KR20090057814A - Photosensitive resin composition for color filter and image sensor color filter using the same - Google Patents

Abstract

A photosensitive resin composition for a color filter and an image sensor color filter using the same are provided to form micro patterns with excellent sensitivity due to a thiol group-containing sensitizer, and to prevent the lower side from being lifted and separated due to a modified compound of glycerol triacrylate. A photosensitive resin composition comprises a carboxyl group-containing acrylic binder resin, a photopolymerizable monomer, a photopolymerizable initiator, and a thiol group-containing sensitizer represented by chemical formula 1; a modified compound of glycerol triacrylate; organic pigment; and solvent. In chemical formula 1, n is an integer of 2 ~ 6; n1 is 0 ~ 5; R is an organic group; R1 and R2 are identical or is selected from the group consisting of hydrogen and substituted or unsubstituted alkyl group.

Description

PHOTOSENSITIVE RESIN COMPOSITION FOR COLOR FILTER AND IMAGE SENSOR COLOR FILTER USING THE SAME}

The present invention relates to a photosensitive resin composition for a color filter and a color filter manufactured using the same, and more particularly, to a photosensitive resin composition for a color filter and a color filter manufactured using the same, which can form a fine pattern with improved sensitivity. It is about.

Electronic display devices used in office automation equipment, portable small televisions, viewfinders of video cameras, etc. Liquid crystal display (LCD), plasma display panel (PDP), organic light emitting diodes (organic light emitting diodes): OLED) and the like, and research and development of technologies related to these are being actively conducted.

The liquid crystal display device, which is one of the display devices, has advantages such as light weight, thinness, low cost, low power consumption, and excellent bonding with an integrated circuit, and thus its use range is expanding for notebook computers, monitors, and TV images. The liquid crystal display device includes a lower substrate on which a black matrix, a color filter, and an ITO pixel electrode are formed, an active circuit unit consisting of a liquid crystal layer, a thin film transistor, and a capacitor layer, and an upper substrate on which an ITO pixel electrode is formed.

The color filter includes a black matrix layer formed in a predetermined pattern on a transparent substrate to shield boundaries between pixels, and a plurality of colors (typically red (R), green (G), and blue () to form each pixel. The pixel parts arranged in order of the three primary colors of B) are sequentially stacked, and the color filter is coated with three or more colors on a transparent substrate by dyeing, printing, electrodeposition, pigment dispersion, or the like. Are manufactured.

In the dyeing method, an image having a dye-based substrate such as natural photosensitive resin such as gelatin, amine-modified polyvinyl alcohol, amine-modified acrylic resin, etc. is formed on the substrate, and then dyed with a dye such as a direct dye to form a colored thin film. In order to form a multi-colored thin film on the same substrate, it is necessary to perform flameproof processing every time the color is changed, so that the process is very complicated and the time is delayed. In addition, although the clarity and dispersibility of the dyes and resins generally used are good, there are disadvantages in that light resistance, moisture resistance and heat resistance, which are the most important characteristics, are poor.

In the printing method, printing is performed using the ink which disperse | distributed the pigment to thermosetting or photocurable resin, and a colored thin film is formed by hardening with heat or light. This method can reduce the material cost compared to other methods, but has a disadvantage in that it is difficult to form highly precise and detailed images, and the thin film layer formed is not uniform.

As another method, the electrodeposition method using the electroprecipitation method is proposed. The electrodeposition method is capable of forming a precise colored net, and has a characteristic of excellent heat resistance and light resistance since pigments are used. However, when the pixel size becomes precise and the electrode pattern becomes fine in the future, color unevenness due to electrical resistance appears on both ends or the thickness of the colored film becomes thick, which makes it difficult to apply to color filters requiring high precision.

On the other hand, the pigment dispersion method is a method of forming a colored thin film by repeating a series of processes of coating-exposure-developing-thermosetting a photopolymerizable composition containing a colorant on a transparent substrate provided with a black matrix. The pigment dispersion method has the advantage of improving heat resistance and durability, which are the most important properties of the color filter, and maintaining the thickness of the film uniformly.

The colored photosensitive resin composition used for manufacturing the color filter according to the pigment dispersion method generally consists of a binder resin, a photopolymerizable monomer, a photopolymerization initiator, an epoxy resin, a solvent and other additives, and the like.

There is a need for a photosensitive resin composition that improves sensitivity as a technique for forming a fine pattern in a short time is required for improving the performance of a liquid crystal display.

Conventional examples of improved sensitivity using thiol compounds include Japanese Patent Publication No. 2004-149755, Korean Patent Publication No. 2007-068356, and Korean Patent Publication No. 2007-073788. However, organic pigments (red, green, blue) In the case of the photosensitive resin composition using a), there is a problem in that the lowering of the adhesive force occurs and the residue remains around the pattern.

Therefore, development of the photosensitive resin composition which can solve such a problem is calculated | required.

The present invention is to provide a photosensitive resin composition for a color filter having an improved sensitivity that can form a fine pattern.

The present invention also provides a color filter made of the photosensitive resin composition for color filters.

The present invention also provides a liquid crystal display device comprising the color filter.

In order to achieve the above object, according to one embodiment of the present invention, [A] carboxyl group-containing acrylic binder resin, [B] photopolymerizable monomer, [C] photopolymerization initiator, [D] containing a thiol group represented by the following formula (1) The photosensitive resin composition for color filters containing a sensitizer, the modified compound of [E] glycerol triacrylate, a [F] pigment, and a [G] solvent is provided.

 [Formula 1]

(Definition of each substituent in the formula (1) is the same as described in the detailed description of the invention.)

Other details of the embodiments of the present invention are included in the following detailed description.

The photosensitive resin composition for color filters according to the present invention has a sensitivity improved by a thiol group-containing sensitizer to form a fine pattern, and a lower tear caused when using a thiol-containing increaser by a modified compound of glycerol triacrylate. The phenomenon can also be prevented.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, whereby the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

Photosensitive resin composition for a color filter according to an embodiment of the present invention is a [A] carboxyl group-containing acrylic binder resin, [B] photopolymerizable monomer, [C] photopolymerization initiator, [D] The modified compound of [E] glycerol triacrylate, a [F] pigment, and a [G] solvent are contained.

[A] carboxyl group-containing acrylic binder resin

The carboxyl group-containing acrylic binder resin is a copolymer of an ethylenically unsaturated first monomer having one or more carboxyl groups and another ethylenically unsaturated second monomer copolymerizable therewith.

Examples of the carboxyl group-containing ethylenically unsaturated first monomer include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, and the like, but are not limited thereto. The carboxyl group-containing acrylic binder resin used in the present invention contains at least one first monomer thereof. The carboxyl group-containing ethylenically unsaturated first monomer is preferably contained in 5 to 50% by weight, preferably 10 to 40% by weight based on the total amount of monomers.

As another ethylenically unsaturated 2nd monomer copolymerizable with the said carboxyl group-containing ethylenically unsaturated monomer, For example, styrene, (alpha) -methyl styrene, vinyltoluene, vinyl benzyl methyl ether, methyl acrylate, methyl methacrylate, ethyl acryl Latex, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-hydroxy ethyl acrylate, 2-hydroxy ethyl methacrylate, 2-hydroxy butyl acrylate, 2-hydroxy butyl methacrylate, Unsaturated carboxylic acid esters such as benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate and phenyl methacrylate; Unsaturated carboxylic acid amino alkyl esters such as 2-amino ethyl acrylate, 2-amino ethyl methacrylate, 2-dimethyl amino ethyl acrylate and 2-dimethyl amino ethyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Vinyl cyanide compounds such as acrylonitrile and methacrylonitrile; Unsaturated amides such as acryl amide and methacryl amide, and the like, and the like, but are not limited thereto. The carboxyl group-containing acrylic binder resin used in the present invention contains at least one second monomer thereof.

Specific examples of the carboxyl group-containing acrylic binder resin composed of such monomers include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacryl Late / 2-hydroxy ethyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxy ethyl methacrylate copolymer, and the like, but the present invention is not limited thereto.

The molecular weight (Mw) of the carboxyl group-containing acrylic binder resin is preferably 5,000 to 100,000, preferably 10,000 to 40,000. In addition, the acid value of the carboxyl group-containing acrylic binder resin is preferably in the range of 15 to 70 mgKOH / g, preferably 20 to 60 mgKOH / g. When the molecular weight and acid value of the carboxyl group-containing acrylic binder resin are in the above range, excellent pixel resolution can be obtained.

The carboxyl group-containing acrylic binder resin is used at 0.1 to 30% by weight based on the total amount of the photosensitive resin composition. If the content of the binder resin is less than 0.1% by weight, the problem that development does not occur in the alkaline developer occurs, whereas if it exceeds 30% by weight, there is a disadvantage in that the surface roughness increases due to the lack of crosslinkability.

[B] photopolymerizable monomer

Examples of the photopolymerizable monomer 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 , Trimethylol propane triacrylate, novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol di Methacrylate, 1,6-hexanediol dimethacrylate, or a combination thereof.

The amount of the photopolymerizable monomer is preferably 0.5 to 30% by weight based on the total amount of the photosensitive resin composition. If the content of the photopolymerizable monomer is less than 0.5% by weight, the phenomenon may occur so excessively that a corner portion of the cured film remaining in the pattern formation may have a problem of forming an unclear agent, and if it exceeds 30% by weight, it is not developed in the alkaline developer. There may be a problem.

[C] photopolymerization initiator

The photoinitiator used in the present invention is a photoinitiator generally used in the photosensitive resin composition, for example, triazine compounds, acetophenone compounds, benzophenone compounds, thioxanthone compounds, benzoin compounds, oxime compounds , Or a combination thereof can be used .

Examples of the triazine compounds include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, and 2- (3 ', 4'-dimeth Methoxy styryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxy naphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(p-methoxy phenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2 -Piphenyl-4,6-bis (trichloromethyl) -s-triazine, bis (trichlorobetayl) -6-styryl-s-triazine, 2- (naphtho 1-yl) -4,6 -Bis (trichloro methyl) -s-triazine, 2- (4-methoxy naphtho 1-yl) -4,6-bis (trichloro methyl) -s-triazine, 2-4-trichloro methyl (Piperonyl) -6-triazine, 2,4-trichloro methyl (4'-methoxy styryl) -6-triazine and the like.

Specific examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, and pt-butyltrichloroacetophenone , pt-butyldichloroacetophenone, 4-chloroacetophenone, 2,2'-dichloro-4-phenoxycetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, and the like.

Examples of the benzophenone compounds include benzophenone, benzoyl benzoic acid, benzoyl benzoic acid methyl, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, and 4,4'- Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.

Examples of the thioxanthone compound include thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-diisopropyl tea. Oxanthone, 2-chloro thioxanthone and the like.

Examples of the benzoin compounds include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyldimethyl ketal, and the like.

Examples of the oxime compound include 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione and 1- (o-acetyloxime) -1- [9-ethyl- 6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone is preferred as the photopolymerization initiator.

In addition to the photoinitiator, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, biimidazole compounds, and the like can also be used as the photopolymerization initiator.

The photopolymerization initiator is preferably used in 0.1 to 10% by weight based on the total amount of the photosensitive resin composition. If the content of the photopolymerization initiator is less than 0.1% by weight, there is a problem in that photopolymerization does not occur sufficiently during exposure in the pattern forming process. If the content is more than 10% by weight, the problem that the unreacted initiator remaining after photopolymerization lowers the transmittance is It is not desirable.

[D] Thiol group-containing sensitizer

As the thiol group-containing sensitizer, a thiol group-containing compound represented by the following formula (1) may be used.

 [Formula 1]

In Chemical Formula 1,

n is an integer from 2 to 6,

n ₁ is 0 to 5, preferably an integer of 1 to 3,

R is a 2- to 6-valent organic group, more preferably a C ₁ to C ₁₈ substituted or unsubstituted alkyl group, C ₆ to C ₃₀ may be a substituted or unsubstituted aryl group,

R ₁ and R ₂ are the same or independently selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group.

Unless stated otherwise in the present specification, "substituted" means that at least one hydrogen atom of the compound is substituted with a halogen group, an alkenyl group, or an alkoxy group.

Unless stated otherwise in the present specification, an alkyl group is a C ₁ to C ₂₀ alkyl group, more preferably C ₁ To an alkyl group of C _6, an alkenyl of the alkenyl group refers to C ₁ to C ₂₀ group, preferably C ₁ And to C ₁₀ alkenyl group, the alkoxy group refers to an alkoxy group of C ₁ to C _20, preferably means an alkoxy group of C ₁ to C _10.

The thiol group-containing sensitizer is preferably contained in 0.01 to 2% by weight based on the total amount of the photosensitive resin composition. When the content of the thiol group-containing sensitizer is 0.01 to 2% by weight, there is an advantage that high sensitivity and sharpness can be obtained.

[E] Modified Compounds of Glycerol Triacrylate

As the modified compound of the glycerol triacrylate, those represented by the following formula (2) can be used.

[Formula 2]

In Chemical Formula 2,

l, m and n are the same or independently of each other an integer of 1 or more, l + m + n is an integer of 3 to 10, preferably l + m + n is an integer of 2 to 5;

The content of the glycerol triacrylate modified compound is preferably included so as to be 0.1 to 10% by weight based on the total amount of the photosensitive resin composition. In the above range, the residues around the pattern and the lower tearing phenomenon can be effectively improved, which is preferable.

[F] Pigments

An organic pigment may be used as the pigment. As the organic pigment, condensed polycyclic pigments such as anthraquinone pigments, perylenes, phthalocyanine pigments, azo pigments, combinations thereof, and the like can be used.

As an organic pigment, the compound classified as a pigment in a color index can be mentioned concretely. Specific examples of such compounds include C.I. Pigment Yellow No. 1, C.I. Pigment Yellow No. 12, C.I. Pigment Yellow No. 13, C.I. Pigment Yellow No. 14, C.I. Pigment Yellow No. 15, C.I. Pigment Yellow No. 16, C.I. Pigment Yellow No. 17, C.I. Pigment Yellow No. 20, C.I. Pigment Yellow No. 24, C.I. Pigment Yellow No. 31, C.I. Pigment Yellow No. 53, C.I. Pigment Yellow No. 83, C.I. Pigment Yellow No. 86, C.I. Pigment Yellow 93, C.I. Pigment Yellow No. 94, C.I. Pigment Yellow No. 109, C.I. Pigment Yellow No. 110, C.I. Pigment Yellow No. 117, C.I. Pigment Yellow No. 125, C.I. Pigment Yellow No. 128, C.I. Pigment Yellow 137, C.I. Pigment Yellow 138, C.I. Pigment Yellow No. 139, C.I. Pigment Yellow No. 147, C.I. Pigment Yellow 148, C.I. Pigment Yellow No. 150, C.I. Pigment Yellow 153, C.I. Pigment Yellow 154, C.I. Pigment Yellow 166, C.I. Pigment Yellow No. 173, C.I. Pigment Orange No. 13, C.I. Pigment Orange No. 31, C.I. Pigment Orange No. 36, C.I. Pigment Orange No. 38, C.I. Pigment Orange No. 40, C.I. Pigment Orange No. 42, C.I. Pigment Orange No. 43, C.I. Pigment Orange No. 51, C.I. Pigment Orange No. 55, C.I. Pigment Orange No. 59, C.I. Pigment Orange No. 61, C.I. Pigment Orange 64, C.I. Pigment Orange 65, C.I. Pigment Orange 71, C.I. Pigment Orange No. 73, C.I. Pigment Red No. 9, C.I. Pigment Red No. 97, C.I. Pigment Red No. 105, C.I. Pigment Red No. 122, C.I. Pigment Red 123, C.I. Pigment Red 144, C.I. Pigment Red 149, C.I. Pigment Red 166, C.I. Pigment Red 168, C.I. Pigment Red 176, C.I. Pigment Red No. 177, C.I. Pigment Red No. 180, C.I. Pigment Red 192, C.I. Pigment Red 215, C.I. Pigment Red 216, C.I. Pigment Red 224, C.I. Pigment Red 242, C.I. Pigment Red No. 254, C.I. Pigment Red No. 264, C.I. Pigment Red No. 265, C.I. Pigment Blue No. 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue No. 60, C.I. Pigment Purple No. 1, C.I. Pigment Purple No. 19, C.I. Pigment Purple No. 23, C.I Pigment Purple No. 29, C.I Pigment Purple No. 32, C.I Pigment Purple No. 36, C.I Pigment Purple No. 38, C.I. Pigment Green No. 7, C.I. Pigment Green No. 36, C.I. Pigment Brown No. 23, C.I. Pigment brown No. 25, etc. are mentioned. These organic pigments can be used individually or in combination of 2 or more types, respectively.

The pigment is preferably included in 1 to 40% by weight, more preferably 5 to 20% by weight based on the total amount of the photosensitive resin composition. If the content of the pigment is less than 1% by weight, the desired color reproducibility may not be obtained. If the content of the pigment is more than 40% by weight, the curing property of the pattern may be remarkably lowered and the adhesion may be degraded.

In addition, the pigment may be dispersed in a solvent to prepare a pigment dispersion first, and then mixed and used in the ink composition for color filters, which may be prepared according to a conventional method for producing a pigment dispersion.

[G] Solvent

As the solvent, a water-soluble organic solvent can be used. As a typical example of the said water-soluble organic solvent, Ethylene glycol, such as ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol ; Glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether ; Glycol ether acetates such as ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate and diethylene glycol monobutyl ether acetate; Propylene glycols such as propylene glycol, dipropylene glycol and polypropylene glycol; Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monomethyl ether; Propylene glycol ethers such as propylene glycol diethyl ether and dipropylene glycol diethyl ether; Propylene glycol ether acetates such as propylene glycol monomethyl ether acetate and dipropylene glycol monoethyl ether acetate; Glycerin, 2- (methoxymethoxy) ethanol, 2-butoxy ethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, 1-methoxy-2-propanol, 1-ethoxy- 2 propanol etc. can be used. Any one of these may be used alone, or two or more thereof may be mixed and used.

The amount of the solvent used is used in the amount of the balance, preferably in an amount of 20 to 90% by weight. It is preferable that the content of the solvent is excellent in the applicability of the photosensitive resin composition and the flatness of the film having a thickness of 3 µm or more can be maintained within the above range.

[H] other additives

The photosensitive resin composition for color filters may optionally further include an epoxy resin in addition to the components of (A) to (G) to improve film crosslinking formation, heat resistance, chemical resistance, and the like of the pattern.

Any of these epoxy resins can be used as long as they are rich in reactivity and excellent in heat resistance and chemical resistance. Specific examples include one or more selected from thermosetting epoxy resins such as ortho cresol novolac epoxy resins, bisphenol A-ECH resins, novolac epoxy resins, brominated epoxy resins, fatty acid epoxy resins, and the like. no. The epoxy resin is preferably added in 0.1 to 10% by weight based on the total amount of the photosensitive resin composition. If the content of the epoxy resin is less than 0.1% by weight, the film crosslinkability is not improved, and thus the chemical resistance may not be improved. If the content of the epoxy resin is more than 10% by weight, the adhesive may be adhered to the glass plate during soft baking, resulting in deterioration of developing processability and the possibility of residue. It is not preferable because there is a problem that increases. Most preferably, ortho cresol novolac epoxy resin may be added at 0.1 to 10% by weight based on the total amount of the photosensitive resin composition.

When the epoxy compound is further included, a radical polymerization initiator such as a peroxide initiator or an azobis-based initiator may be further included.

In addition, the photosensitive resin composition of the present invention may optionally further include additives such as a dispersant, a silane coupling agent, and a surfactant, within a range that does not impair the physical properties of the composition.

The dispersant may be used to uniformly disperse the pigment in a solvent, preferably at least one selected from the group consisting of polyester, polyethyleneimine, polyurethane, and acrylic acid. The dispersant may be included in an amount of 0.001 to 100 parts by weight based on 100 parts by weight of the pigment.

The silane coupling agent may be used to prevent stains or spots during coating, leveling properties, or the generation of residues due to undeveloped, preferably malonic acid; 3-amino-1,2-propanediol; The silane coupling agent which has a vinyl group or a (meth) acryloxy group can be used.

The surfactant may be used to uniformly disperse the pigment component in the solvent and improve leveling properties, and preferably a fluorine-based surfactant may be used. In the case of the fluorine-based surfactant, not only the electrical property is excellent, but also the leveling property is high at high speed coating, and since there are few bubbles, the film defect is small. It can be given. The fluorine-based surfactant may be made of polyether co-modified silicone, and specific examples include FC-430, F-475, etc. of 3M, but are not limited thereto. The said surfactant can be used individually or in mixture of 2 or more types. The surfactant may be included in an amount of 0.01 to 5 wt% based on the total amount of the photosensitive resin composition. If it is out of the above range, there is a problem that foreign matter occurs after development is not preferable.

According to another embodiment of the present invention provides a color filter including a pattern manufactured using the photosensitive resin composition having the above configuration.

The color filter may have a transmittance of 90 to 100% at a wavelength of 500 nm to 570 nm.

The photosensitive resin composition of this invention is apply | coated in thickness of 0.5-10 micrometers, for example using suitable methods, such as spin coating, slit coating, roller coating, and spray coating, on the glass substrate for color filters. After application, the active line is irradiated to form a pattern required for the color filter. As a light source used for irradiation, UV light of 190-450 nm, Preferably 200-400 nm area | region is irradiated, for example, electron beam and X-ray irradiation are also suitable. After irradiating the light, the coating layer is treated with an alkaline developer, so that the unilluminated portion of the coating layer is dissolved and a pattern necessary for the color filter is formed. By repeating this process in accordance with the required number of colors, a color filter having a desired pattern can be obtained. Further, in the above process, crack resistance, solvent resistance, and the like can be further improved by heating the image pattern obtained by development again or curing by active ray irradiation or the like.

Hereinafter, the present invention will be described in more detail with reference to examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example 1 Preparation of Photosensitive Resin Composition

Using the components shown in Table 1 below, the photosensitive resin compositions of Example 1 and Comparative Examples 1 to 3 were prepared.

 First, [C] a photoinitiator, [D] trimethylolpropane tris-3-mercapto propionate (TMMP, Aldrich), and [H] ortho cresol novolac epoxy resin (Nippon Kayaku Co.) After dissolving in propylene glycol monomethyl ether, the mixture was stirred at room temperature for 2 hours.

[A] carboxyl group-containing acrylic binder resin (methacrylic acid / benzyl methacrylate = 30: 70 (w / v), molecular weight (Mw) = 20,000), [B] dipentaerythritol hexaacrylate, and [ E] trimethylolpropane polypropoxylate triacrylate (Megachem) was added and stirred at room temperature for 2 hours. [F] Pigment Green No. 36 was added thereto, followed by stirring at room temperature for 1 hour. Then, [H] methacryloxy silane coupling agent (Chiso Corp.) and [H] fluorine-based surfactant (F-475, DIC Corp.) were added and stirred at room temperature for 1 hour. The solution was filtered three times to remove impurities to prepare a photosensitive resin composition.

Ingredient (unit g) Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 [A] carboxyl group-containing acrylic binder resin 15 15 15 15 15 15 [B] photopolymerizable monomer 4 4 4 4 4 4  [c] photopolymerization initiator TAZ-110 (Midori Kagaku Corporation) 0.5 0.3 0.5 0.5 0.5 0.3 Igacure 907 (Shibagaiki Co., Ltd.) 0.5 0.3 0.5 0.5 0.5 0.3 3 [4,4'-bis (diethylamino) benzophenone (Hodogaya Co., Ltd.) 0.5 0.3 0.5 0.5 0.5 0.3 [D] Thiol group-containing sensitizer 0.2 0.2 - - 0.2 - [E] Modified Compounds of Glycerol Triacrylate One One - One - - [F] Pigment Green No. 36 7 7 7 7 7 7 [G] Solvent 70.6 71.2 71.8 70.8 71.6 72.4 [H] other additives Ortho Cresol Novolak Epoxy Resin 0.3 0.3 0.3 0.3 0.3 0.3 Methacryloxy silane coupling agent 0.2 0.2 0.2 0.2 0.2 0.2 Fluorinated Surfactant 0.2 0.2 0.2 0.2 0.2 0.2

<Physical evaluation>: evaluation of the sensitivity, tearing, and residue around the pattern

The photosensitive resin compositions of Examples 1 to 2 and Comparative Examples 1 to 4 were respectively applied to a thickness of 1 to 2 μm on a 1 mm thick glass substrate degreased and washed at 80 ° C. for 2 minutes on a hot plate. Drying gave 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, followed by development for 30 seconds at 30 ° C. and atmospheric pressure using an aqueous 1% potassium hydroxide solution. The photomask used in this experiment can express line widths of 2, 3, 5, 7, 10, and 50 µm. After development, the pattern was obtained by drying at 220 ° C. for 40 minutes in a hot air circulation drying furnace. The obtained pattern was evaluated for sensitivity, lower tearing, and residues around the pattern based on the following criteria, which are shown in Table 2 below.

(1) sensitivity

As an extent to which the pattern of 2, 3, 5, 7, 10, and 50 micrometer line widths remain with respect to the pattern manufactured using the photosensitive resin composition of Examples 1-2 and Comparative Examples 1-4 using the optical microscope Sensitivity was evaluated.

○: excellent sensitivity-pattern with a line width of 2 μm remains without tearing

(Triangle | delta): Good sensitivity-When the pattern of 3 micrometers of line widths remains without tearing.

X: Inferior sensitivity-When the pattern of the line width 2 micrometers and 3 micrometers was not torn off

(2) lower tearing

Using a scanning electron microscope (SEM), the presence or absence of bottom tearing was determined with respect to a pattern having a line width of 50 µm prepared using the photosensitive resin compositions of Examples 1 to 2 and Comparative Examples 1 to 4.

○: lower tearing

△: weak level tearing

×: no tearing

(3) around the pattern Residue

The presence or absence of the residue was determined about the pattern of the 50 micrometer line width manufactured using the photosensitive resin composition of Examples 1-2 and Comparative Examples 1-4 by a scanning electron microscope (SEM) and an optical microscope.

○: residue

△: weak level residue

×: no residue

Sensitivity Lower tearing Residue around pattern Example 1 ○ × × Example 2 ○ × × Comparative Example 1 △ × △ Comparative Example 2 △ × × Comparative Example 3 ○ ○ ○ Comparative Example 4 × × △

<Comparison of Sensitivity Enhancement Effects>

The sensitivity of the photosensitive resin compositions of Examples 1 and 2 including the thiol group-containing sensitizer and the modified compound of glycerol triacrylate was higher than that of the photosensitive resin composition of Comparative Example 1 containing no thiol group-containing sensitizer. .

In addition, in the composition of Example 2, Comparative Example 4 except the thiol group-containing sensitizer appeared very low sensitivity. In other words, the thiol group-containing sensitizer improves the sensitivity, in some cases it was confirmed that there is an effect that can be used to lower the content of the photopolymerization initiator.

<Comparing effect of lower tearing and residues>

The pattern prepared from the photosensitive resin compositions of Examples 1 and 2 using a thiol group-containing sensitizer and a glycerol triacrylate-modified compound in an appropriate amount was confirmed that no tearing and residues appeared.

The pattern made of the photosensitive resin compositions of Comparative Examples 1 and 4 without using a thiol group-containing sensitizer and a glycerol triacrylate-modifying compound showed no lower tearing, and the residue appeared at a weak level, but the thiol group-containing sensitizer was used. Comparative Example 3, which was used and did not use a glycerol triacrylate modified compound, showed significant levels of bottom tearing and residue.

Therefore, it was confirmed that the glycerol triacrylate-modified compound improved the lower tearing phenomenon and residue generation that appeared when using the thiol group-containing sensitizer.

The present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications may be made by those skilled in the art within the scope of the technical idea of the present invention. It is possible.

Claims (7)

[A] carboxyl group-containing acrylic binder resin, [B] photopolymerizable monomer, [C] photopolymerization initiator, [D] thiol group-containing sensitizer represented by the following formula (1), [E] glycerol triacrylate modified compound, [F ] Photosensitive resin composition containing organic pigment and [G] solvent.  [Formula 1]

(In Formula 1, n is an integer from 2 to 6, n ₁ is 0 to 5, R is a 2- to 6-valent organic group, R ₁ and R ₂ are the same or independently selected from the group consisting of hydrogen and a substituted or unsubstituted alkyl group.) The method of claim 1, 0.1-30 wt% of carboxyl group-containing acrylic binder resin 0.5-30 wt% of photopolymerizable monomer 0.1 to 10% by weight of photopolymerization initiator Thiol group-containing sensitizer 0.01 to 2% by weight 0.1 to 10% by weight of modified compound of glycerol triacrylate 1 to 40% by weight of organic pigment And a solvent as the remaining amount. The method of claim 1, The modified compound of the glycerol triacrylate is represented by the following formula (2). [Formula 2]

(In Formula 2, l, m, and n are the same or independently of each other an integer of 1 or more, and 1 + m + n is an integer of 3 to 10.) The method of claim 1, The photosensitive resin composition is a photosensitive resin composition which further contains an epoxy resin in 0.1 to 10 weight% with respect to the photosensitive resin composition total amount. The method of claim 1, The photosensitive resin composition which further contains 0.001-100 weight part with respect to 100 weight part of pigments at least 1 type of dispersing agent chosen from the group which consists of polyester type, polyethyleneimine type, polyurethane type, and acrylic acid type. The method of claim 1, The photosensitive resin composition is a photosensitive resin composition further comprises 0.01 to 5% by weight of the fluorine-based surfactant based on the total amount of the photosensitive resin composition. The color filter containing the pattern manufactured from the photosensitive resin composition of any one of Claims 1-6.