positive voltage is applied to the electrode on the color filter in the electrodeposition tank, the negatively charged polymer is precipitated to form a color pattern. This method is excellent in heat resistance, light resistance and chemical resistance because thermosetting resin is used in the polymer resin, but the electrode pattern forming process is complicated and the light transmittance is insufficient.

At present, the most common method used for manufacturing color filters of LCD is pigment dispersion method. The main components of color photoresistor used are photopolymerization initiator, monomer, binder ( It consists of binders and organic pigments that implement color. The photopolymerization initiator is a high sensitivity compound that generates radicals by receiving light, and a triazine-based bistrithionethyl compound having excellent stability is mainly used. Monomolecules are compounds that bind in the form of a polymer that freezes the polymerization reaction due to radicals generated by exposure and does not dissolve in the developing solution. The binder serves to stabilize the pigment dispersion and increase reliability of heat resistance, light resistance, chemical resistance and the like of the RGB pattern.

The inventors of the present invention improved the photocurable resin composition of the pigment dispersion method, which is mainly used in the manufacture of color filters of LCDs because of excellent resolution and reliability among various color filter manufacturing methods, and thus, problems such as heat resistance and light transmission characteristics noted above. In order to solve the problem and to develop a photocurable resin composition capable of making a color filter excellent in heat resistance, photosensitivity and transparency, the results of intensive research have led to the completion of the present invention.

The present invention is to provide a photocurable resin composition for a color filter having improved heat resistance and transparency to solve the problems such as discoloration and deformation of the resin at high temperature, which is a disadvantage of the conventional pigment dispersion method, and the resulting decrease in light transmission properties. .

Accordingly, the present invention is a photocurable resin for color filters in which (A) a polymer binder, (B) a photopolymerizable compound, (c) a photopolymerization initiator, and (D) a pigment are dissolved or dispersed in an (E) organic solvent. In the composition, the polymer binder (A) provides a photocurable resin composition for a color filter comprising a photopolymerizable prepolymer represented by the following formula (1).

Formula 1

In this formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and n is 0 or an integer between 1 and 100.

The photopolymerizable prepolymer included in the polymer binder (A) of the photocurable resin composition for color filters of the present invention may be used in an amount ranging from 0.1% by weight (wt%) to 50% by weight based on the total resin composition. Preferably, it is used in an amount in the range of 0.1% to 30% by weight based on the total resin composition.

As described above, the photopolymerizable prepolymer of the present invention provides improved heat resistance and optical properties to the photocurable resin composition of the present invention, and is obtained by reacting a photocurable monomer with an epoxy resin as shown in Scheme 1 below.

Photocurable monomer epoxy resin (Formula 2)

Photopolymerizable Prepolymer (Formula 1)

In this formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and n is 0 or an integer between 1 and 100.

In the reaction, the photocurable monomer and the epoxy resin may be used in the range of 0.5 to 5.0: 0.5 to 5.0 equivalent ratio.

Examples of the photocurable monomer used in the preparation of the photopolymerizable prepolymer contained in the polymer binder of the present invention include unsaturated carboxylic acid or unsaturated sulfonic acid, and specific examples of the unsaturated carboxylic acid include methacrylic acid, acrylic acid, Itaconic acid. Maleic acid, fumaric acid, and the like. Specific examples of the unsaturated sulfonic acid include isopren sulfonic acid and styrene sulfonic acid, which may be used alone or in combination.

In addition, the epoxy resin of the formula (2) used in the preparation of the photopolymerizable prepolymer contained in the polymer binder of the present invention is bisphenol A type epoxy resin, bisphenol F type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, naphthalene Epoxy resin containing a group, epoxy resin containing a cyclohexane group, specific examples include EOCN1020 (Nippon Kayaku Co., epoxy equivalent = 202, NC-9110 (Nippon Kayaku Co., epoxy equivalent = 231), EHPE-3150 (Dicel Chemical Co., epoxy equivalent = 182, TEPIC (Nissan Chemical Co., epoxy equivalent = 105, YX-4000 (Yuka Shell Co., epoxy equivalent = 193)) and the like.

When the epoxy resin and the photocurable monomer are reacted in the presence of an organic solvent such as methyl ethyl ketone, THF, DMF or the like with an ionic catalyst such as triphenylphosphine, amine and tetramethylammonium chloride in a temperature range of 70 to 120 ° C The photopolymerizable prepolymer of the present invention can be obtained.

In addition to such a photopolymerizable prepolymer, an acid monomer may be additionally added to the polymer binder (A) component of the present invention to further improve photocuring reactivity.

Accordingly, in a second aspect, the present invention provides a photocurable resin for color filters in which (A) a polymer binder, (B) a photopolymerizable compound, (c) a photopolymerization initiator, and (D) a pigment are dissolved or dispersed in an (E) organic solvent. In the composition, the polymer binder (A) is a mixture of a photopolymerizable prepolymer and an acid monomer represented by the formula (1) or a copolymer of a photopolymerizable prepolymer and an acid monomer or a homopolymer of an acid monomer and an homopolymer of a photopolymerizable prepolymer. It provides a photocurable resin composition for a color filter comprising a mixture with.

In such an embodiment, the photopolymerizable prepolymer represented by the formula (1) is as described in the first embodiment described above. Another polymer binder component, an acid monomer, is a compound having at least one carbonic acid in a molecule, for example, an unsaturated mono-carbonic acid or an unsaturated di-carbonic acid. acid). Also possible are unsaturated sulfonic acids having at least one sulfonic acid in the molecule. Specific examples of the unsaturated carboxylic acid include methacrylic acid (methacrylic acid), acrylic acid (acrylic acid), maleic acid (maleic acid), fumaric acid (fumaric acid). Specific examples of the unsaturated sulfonic acid include isopren sulfonic acid and styrene sulfonic acid, which may be used alone or in combination.

Such acid monomers may be added together with the above-mentioned photopolymerizable prepolymers or the acid monomers may be added as a copolymer of photopolymerizable prepolymer and acid monomer of Formula 1, or homopolymers of the photopolymerizable prepolymer of Formula 1 It may be added in a mixture with an acid monomer homopolymer.

The amount of acid monomer added is suitably 5 wt% to 50 wt% with respect to the total weight of the polymer binder, and more preferably 10 wt% to 40 wt%.

The homopolymer of the photopolymerizable prepolymer uses a weight average molecular weight ranging from 10,000 to 500,000, and the homopolymer of an acid monomer uses a weight average molecular weight ranging from 5,000 to 500,000.

The copolymer of the photopolymerizable prepolymer and the acid monomer is obtained by reacting at a weight ratio of 5 to 70 wt% of the acid monomer with respect to the photopolymerizable prepolymer, and preferably has a weight average molecular weight ranging from 10,000 to 500,000.

As described above, the polymer binder containing the acid monomer shows alkali solubility, and in particular, the polymer binder using the acid monomer containing the above amount is excellent in solubility in the alkali developer and does not cause undissolved products and excellent adhesion to the substrate. It exhibits excellent characteristics in color pixel formation.

Hereinafter, the components of the photocurable resin composition according to the present invention will be described in more detail.

A. Polymeric Binders

The polymer binder plays a role of stabilizing pigment dispersion and increasing reliability of heat resistance, light resistance, chemical resistance, etc. of an RGB pattern, and is generally composed of an individual or a mixture of acrylic or methacrylate monomers and acid monomers, or Copolymers of acrylic monomers or methacrylate monomers with acid monomers or mixtures of individual homopolymers are used. Specific examples of commonly used acrylic or methacrylate monomers are as follows. Methyl methacrylate, methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate , 2-hydroxy ethyl methacrylate, 2-hydroxy ethyl acrylate, benzyl methacrylate, benzyl acrylate, etc. Unsaturated carboxylic acid amino alkyl esters such as unsaturated carboxylic acid alkyl esters, amino ethyl acrylates, unsaturated carboxylic acid glycidyl esters such as glycidyl methacrylate, glycidyl acrylate, etc. Can be mentioned.

In addition to such acrylic or methacrylate monomers, the polymeric binder used in the present invention is characterized by including a photopolymerizable prepolymer represented by Formula 1 to improve heat resistance and optical properties, and further contains an acid monomer. can do.

The photopolymerizable prepolymer, which is a feature of the present invention, is suitable in an amount of 0.1 wt% to 50 wt% with respect to the total resin composition, and more preferably in an amount of 1 wt% to 30 wt%. If it is used less than 0.1% by weight or more than 50% by weight, various properties such as resolution, heat resistance and optical properties will be poor.

When acid monomer is used in less than 5% by weight or in excess of 50% by weight, various properties such as resolution, heat resistance and optical properties become poor. Therefore, the amount of 5 wt% to 50 wt% of the total weight of the polymer binder is appropriate. Is preferably in an amount of 10 wt% to 40 wt%.

B. Photopolymerizable Compounds

The photopolymerizable compound used in the present invention is a photopolymerizable monomer compound having a carbon-carbon double bond, and is a compound that is polymerized by radicals generated by exposure and binds in a polymer form that is insoluble in a developing solution. Specific examples are as follows: aromatic vinyl compounds such as styrene, α-methylstyrene, and vinyl toluene, methyl methacrylate and methyl acrylate. methyl acrylate, ethyl methacrylate, ethyl acrylate, butyl methacrylate, butyl acrylate, 2-hydroxy ethyl methacrylate (2-hydroxy unsaturated carboxylic acid alkyl esters such as ethyl methacrylate), 2-hydroxy ethyl acrylate, benzyl methacrylate, benzyl acrylate, and amino ethyl acrylate. Unsaturated carboxylic acid glycidyl esters such as carboxylic acid amino alkyl esters, glycidyl methacrylate, glycidyl acrylate, Vinyl cyanide compounds, such as carboxylic acid vinyl esters, such as vinyl acetate and a vinyl propionate, methacrylonitrile, acrylonitrile, and the (alpha)-chloro acrylonitrile, 1, 3- butadiene, and 2-methyl- 1 Aliphatic conjugated diene compounds such as, 3-butadiene and isoprene, polystyrenes having a methacryloyl group and an acryloyl group at their ends, polymethyl acrylate, polyacrylate, polybutyl meta Macromonomer such as acrylate, polybutyl acrylate, polysilicon, hexanediol diacrylate (HDDA), hexanediol dimethacrylate (HDDM), neopentyl glycol diacrylate (NPGDA), neopentyl Glycol Dimethacrylate (NPGDM), Diethylene Glycol Diacrylate (DEGDA), Diethylene Glycol Dimethacrylate (DEGDM), Tripropylene Glycol Diacrylate (TPGDA), Tripropylene Glycol Dimetha Relate (TPGDM), Polyethylene Glycol Diacrylate (PEGDA), Polyethylene Glycol Dimethacrylate (PEGDM), Trimethyloyl Propane Triacrylate (TMPTA), Trimethyloyl Propane Trimethacrylate (TMPTM), Propionic Acid Polyfunctional acrylics, such as pentaerythritol triacrylate (PDPTA), propionate dipentaerythritol trimethacrylate (PDPTM), dipentaerythritol hexaacrylate (DPHA), dipentaerythritol hexamethacrylate (DPHM) A monomer etc. are mentioned.

When using less than 1% by weight and more than 30% by weight, such properties as poor resolution, heat resistance, optical properties, etc. are poor, it is preferable that the photopolymerizable compound contains 1 wt% to 30 wt% of the total resin composition.

C. Photopolymerization Initiator

The photoinitiator used in the present invention may use any photoinitiator known so far. Specific examples thereof include benzoin such as benzoin, benzoin methyl ether and benzoin ethyl ether, alkyl ethers thereof, acetophenone, 2,2-dimethoxy-2-phenylacetophenone and 1,1-dichloroacetophenone. Anthraquinones, such as acetone phenone, 2-methyl anthraquinone, 2-amyl anthraquinone, 2-t-butyl anthraquinone, and 1-chloro anthraquinone, 2, 4- dimethyl thioxanthone, 2, 4- Thioxanthones such as diisopropyl thioxanthone and 2-chloro thioxanthone, ketals such as acetophenone dimethyl ketal, benzyl dimethyl ketal, benzophenones such as benzophenone, and 2 (2'-furylethylidene ) -4,6-bis (trichloromethyl) -s-triazine (trade name: TFE triazine; manufactured by Sanwa Chemical Co., Ltd.), 2 [2 '(5'-methylfuryl) ethylidene] -4, Triazines such as 6-bis (trichloromethyl) -s-triazine (trade name: TME triazine; manufactured by Sanwa Chemical Co., Ltd.), 2,2'-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenylbisimidazole (trade name; ratio Imidazole, and the Black Sea Chemical Co., Ltd.) etc. are mentioned.

The photopolymerization initiator may be used in one kind or a mixture of two or more kinds, preferably used in the range of 0.05 wt% to 10 wt% relative to the total resin composition. If it is used less than 0.05 wt% photocuring is not achieved, when using more than 10 wt% is a significant reduction in physical properties.

D. Pigment

As the pigment used in the present invention, a pigment such as azo-based, anthraquinone-based, indigo-based, phthalocyanine-based, and the like may be used to implement color, which is represented by a color index as follows. As yellow pigment, CI20, CI24, CI83, CI86, CI93, CI109, CI110, CI117, CI125, CI137, CI138, CI139, CI147, CI148, CI153, CI 154, CI166, CI168 and the like, and red pigments CI9, CI97, CI122, CI123, CI149, CI168, CI177, CI180, CI192, CI215, CI216, CI217, CI220, CI223, CI223, CI224, CI226, CI227, CI228, CI240 etc. are mentioned. Color pigments include CI19, CI23, CI29, CI30, CI37, CI40, CI50, and blue pigments such as CI15, CI15: 6, CI22, CI60, CI64, etc. Examples of green pigments include CI7 and CI36.

Each pigment is preferably used in the range of 1 wt% to 50 wt% with respect to the total resin composition. If you use less than 1 wt% color does not appear well, if you use more than 50 Wt% is a significant decrease in physical properties.

E. Organic Solvents

As the organic solvent for dissolving or suspending the components of the photocurable resin composition described above, a generally known organic solvent may be used. Specifically, for example, 3-methoxypropionate methyl ester, 3-methoxypropionate ethyl ester, 3 Ketones such as 3-alkoxypropionic acid alkyl esters such as ethoxypropionate methyl ester and 3-ethoxypropionate ethyl ester, methyl ethyl ketone, cyclohexanone and methylcyclohexanone, propylene glycol monomethyl ether, propylene glycol monopropyl ether Propylene glycol monoalkyl ether acetates such as propylene glycol monoalkyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, N-methylpyrrolidone, dimethyl sulfoxide, etc. Can be mentioned.

The organic solvent may be used alone or in combination of two or more thereof, and may be used in a range of 20 wt% to 95 wt% with respect to the total resin composition. The use of less than 20 wt% and more than 95 wt% degrades the coating properties significantly.

Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited based on this Example.

(Examples 1-5)

Following the mixing composition shown in Table 1 was mixed uniformly using a mixer to prepare a photocurable resin composition for color filters. The resin composition thus obtained was evaluated in accordance with the following method, and the results are shown in Table 2. In the evaluation, the samples were measured by spin coating each resin composition on a glass substrate, drying at 80 ° C. for 30 minutes, and then forming a film having a thickness of about 1 μm.

(Assessment Methods)

1) Dryness of coating

The dryness of a coating film is judged by the state at the time of removing after pressing a negative film to a coating film.

(Circle): A coating film does not adhere to a film at all.

(Triangle | delta): A coating film sticks to a film slightly.

X: A coating film is affixed on a film.

2) resolution

A mask having a line width of 10 μm was placed on the coating film, exposed to an intensity of 500 mJ / cm 2 using a 1 kw ultra-high pressure mercury lamp, and then developed using a 1% Na ₂ CO ₃ aqueous solution to evaluate the condition.

(Circle): There is no abnormality in a developing pattern.

(Triangle | delta): There exists some damage to a developing pattern.

X: The developing pattern does not appear.

3) heat resistance

After leaving for 30 minutes at 150 ° C. after exposure, the mixture was heated at 250 ° C. for 1 hour, and then changes in discoloration and fading were evaluated.

(Circle): There is no discoloration and a fading.

X: There is discoloration and fading.

(Comparative Examples 1 to 3)

The comparative group was carried out in the same manner as in Examples 1 to 5 according to the composition shown in Table 1 and the characteristics were evaluated and the results are shown in Table 2.

Composition table by component (unit: wt%) ingredient Example 1 Example 2 Example 3 Example 4 Example 5 Comparative Example 1 Comparative Example 2 Comparative Example 3 Photopolymerizable prepolymer ¹ 7.0 8.0 9.0 10.0 11.0 - - - Benzyl methacrylate - - - - - 7.0 - - Methacrylic acid 3.0 3.4 3.9 4.3 4.7 3.0 - - Benzyl methacrylate / methacrylic acid copolymer ² - - - - - - 10.0 15.0 Dipentaerythritol hexaacrylate (DPHA) 5.0 5.7 6.5 7.2 7.9 5.0 5.0 7.5 Photopolymerization Initiator ³ 1.0 1.1 1.3 1.4 1.6 1.0 1.0 1.5 C.I. Pigment Blue [15: 6] 9.0 9.0 9.0 9.0 9.0 9.0 9.0 9.0 C.I. Pigment Violet [23] 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 Propylene Glycol Monomethyl Ether Acetate 60.0 58.3 56.3 54.6 52.8 60.0 60.0 53.5 Cyclohexanone 14.0 13.5 13.0 12.5 12.0 14.0 14.0 12.5 1) Photopolymerizable prepolymer: The photopolymerizable prepolymer used in this example is a photopolymerizable prepolymer using methacrylic acid as a photocurable monomer and YX-4000H (Yuka Shell Co., Epoxy equivalent = 193) as an epoxy resin. The polymer was prepared. R ₁ , R ₂ , R ₃ , R ₄ and R ₅ in Formula (1) of the photopolymerizable prepolymer used in this example are methyl (CH ₃ ) groups. 2) Benzyl methacrylate / methacrylic acid copolymer The copolymer used in the comparative example was a copolymer obtained with a weight ratio (wt%) ratio of benzyl methacrylate monomer and methacrylic acid monomer as 7: 3, and a weight average molecular weight of about 20,000 was used. Photopolymerization Initiator: The photoinitiator used in this example was prepared as 2 (2'-furylethylidene) -4,6-bis (trichloromethyl) -s-triazine [trade name: TFE triazine; Sanwa Chemical Co., Ltd. was used.

Evaluation table according to each composition Evaluation item Dryness of coating resolution Heat resistance Example 1 ○ ○ ○ Example 2 ○ ○ ○ Example 3 ○ ○ ○ Example 4 ○ ○ ○ Example 5 ○ ○ ○ Comparative Example 1 × △ × Comparative Example 2 △ ○ × Comparative Example 3 △ △ ×

As can be seen from Table 2, the photocurable resin composition containing the photopolymerizable prepolymer of the present invention was more effective in terms of coating film dryness, resolution, and particularly heat resistance than the resin composition of the prior art.

As described above, the photocurable resin composition according to the present invention is very excellent in dryness and heat resistance of a coating film by using a high heat resistance and high transparency acrylic photopolymerizable prepolymer. Therefore, by using the photocurable resin composition for color filters according to the present invention, it is possible to produce a high-performance color filter without discoloration and deformation of the resin and deterioration of light transmission properties even at a high process temperature in manufacturing a liquid crystal color display device. .

Claims (11)

(A) A polymeric binder, (B) photopolymerizable compound, (C) photoinitiator, and (D) pigment which melt | dissolved or disperse | distributed in the organic solvent, WHEREIN: A polymeric binder (A) is represented by following General formula (1). A photocurable resin composition for a color filter comprising a photopolymerizable prepolymer: Formula 1 In this formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and n is 0 or an integer between 1 and 100. The photocurable resin composition for a color filter according to claim 1, wherein the photopolymerizable prepolymer is contained in an amount of 0.1 wt% to 50 wt% based on the total resin composition. The photocurable resin composition for a color filter according to claim 1, wherein the photopolymerizable prepolymer is prepared by reacting a photocurable monomer with an epoxy resin represented by the following Chemical Formula 2 as shown in Scheme 1. Scheme 1 Photocurable monomer epoxy resin (Formula 2) Photopolymerizable Prepolymer (Formula 1) In this formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and n is 0 or an integer between 1 and 100. The photocurable monomer of claim 3, wherein the photocurable monomer is methacrylic acid, acrylic acid, or itaconic acid. Maleic acid (maleic acid), fmaric acid (fumaric acid), isopren sulfonic acid (isopren sulfonic acid), styrene sulfonic acid (styrene sulfonic acid), and the like. The photocurable resin composition for color filters according to claim 3, wherein the epoxy resin comprises a biphenyl type epoxy resin. The photocurable resin composition for color filters according to claim 3, wherein the equivalent ratio of the photocurable monomer and the epoxy resin is 0.5 to 5.0: 0.5 to 5.0. (A) Polymer binder, (B) photopolymerizable compound, (c) photoinitiator, and (D) pigment in photocurable resin composition for color filters in which (E) organic solvent is dissolved or dispersed. ) Comprises a mixture of a photopolymerizable prepolymer and an acid monomer represented by Formula 1 or a copolymer of a photopolymerizable prepolymer and an acid monomer or a mixture of a homopolymer of an photopolymerizable prepolymer and an homopolymer of an acid monomer. Photocurable resin composition for color filters. Formula 1 In this formula, R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are hydrogen atoms or alkyl groups having 1 to 10 carbon atoms, and n is 0 or an integer between 1 and 100. The photocurable resin composition for a color filter according to claim 7, wherein the acid monomer comprises an unsaturated carboxylic acid containing at least one carboxylic acid in a molecule or an unsaturated sulfonic acid containing at least one sulfonic acid in a molecule. The method of claim 7, wherein the copolymer of the photopolymerizable prepolymer and the acid monomer is obtained by reacting at a weight ratio of 5 to 70 wt% of the acid monomer to the photopolymerizable prepolymer, and has a weight average molecular weight ranging from 10,000 to 500,000. Photocurable resin composition for color filters. 8. The photocurable resin composition for color filters according to claim 7, wherein the homopolymer of the photopolymerizable prepolymer has a weight average molecular weight in the range of 10,000 to 500,000. 8. The photocurable resin composition for color filters according to claim 7, wherein the homopolymer of the acid monomer has a weight average molecular weight in the range of 5,000 to 500,000.