KR19990047373A - Color resist resin composition - Google Patents

Abstract

The color resist resin composition of the present invention is (A) copolymerized with monomers of the following structural formulas (I), (II) and (III), and the molar ratio of the monomers (I), (II) and (III) in the copolymer 1-40 weight part of cardo-type binder resins which are 1: 2-4: 2-8; (B) 0.1-10 weight part of photopolymerizable monomers; (C) 0.1-10 weight part of photoinitiators; (D) 0.1-10 weight part of epoxy resins; (E) 1-40 weight part of pigments; And (F) 20 to 80 parts by weight of the solvent.

R is a hydrogen atom; Alkyl groups, allyl groups, phenyl groups or benzyl groups having 1 to 10 carbon atoms; Or an ethoxy group having 1 to 8 carbon atoms, and X is a halogen atom.

The binder resin, the photopolymerizable monomer and the epoxy resin used in the present invention are treated with an acid anhydride, and the binder resin preferably has a weight average molecular weight of 1000 to 20000. In the color resist resin composition of the present invention, other additives may be added as necessary.

Description

[Name of invention]

Color resist resin composition

Detailed description of the invention

[Field of Invention]

The present invention relates to a color resist resin composition. More specifically, the present invention relates to a color resist resin composition for forming a color filter for use in a liquid crystal display, an optical filter of a camera, and the like. More specifically, the present invention relates to an alkali aqueous solution developing type color resist resin composition used in a color filter.

[Background of invention]

Color filters are used in liquid crystal displays, optical filters of cameras, and the like, and are manufactured by forming a thin region colored in three or more colors and coating a thin film with a photoresist on a solid state imaging device or a transparent substrate. The thin film coating of the color filter is formed by dyeing, printing, pigment dispersion or electrodeposition.

In the case of the dyeing method, an image having a dyeing base material such as a natural photosensitive resin such as gelatin, an amine modified polyvinyl alcohol, an amine modified acrylic resin and the like is formed on the substrate before dyeing with a dye such as a direct dye. Because it needs to be formed on the phase, it is necessary to perform flameproof processing every time the color is changed, and the process is very complicated and the process time is long. In addition, the dyes and resins generally used have good clarity and dispersibility, but have disadvantages such as poor light resistance, moisture resistance, and most importantly, heat resistance. For example, Korean Patent Publication No. 91-4717 and Korean Patent Publication No. 94-7778 use azo compounds and azide compounds as dyes, but have a disadvantage in that heat resistance and durability are inferior to pigment dispersion methods.

Printing method uses ink in which pigment is dispersed in thermosetting or photocuring resin, and after printing, curing with heat or light can reduce material cost compared to other methods, but highly precise and detailed image formation This is difficult and there is a disadvantage that the thin film layer formed is not uniform. For example, Korean Patent Publication Nos. 95-703746 and 96-11513 propose a method of manufacturing a color filter using an inkjet method. Since the color resist composition dispersed in the nozzle is dye-like for printing delicate and accurate pigments, durability and heat resistance are inferior as in the dyeing method.

Korean Patent Publication Nos. 93-700858 and 96-29904 propose an electrodeposition method using an electroprecipitation method. The electrodeposition method is capable of forming a fine colored net and uses pigments, so it has excellent heat resistance and light resistance. In the future, when the pixel size becomes precise and the electrode pattern becomes fine, it is difficult to apply color filters that require high precision because colored stains due to electrical resistance appear on both ends or the thickness of the colored film becomes thick.

Pigment dispersion is a method formed by repeating a series of steps of coating, phase exposing, developing, and thermosetting a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix. This pigment dispersion method has the advantage of improving the heat resistance and durability, which is the most important property of the color filter, and maintaining the thickness of the film uniformly. For example, Korean Patent Publication No. 92-702502, Patent Publication No. 94-5617, Patent Publication No. 95-11163, and Patent Publication No. 95-700359 have proposed a method for producing color resist using pigment dispersion.

The photosensitive resin composition used in the pigment dispersion method is generally composed of a binder resin, a photopolymerizable monomer, a photopolymerization initiator, a solvent, and other additives. Among them, the dispersion of the pigment is important, which is influenced by the binder resin, which serves as a kind of dispersant. Receive. As the binder resin used in the pigment dispersion method, for example, the photosensitive polyimide resin disclosed in Japanese Patent Application Laid-open No. 60-237403, the acrylic polymer described in Japanese Patent Application Laid-open Nos. Hei 1-200353, Hei 4-7373, Hei 4-91173 and the like. And a photosensitive resin composed of an azide compound, a radically polymerized photosensitive resin composed of an acrylate monomer, an organic polymer binder, and a photopolymerization initiator described in JP-A-152449, JP-A 4-163552; Various kinds of photosensitive resins including a phenol resin, a crosslinking agent having an N-methylol structure, and a photoacid generator disclosed in Korean Patent Publication No. 92-5780 have been proposed. However, the use of photosensitive polyimide or phenolic resins as binder resins according to the pigment dispersion method is disadvantageous in that it has high heat resistance but low sensitivity and development with an organic solvent. In addition, conventional systems using azide compounds as photosensitizers have problems of low sensitivity, poor heat resistance, and effects of oxygen upon exposure. In order to avoid this, it is necessary to install an oxygen barrier film or expose it in an inert gas, and there are problems such as complicated process and expensive equipment. In addition, the photosensitive resin which forms the image using the acid generated by the exposure is highly sensitive and has the advantage of not being affected by oxygen when exposed. However, the heating process is required during the exposure and development, and the heating time is sensitive to the pattern formation. There is a problem that the process control is difficult because of the reaction.

In order to solve this problem, Japanese Patent Publication Nos. 7-64281, 7-64282, 8-278630, 6-1938, 5-339356 and 95-702313 have a cardo system. Patents for producing color filters using binder resins are described. In general, a resin having a cardo-based resin is highly sensitive and is free from oxygen, and has good heat resistance, shrink resistance, and transparency. On the other hand, if the molecular weight is too high, processing of the color filter composition is difficult and there may be a problem with adhesion to the substrate, and because the chemical resistance is poor, an epoxy resin is introduced to supplement the chemical resistance, but the chemical resistance evaluation criteria are insufficient. .

In addition, since there is no place to react with the alkaline developing aqueous solution in the photosensitive resin composition itself, there may be a problem in that developability is deteriorated and a residue after development remains. In this case, in order to improve the developability, Japanese Patent Laid-Open No. Hei 4-363311 improved the developability by treating the cardo-based binder resin with an acid anhydride to form an alkali soluble resin. In order to further improve developability, Japanese Patent No. Hei 5-70528 was also subjected to an acid anhydride treatment. After such treatment, there may be a problem that a residue remains after development.

Therefore, the present inventors have developed a color resist resin composition having high sensitivity and excellent in heat resistance, shrinkage resistance, transparency, chemical resistance, and developability.

[Purpose of invention]

An object of the present invention is to provide a color resist resin composition having high sensitivity without being affected by oxygen when exposed.

Another object of the present invention is to provide a color register resin composition which can improve chemical resistance and reduce a change in pattern.

Still another object of the present invention is to provide a color resist resin composition capable of improving heat resistance and reducing the color difference of a coating film.

Another object of the present invention is to provide a color resist resin composition having good photosensitive resin characteristics such as shrinkage resistance and transparency.

Still another object of the present invention is to provide a color resist resin composition having a small film thickness difference between the central portion and the peripheral portion of the coating film and excellent surface smoothness.

Still another object of the present invention is to provide a pigment dispersion type color resist resin composition for producing color filters of a liquid crystal display or a camera view finder.

Another object of the present invention is to provide a color resist resin composition having excellent developability and leaving no residue on the pattern.

[Summary of invention]

The color resist resin composition of the present invention

(A) copolymerized with monomers of the following structural formulas (I), (II) and (III), wherein the molar ratio of monomers (I), (II) and (III) in the copolymer is from 1: 2 to 4: 2 to 1-40 weight part of cardo-based binder resin of 8;

R is a hydrogen atom; Alkyl groups, allyl groups, phenyl groups or benzyl groups having 1 to 10 carbon atoms; Or an ethoxy group having 1 to 8 carbon atoms, and X is a halogen atom.

(B) 0.1-10 weight part of acrylic photopolymerizable monomer;

(C) 0.1-10 weight part of photoinitiators;

(D) 0.1-10 weight part of epoxy resins;

(E) 1-40 weight part of pigments; And

(F) 20 to 80 parts by weight of the solvent;

It is characterized by consisting of.

It is preferable to have a weight average molecular weight of the said binder resin 1000-20000 used by this invention. In the color resist resin composition of the present invention, other additives may be added as necessary.

Hereinafter, specific contents of the present invention will be described in detail below.

Detailed Description of the Invention

The color resist resin composition of this invention copolymerizes the compound represented by the said structural formula (I), (II), and (III), and the molar ratio of each monomer in the copolymer is 1: 2-4: 2-8. It consists of a binder resin, a photopolymerizable monomer, a photoinitiator, an epoxy resin, a pigment, and a solvent containing at least 1 or more series bonds.

The binder resin in the present invention preferably has a weight average molecular weight of 1000 to 20000. Binder resin is used at 1-40 weight part with respect to the whole resin composition. In order to make said binder resin into alkali-soluble resin, it processes with the acid anhydride which has a following structural formula.

R ₁ and R _{2 in the above} is a hydrogen atom; C1-C10 alkyl group, allyl group, phenyl group, benzyl group; Or an ethoxy group having 1 to 8 carbon atoms.

Acrylic photopolymerizable monomers used in the present invention include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, Pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate , Trimethylolpropane triacrylate, noblock epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimetha Acrylate, 1,6-hexanediol dimethacrylate monomer, and the like. Acrylic photopolymerizable monomer is used in 0.1-10 weight part with respect to the whole resin composition. The photopolymerizable monomer is treated with an acid anhydride in order to facilitate dissolution in an aqueous alkali solution.

The photopolymerization initiator used in the present invention is acetophenone derivatives commonly used. Specific examples include 2,2'-diethoxyacetophenol, 2,2'-dibutoxyacetophenone and 2-hydroxy-2-methyl. Proriophenol, pt-butyltrichloroacetophenol, p, -t-butyldichloroacetophenol, benzophenone, 4-chloroacetophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholino propane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and the like are used. The photoinitiator is used in 0.1-10 weight part with respect to the whole resin composition.

As the epoxy resin used in the present invention, for example, a phenol noblock epoxy resin, a tetramethyl bi-phenyl epoxy resin, a bisphenol A resin or the like is used. An epoxy resin is used at 0.1-10 weight part with respect to the whole resin composition. Such an epoxy resin is treated with an acid anhydride to facilitate dissolution in an aqueous alkali solution.

As the pigment used in the present invention, inorganic pigments such as carbon black may be used in addition to organic pigments such as anthraquinone pigments, conylene-based condensed polycyclic pigments, phthalocyanine pigments, and azo pigments. It can be mixed and used. The pigment is used in 1 to 40 parts by weight based on the total resin composition.

In the present invention, ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether, and the like can be used as a solvent or used alone. The solvent is used at 20 to 80 parts by weight based on the total resin composition.

It is also preferred in the present invention to use a dispersant to disperse in the mixture. It may be used by internal addition to the pigment in the form of surface treatment of the pigment in advance, or may be used in the form of external addition to the pigment. As such, nonionic, anionic or cationic acid may be used, such as polyalkylene glycols and esters thereof, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alkoxyalkylene oxide adducts, sulfur Phonic acid ester, sulfonate, carboxylic acid ester, carboxylate, alkylamide alkylene oxide adduct, alkylamine, etc. can be used. These may be added alone or in combination of two or more. The amount of the dispersant added is preferably 0 to 20% by weight based on 1 part by weight of the pigment.

The mixture of the present invention can be applied to the photosensitive resin composition with a thickness of, for example, 0.5 to 10μm using a suitable method such as spin coating, roller coating, spray coating on the glass substrate for color filters. After application, the active line is irradiated to form the necessary pattern for the color filter. As a light source used for irradiation, UV irradiation of 190 nm-450 nm, preferably 200 nm-400 nm region is used, and electron beam and X-ray irradiation are also suitable. After the irradiation, the application layer is treated with a developer to dissolve the unirradiated portion of the application layer and form a pattern necessary for the color filter. By repeating this process in accordance with the required number of colors, a color filter having a desired pattern can be obtained. In addition, the image pattern obtained by the development in the above process can be heated again or cured by actinic radiation, and the crack resistance, solvent resistance and the like can be improved.

The color resist resin composition of this invention is a resin composition developed in alkaline aqueous solution. The color resist resin composition of this invention is a composition used in order to form the pattern of a color filter, and a protective film is apply | coated on the pattern surface. This protective film composition has the same composition as the color resist resin composition containing no pigment. The protective film composition for color filters is also a resin composition developed in alkaline aqueous solution.

The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.

EXAMPLE

Example 1

The color resist resin composition which concerns on this invention was prepared. Each component and content used are shown in Table 1 below.

TABLE 1

Treatment of Acid Anhydrides

(1) binder resin

1.5 Kg of ethylene glycol acetate and 0.5 Kg of cyclohexanone were added to the cardo-based binder resin 303 g, and then 96 g of acetic anhydride and 1 g of tetraethylammonium bromide were added and mixed, and the mixture was slowly heated to a temperature of 110 ° C. for 1 hour. .

(2) photopolymerizable monomer

1.5 Kg of ethylene glycol acetate and 0.5 Kg of cyclohexanone were added to 298 g of pentaerythritol acrylate, and then mixed with 96 g of acetic anhydride and 1 g of tetraethylammonium bromide, and slowly heated to a temperature of 110 ° C. for 1 hour. I was.

(3) epoxy resin

Ethylene glycol acetate 1.5Kg and cyclohexanone 0.5Kg were added to 436 g of phenol noblock type epoxy resin (EPPN-201), 96 g of acetic anhydride and 1 g of tetraethylammonium bromide were added thereto, and the mixture was gradually heated to a temperature of 110 ° C. It was added and reacted for 1 hour.

The photopolymerization initiator was dissolved in the solvent of Table 1 and stirred at room temperature for 2 hours. The photopolymerizable monomer and the binder resin were added and stirred at room temperature for 2 hours. Pigments and other additives were added and stirred at room temperature for 1 hour. Filtration was carried out three times to remove impurities, to prepare a color resist resin composition according to the present invention.

Comparative Example 1

A resin composition was prepared in the same manner as in Example 1, except that the epoxy resin was not treated with acetic anhydride.

Comparative Example 2

A resin composition was prepared in the same manner as in Example 1, except that no epoxy resin was added.

Comparative Example 3

A resin composition was prepared in the same manner as in Example 1, except that the epoxy resin and the photopolymerizable monomer were not treated with acetic anhydride.

Comparative Example 4

A resin composition was prepared in the same manner as in Example 1 except that the epoxy resin, the photopolymerizable monomer and the binder resin were not treated with acetic anhydride.

Patterning Assessment:

A colored thin film was formed with the resin composition prepared according to the above Examples, and the developability, adhesion, heat resistance, and chemical resistance were measured as follows, and the results are shown in Table 2.

(2) developability

The photosensitive resin composition was applied to a glass substrate having a chromium coated thickness of 1 mm to a thickness of 1 to 2 μm, and dried in a hot air circulation drying furnace at a constant time (1 minute) and at a constant temperature (80 ° C.) to obtain a coating film. Subsequently, a photomask was placed on the coating film and exposed using a high pressure mercury lamp having a wavelength of 365 nm, and then developed for 30 seconds at 30 ° C. and atmospheric pressure using a 1% Na ₂ CO ₃ aqueous solution. After development, the pattern was obtained by drying at a constant time (30 minutes) and a constant temperature (230 ° C.) in a hot air circulation drying furnace to evaluate the residue visually.

○ Excellent developability: No residue is left on the pattern.

△ Good developability: Some residue remains on the pattern.

X Poor developability: A lot of residue remains on a pattern.

(2) adhesive

The photosensitive resin composition was applied to a chromium coated 1 mm thick glass substrate at a thickness of 1 to 2 μm, and dried in a hot air circulation drying furnace at a constant time (1 minute) and at a constant temperature (80 ° C.) to obtain a coating film. Irradiated with an ultra-high pressure mercury lamp having a wavelength of 365 nm, and subsequently heated in a hot air circulation drying furnace at 230 ° C. for 30 minutes, and then engrave 100 check boards of 1 mm × 1 mm, and visually inspect the peeling state after the peering experiment by adhesive tape. Was determined.

○: No change at 100/100.

△: 80/100 to 99/100

×: 0/100 × 79/100

(3) heat resistance

The photosensitive resin composition was applied to a chromium coated 1 mm thick glass substrate with a thickness of 1 to 2 μm, and dried in a hot air circulation drying furnace at a constant time (1 minute) and at a constant temperature (80 ° C), followed by a wavelength of 365 nm. Irradiated with an excited high-pressure mercury lamp and then heated in a hot air circulation drying furnace at 230 ° C. for 30 minutes to obtain a coating film. This was heated in a hot air circulation drying furnace at a constant time (1 hour) and at a constant temperature (250 ° C), and then the color difference (ΔE) of the coating film was measured to evaluate heat resistance.

○: color difference (ΔE) is 3 or less

Δ: color difference ΔE is 3 to 5

X: Color difference (ΔE) is 5 or more

(4) chemical resistance

The photosensitive resin composition was applied to a thickness of 1 to 2 μm on a chromium-coated glass substrate subjected to degreasing, and then dried in a hot air circulation drying furnace at a predetermined time (1 minute) and at a constant temperature (80 ° C), followed by 365 nm. Irradiated with an ultra-high pressure mercury lamp having a wavelength of 1, followed by developing for 30 seconds at 30 ° C. and atmospheric pressure using an aqueous 1% Na ₂ CO ₃ solution, and then drying at 230 ° C. for 30 minutes in a hot air circulation drying furnace to obtain a pattern. It was. This pattern was immersed in 5% aqueous sulfuric acid solution for 10 minutes, 20 minutes and 30 minutes and the change of the pattern was observed.

○: no change in pattern after 30 minutes

△ No change of pattern between 10 and 30 minutes

Pattern change before 10 minutes

The change in the pattern indicates the swelling, peeling, melting, and the like of the pattern.

TABLE 2

Simple modifications or changes of the present invention can be easily carried out by those skilled in the art, and all such modifications or changes can be seen to be included in the scope of the present invention.

Claims (8)

(A) copolymerized with monomers of the following structural formulas (I), (II) and (III), wherein the molar ratio of monomers (I), (II) and (III) in the copolymer is from 1: 2 to 4: 2 to 1-40 weight part of cardo-based binder resin of 8; R is a hydrogen atom; Alkyl groups, allyl groups, phenyl groups or benzyl groups having 1 to 10 carbon atoms; Or an ethoxy group having 1 to 8 carbon atoms, and X is a halogen atom. (B) 1 to 20 parts by weight of the photopolymerizable monomer; (C) 0.1-10 weight part of photoinitiators; (D) 0.1-10 weight part of epoxy resins; (E) 1-40 weight part of pigments; And (F) 20 to 80 parts by weight of the solvent; The color resist resin composition characterized by the above-mentioned. The color resist resin composition according to claim 1, wherein the epoxy resin is selected from the group consisting of phenol noblock epoxy resins, tetramethyl bi-phenyl epoxy resins, and bisphenol A epoxy resins. The color resist resin composition according to claim 1, wherein the binder resin, the photopolymerizable monomer and the epoxy resin are treated with an acid anhydride having the following structural formula. R ₁ and R ₂ are hydrogen atoms; C1-C10 alkyl group, allyl group, phenyl group, benzyl group; Or an ethoxy group having 1 to 8 carbon atoms. The color resist resin composition according to claim 1, 2 or 3, wherein the color resist resin composition is an alkali developing resin composition developed in an aqueous alkali solution. (A) copolymerized with monomers of the following structural formulas (I), (II) and (III), wherein the molar ratio of monomers (I), (II) and (III) in the copolymer is from 1: 2 to 4: 2 to 1-40 weight part of cardo-based binder resin of 8; R is a hydrogen atom; Alkyl groups, allyl groups, phenyl groups or benzyl groups having 1 to 10 carbon atoms; Or an ethoxy group having 1 to 8 carbon atoms, and X is a halogen atom. (B) 1 to 10 parts by weight of the photopolymerizable monomer; (C) 0.1-10 weight part of photoinitiators; (D) 1-10 weight part of epoxy resins; And (E) 20 to 80 parts by weight of the solvent; The protective film composition for color filters which consists of a. The protective film composition for a color filter according to claim 5, wherein the binder resin, the photopolymerizable monomer and the epoxy resin are treated with an acid anhydride having the following structural formula. R ₁ and R ₂ are hydrogen atoms; C1-C10 alkyl group, allyl group, phenyl group, benzyl group; Or an ethoxy group having 1 to 8 carbon atoms. The protective film composition for a color filter according to claim 5, wherein the epoxy resin is selected from the group consisting of phenol noblock epoxy resins, tetramethyl bi-phenyl epoxy resins, and bisphenol A type epoxy resins. The protective film composition for color filters according to claim 5, 6 and 7, wherein the protective film composition is an alkali developing resin composition developed in an aqueous alkali solution.