KR20090065220A - Photosensitive resin composition and black matrix using the same - Google Patents

Abstract

A photosensitive resin composition containing a leveling agent and a display unit employing an optical shield layer manufactured by the same are provided to ensure excellent film uniformity, development and printing margin. A photosensitive resin composition comprises: 1-40wt% of acrylic binder resin; 1-20wt% of photo-polymerizable monomers; 0.1-10wt% of photo-polymerizable initiator; 5-40wt% of pigments; 0.03-0.5wt% of leveling agent selected from the group consisting of a silicone-based compound represented by the formula 1, a fluorine-based compound represented by the formula 2 and their mixture; and solvents. In the formula 1, N is an integer of 1 to 5; and R1, R2, R3 and R4 are identically or independently substituted or non-substituted alkyl groups or substituted or non-substituted aryl groups. In the formula 2, P is an integer of 1 to 10; q is an integer of 0 to 30; m is an integer of 0 to 2; R5 is hydrogen, substituted or non-substituted alkyl group or halogen element; and R6 is hydrogen, substituted or non-substituted alkyl group, halogen element, epoxy group or (meth)acrylate group.

Description

Photosensitive resin composition and light-shielding layer manufactured using the same {PHOTOSENSITIVE RESIN COMPOSITION AND BLACK MATRIX USING THE SAME}

The present invention relates to a photosensitive resin composition and a light shielding layer prepared using the same, more particularly, excellent film uniformity and developability, and excellent ink spreadability when ink is printed on a pattern of a formed light shielding layer. The present invention relates to a photosensitive resin composition capable of preventing overflow of ink and a light shielding layer manufactured using the same.

The color filter is used in a liquid crystal display device, an optical filter of a camera, and the like, and is manufactured by coating a fine region colored with three or more colors on a solid state imaging device or a transparent substrate. Such colored thin films are usually formed by dyeing, printing, electrodeposition, pigment dispersion, inkjet, or the like.

In the dyeing method, an image having a dye-based base material such as natural photosensitive resin, such as gelatin, amine-modified polyvinyl alcohol, and amine-modified acrylic resin, is formed on a 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 commonly used dyes and resins themselves are good, there are disadvantages in that light resistance, moisture resistance and heat resistance, which are the most important characteristics, are bad. For example, although Korean Patent Publication No. 1991-4717 and Korean Patent Publication No. 1994-778 use azo compounds and azide compounds as dyes, they have disadvantages of low heat resistance and durability as compared to pigments.

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. According to this method, the material cost can be reduced compared to other methods, but it is difficult to form highly precise and detailed images, and the thin film layer formed is not uniform. Republic of Korea Patent Publication No. 1995-9003746 and Republic of Korea Patent Publication No. 1996-11513 propose a method of manufacturing a color filter using the inkjet method, the color resist composition sprayed from the nozzle for the printing of a delicate and accurate pigment dye type As a result, the durability and heat resistance are inferior to the dyeing method.

On the other hand, Korean Patent Publication No. 199-7000858 and Korean Patent Publication No. 1996-29904 propose an electrodeposition method using an electroprecipitation method. The electrodeposition method can form a precise colored film and uses a pigment so that heat resistance and It has excellent light resistance, but when the pixel size becomes precise and the electrode pattern becomes fine in the future, color unevenness appears due to electric resistance on both ends or the thickness of the color film becomes thick, so it is applied to color filter requiring high precision. Is difficult.

The pigment dispersion method is a method in which a colored thin film is formed by repeating a series of processes of coating-exposure-developing-thermosetting a photopolymerizable composition containing a colorant on a transparent substrate provided with a light shielding layer (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. In addition, since the fine pattern is excellent in implementation and the manufacturing method is relatively easy, it is commonly adopted. For example, Republic of Korea Patent Publication No. 1992-7002502, Republic of Korea Patent Publication 199-5617, Republic of Korea Patent Publication 1995-11163, Republic of Korea Patent Publication 1995-700359 and the like proposed a method for producing a color resist using pigment dispersion have.

However, the method requires coating, exposure, development and curing for red (R), green (G) and blue (B), respectively, in order to form a pixel, resulting in too long a manufacturing process line and an interprocess control factor. As the number increases, there is a difficulty in yield management. In addition, there is a problem in the actual production process, such as the need to increase the thickness of the coating film as a high color reproduction ratio and high contrast ratio is required in the monitor, TV, and the like.

In order to overcome this problem, a number of new process methods have recently been used to replace the conventional pigment dispersion method, which is representative of inkjet printing. In the inkjet printing method, a light shielding layer (black matrix) is formed on a glass substrate and ink is injected into the pixel space. The inkjet printing method does not require a separate coating, exposure, development, or the like process in manufacturing the color filter, so that materials required for the process may be reduced and the process may be simplified.

Ink injected into the pixel space is generally a liquid composition having a hydrophilic property, including a pigment, a solvent, other dispersants and the like. Since the ink is a volatile solution, in order to inject the ink into the pixel space of the color filter substrate, it is necessary to inject a larger amount of ink than the desired height in consideration of volatilization of the ink. Therefore, a problem arises in that ink overflows to the surface of the light shielding layer and ink spreads between adjacent pixel spaces. In addition, when the ink bleeding occurs between the pixel spaces, the color characteristics of the liquid crystal display device are lowered, and further, the display quality is deteriorated.

The present invention provides a photosensitive resin composition which is excellent in film uniformity and developability, is excellent in spreadability of ink, can prevent ink overflow, and is excellent in printing margin.

This invention also provides the light shielding layer manufactured using the said photosensitive resin composition.

However, technical problems to be achieved by the present invention are not limited to the above-mentioned problems, and other technical problems will be clearly understood by those skilled in the art from the following description.

According to one embodiment of the invention, (A) acrylic binder resin; (B) photopolymerizable monomers; (C) photoinitiator; (D) pigments; (E) a leveling agent selected from the group consisting of a silicone compound of formula 1, a fluorine compound of formula 2, and a mixture thereof; And (F) a solvent.

[Formula 1]

[Formula 2]

(In Chemical Formulas 1 and 2,

n is an integer from 1 to 5,

R ₁ , R ₂ , R ₃ , and R ₄ are the same or independently selected from the group consisting of a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group,

p is an integer from 1 to 10,

q is an integer from 0 to 30,

m is an integer from 0 to 2,

R ₅ is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and halogen,

R ₆ is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, a halogen, an epoxy group, and a (meth) acrylate group.)

According to another embodiment of the present invention, a light blocking layer made of the photosensitive resin composition is provided.

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

The photosensitive resin composition of the present invention is excellent in film uniformity and developability, and when the ink is printed on the pattern of the formed light shielding layer, the ink spreadability is excellent and the ink can be prevented from overflowing.

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, by which 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 according to an embodiment of the present invention, (A) acrylic binder resin; (B) photopolymerizable monomer; (C) photoinitiator; (D) pigments; (E) a leveling agent selected from the group consisting of the silicone compound of Formula 1, the fluorine compound of Formula 2, and mixtures thereof; And (F) a solvent.

Hereinafter, each component included in the photosensitive resin composition for color filters will be described in detail.

(A) Acrylic Binder Resin

The 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. At this time, the carboxyl group-containing ethylenically unsaturated first monomer is in the range of 5 to 50% by weight, preferably 10 to 40% by weight based on the total copolymer. It is preferable that it is 3,000-100,000, and, as for the molecular weight (Mw) of the said acrylic binder resin, it is more preferable that it is 10,000-20,000. In addition, the acid value of the acrylic binder resin is in the range of 15 to 200 mgKOH / g, preferably 20 to 150 mgKOH / g. When the molecular weight and acid value of the acrylic binder resin are in the above range, an excellent pixel resolution can be obtained.

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 acrylic binder resin used in the present invention contains at least one first monomer thereof.

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 acrylic binder resin used in the present invention contains at least one second monomer thereof.

Specific examples of the acrylic binder resin composed of the monomers described above include methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 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 acrylic binder resin is preferably included in 1 to 40% by weight based on the total amount of the photosensitive resin composition. If the content of the binder resin is less than 1% by weight, there is a concern that development does not occur in the alkaline developer, and if it exceeds 40% by weight, crosslinkability may be insufficient and surface roughness may increase.

(B) photopolymerizable monomer

The photopolymerizable monomer used in the present invention can be used without limitation as long as it is generally used in the photosensitive resin composition for color filters. Typically ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, pentaerythritol diacrylate, penta Erythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A diacrylate, trimethylolpropane triacrylate, Novolac epoxy acrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4-butanediol dimethacrylate, 1,6- Acrylic photopolymerizable monomers, such as hexanediol dimethacrylate, can be used.

The photopolymerizable monomer is preferably included in 1 to 20% by weight based on the total amount of the photosensitive resin composition. If the content of the photopolymerizable monomer is less than 1% by weight, a problem occurs that the edges of the pattern are not formed cleanly, whereas if the content of the photopolymerizable monomer exceeds 20% by weight, the developer is not developed in the alkaline developer.

(C) photopolymerization initiator

The photoinitiator used in the present invention is a photoinitiator generally used in the photosensitive resin composition, for example, triazine compound, acetophenone compound, benzophenone compound, thioxanthone compound, benzoin compound, oxime compound Etc. 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, etc. are mentioned.

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 (diethyl amino) 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. Orcanthone, 2-chloro thioxanthone and the like.

The benzoin-based compound includes 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 photopolymerization initiator, 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 included 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, photopolymerization does not occur sufficiently during exposure in the pattern forming process, whereas if it exceeds 10% by weight, the unreacted initiator remaining after the photopolymerization may cause a problem of lowering the transmittance.

(D) pigment

As the pigment, a black pigment may be used. For example, aniline black, perylene black, titanium black, carbon black, or the like may be used. Moreover, as a color correction agent, organic pigments, such as condensed polycyclic pigments, such as an anthraquinone pigment and a perylene pigment, a phthalocyanine pigment and an azo pigment, can be added and used. These pigments can be used individually by 1 type or in mixture of 2 or more types.

The pigment may be included in the photosensitive resin composition as a dispersion, wherein the pigment dispersion solvent is ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl Ethers and the like can be used, of which propylene glycol methyl ether acetate is most preferred.

In addition, a dispersing agent may be further used as needed so that the said pigment component may be disperse | distributed uniformly in a pigment dispersion liquid, and a pigment may be surface-treated with a dispersing agent and used. For this purpose both nonionic, anionic or cationic dispersants can be used, for example polyalkylene glycols and their esters, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, Sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylates, alkylamide alkylene oxide adducts, alkylamines and the like can be used. These dispersants can be used individually by 1 type or in combination of 2 or more types as appropriate.

In addition, by using an acrylic binder resin in addition to the dispersant, it is possible not only to improve the stability of the pigment dispersion liquid, but also to improve the pattern of the pixel.

The black pigment is preferably contained in 5 to 40% by weight based on the total amount of the photosensitive resin composition. When the content of the pigment is less than 5% by weight, the coloring effect is insignificant, whereas when the content of the pigment is more than 40% by weight, there is a disadvantage in that the developing performance is sharply reduced.

In addition, when the pigment further comprises an organic pigment as a color correction agent, the organic pigment is preferably included in 0.1 to 2 parts by weight based on 100 parts by weight of black pigment.

(E) Leveling agent

As the leveling agent, one selected from the group consisting of a silicone compound of Formula 1, a fluorine compound of Formula 2, and a mixture thereof is used. The leveling agent increases the hydrophobicity of the surface of the light shielding layer to improve the processability of the inkjet method.

First, the silicone compound leveling agent of Formula 1 is as follows.

[Formula 1]

In Chemical Formula 1,

n is an integer from 1 to 5,

R ₁ , R ₂ , R ₃ , and R ₄ may each be the same or independently selected from the group consisting of a substituted or unsubstituted alkyl group, and a substituted or unsubstituted aryl group, preferably C ₁ to C It may be selected from the group consisting of ₂₀ substituted or unsubstituted alkyl group, phenyl group, and benzyl group.

The silicone compound leveling agent of Chemical Formula 1 may be prepared by copolymerizing dimethylsilicone and polyoxyalkylene or by copolymerizing dimethylsiloxane and polyoxyalkylene.

Representative examples of the silicone compound leveling agent of Formula 1 include EFKA 3031 (Ciba), EFKA 3032 (Ciba), EFKA 7310 (Ciba), EFKA7315 (Ciba) And EFKA 3036 (Ciba).

In addition, the fluorine-based compound leveling agent of Formula 2 is as follows.

[Formula 2]

In Chemical Formula 2,

p is an integer from 1 to 10,

q is an integer from 0 to 30,

m is an integer from 0 to 2,

R ₅ may be selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and halogen. In this case, the alkyl group is preferably CH ₃ , and the halogen is preferably Cl or F.

In addition, R ₆ may be selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, a halogen, an epoxy group, and a (meth) acrylate group. In this case, the alkyl group is preferably CH ₃ , and the halogen is preferably Cl or F.

Representative examples of the fluorine-based compound leveling agent of Formula 2 include F411, F444, F470, F489, and F178K (DIC Corporation) having a perfluoroalkyl group.

Unless stated otherwise in the present specification, "substituted" means that at least one of the hydrogen atoms in the compound is substituted with one selected from the group consisting of alkyl group, aryl group, hydroxyl group, alkoxy group, cycloalkyl group, and halogen. do.

Unless otherwise noted herein, the alkyl group is an alkyl group of C ₁ to C _30, preferably C ₁ to an alkyl group of C _20, aryl group refers to C ₆ to an aryl group of C _30, preferably C ₆ to C The aryl group of ₁₂ is an alkoxy group, a C ₁ to C ₃₀ alkoxy group, preferably a C ₁ to C ₁₅ alkoxy group, a cycloalkyl group is a C ₃ to C ₃₀ cycloalkyl group, preferably C ₆ To a cycloalkyl group of C ₁₂ .

The leveling agent selected from the group consisting of the silicone compound of Formula 1, the fluorine-based compound of Formula 2, and mixtures thereof is preferably included in an amount of 0.03 to 0.5% by weight, and 0.05 to 0.2% by weight based on the total amount of the photosensitive resin composition. More preferably included. When the content of the leveling agent is less than 0.03% by weight, there is a problem in that the thickness uniformity of the photosensitive resin composition is decreased during coating, which is not preferable. When the content of the leveling agent exceeds 0.5% by weight, the surface of the formed light shielding layer pattern exhibits too strong hydrophobicity, resulting in overcoat. There is a problem that is not coated is not preferable.

(F) solvent

The solvent includes ethylene glycol acetate, ethyl cellosolve, propylene glycol methyl ether acetate, ethyl lactate, polyethylene glycol, and the like, and any one of these may be used alone, or two or more thereof may be mixed.

Moreover, as said solvent, Ethylene glycol, such as ethylene glycol and diethylene glycol; Glycol ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, ethylene glycol diethyl ether and 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; Propylene glycols such as propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene monobutyl ether, propylene glycol dimethyl ether, dipropylene glycol dimethyl ether, propylene glycol diethyl ether and dipropylene glycol diethyl ether Ethers; Propylene glycol ether acetates such as propylene glycol monomethyl ether acetate and dipropylene glycol monoethyl ether acetate; Amides such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide; Ketones such as methyl ethyl ketone (MEK), methyl isobutyl ketone (MIBK) and cyclohexanone; Petroleum such as toluene, xylene and solvent naphtha; Ester, such as ethyl acetate, butyl acetate, ethyl lactate, etc. can be used. These solvent can be used individually by 1 type or in mixture of 2 or more types.

The solvent is preferably used in the amount of the balance having a viscosity such that the photosensitive resin composition can be applied to the substrate, more preferably in the amount of 20 to 80% by weight. In the said range, the applicability | paintability of the photosensitive resin composition is excellent and the flatness of the apply | coated film can be maintained.

(G) other additives

The photosensitive resin composition may further include a dispersant so that the pigment component (D) is uniformly dispersed in the solvent (G) in addition to the components of the above (A) to (F).

As the dispersant, both nonionic, anionic or cationic dispersants may be used, for example, polyalkylene glycols and esters thereof, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, Sulfonic acid esters, sulfonates, carboxylic acid esters, carboxylates, alkylamide alkylene oxide adducts, alkylamines and the like can be used. These dispersants can be used individually by 1 type or in combination of 2 or more types as appropriate.

The dispersant is preferably added in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the pigment.

In addition, the photosensitive resin composition may further include a silane coupling agent in order to improve the adhesion of the light shielding layer pattern.

Examples of the silane coupling agent include 3-methacryloxy propyl trimethoxy silane; Silane coupling agents having a malonic acid, 3-amino-1,2-propanediol, a vinyl group or a (meth) acryloxy group, and the like can be used. The silane coupling agent may be added in an amount of 0.01 to 2 wt% based on the total amount of the photosensitive resin composition.

In addition, the photosensitive resin composition may further include other additives such as a surfactant, an antioxidant, and a stabilizer within a range that does not impair the physical properties of the composition.

The photosensitive resin composition of this invention is an alkali developing type composition which can be hardened by irradiation of light and can be developed by alkaline aqueous solution. The photosensitive resin composition is laminated on a substrate, and then irradiated with an active line to form a pattern required for a color filter, and reacts with light. At this time, compared with the unreacted portion, the solubility in the solvent is drastically lowered, and only the unreacted portion is selectively dissolved. A solution for removing such an unexposed portion is called a developer, and there are two types of developers, an organic solvent type and an alkali developer type. The organic solvent type causes air pollution and is harmful to the human body, but the photosensitive resin composition of the present invention does not cause environmental pollution.

The photosensitive resin composition of this invention can be used for manufacture of the light shielding layer for color filters of a liquid crystal display. The light shielding layer made of the photosensitive resin composition of the present invention preferably has a surface roughness of 50 kPa or more, and a contact angle between the surface of the light shielding layer and water is preferably 100 ° or more.

The photosensitive resin composition is applied to a glass substrate using a suitable method such as spin coating, roller coating, slit coating, spray coating, or the like, for example, at a thickness of 0.5 to 10 m. 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 alkali developer to dissolve the non-exposed portions of the coating 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. 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 are not intended to limit the scope of the present invention.

Example 1

Using the following components, a photosensitive resin composition was prepared as follows. That is, after dissolving the photopolymerization initiator in a solvent, it was stirred at room temperature for 2 hours. Then, an acrylic binder resin and an acrylic photopolymerizable monomer were added and stirred at room temperature for 2 hours. Pigments, fluorine compound leveling agents, And the silane coupling agent was added and stirred at room temperature for 1 hour. Filtering three times to remove impurities to prepare a photosensitive resin composition.

8 g of acrylic binder resin (A)

(a1) / (a2) = 30/70 (w / w), molecular weight (Mw) = 15,000

(a1): methacrylic acid

(a2): benzyl methacrylate

(B) Acrylic Photopolymerizable Monomer

Dipentaerythritol triacrylate 2.5g

(C) photopolymerization initiator

1.2 g of STR-A (respesa)

0.1 g of Igacure 369 (Shiba-Gaiiza)

(D) pigment 8 g

CI-M-050 (Sakata Ings)

(E) 0.1 g of leveling agent

F-489 (DIC Corporation)

(F) solvent

65 g of propylene glycol monomethyl ether

15 g of cyclohexanone

(G) Other additives

0.1 g of silane coupling agent (3-methacryloxypropyl trimethoxy silane)

Example 2

Except having used EFKA 3036 (Shiba Corporation) as a leveling agent, it carried out similarly to Example 1, and manufactured the photosensitive resin composition.

Comparative Example 1

A photosensitive resin composition was prepared in the same manner as in Example 1 except that no leveling agent was added.

[Property evaluation]

For the photosensitive resin compositions prepared in Examples 1 to 2 and Comparative Example 1, film uniformity, developability, surface roughness, contact angle, spreadability to ink, and repellency of the light shielding layer surface were evaluated, and the results are shown in Table 1 below. Shown in

(1) membrane uniformity

The photosensitive resin composition was applied on a 1 mm thick chromium coated glass substrate by degreasing, and dried at 80 ° C. for 1 minute on a hot plate 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, followed by development for 100 seconds at 30 ° C. and atmospheric pressure using a 1% potassium hydroxide aqueous solution. After development, the pattern was obtained by drying at 220 ° C. for 40 minutes in a hot air circulation drying furnace and measuring the presence or absence of irregularities in the pattern height.

 (Circle): Height difference ((DELTA) H) of a pattern on the same board | substrate is ± 0.2 or less

 Δ: height difference ΔH of the pattern on the same substrate is ± 0.2 to ± 0.3

 X: The height difference (ΔH) of the pattern on the same substrate is ± 0.3 or more

(2) developability

The photosensitive resin composition was apply | coated to the thickness of 2 micrometers on the chromium-coated glass substrate of the thickness which wash | cleaned degreasing, and it dried at 80 degreeC for 1 minute on a hotplate, and obtained the 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 100 seconds at 30 ° C. and atmospheric pressure using a 1% potassium hydroxide aqueous solution. After development, the pattern was obtained by drying at 220 ° C. for 40 minutes in a hot air circulation drying furnace to evaluate the patternability by an optical microscope.

 ○ Excellent fairness: no residual film on pattern and non-exposed glass substrate

 Good processability: When there is a residual film on the pattern, but there is no residual film on the unexposed glass substrate.

 × Poor processability: When there is residual film on pattern and unexposed glass substrate

(3) surface roughness

The photosensitive resin composition was apply | coated to the thickness of 2 micrometers on the chromium-coated glass substrate of the thickness which wash | cleaned degreasing, and it dried at 80 degreeC for 1 minute on a hotplate, and obtained the 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 100 seconds at 30 ° C. and atmospheric pressure using a 1% potassium hydroxide aqueous solution. After development, the pattern was obtained by drying at 220 ° C. for 40 minutes in a hot air circulation drying furnace and evaluated through a contact surface roughness meter. The measured value is in Å.

(4) contact angle

The photosensitive resin composition was apply | coated to the thickness of 2 micrometers on the chromium-coated glass substrate of the thickness which wash | cleaned degreasing, and it dried at 80 degreeC for 1 minute on a hotplate, and obtained the coating film. Subsequently, the coating film was covered with a metal plate half and exposed using a high pressure mercury lamp having a wavelength of 365 nm, followed by development for 100 seconds at 30 ° C. and atmospheric pressure using a 1% potassium hydroxide aqueous solution. After development, the specimen was obtained by drying at 220 ° C. for 40 minutes in a hot air circulation drying furnace, and the contact angle of the formed light shielding layer surface was measured by using a contact angle meter with one drop of distilled water and ink (green).

(5) spreadability

The photosensitive resin composition was apply | coated to the thickness of 2 micrometers on the chromium-coated glass substrate of the thickness which wash | cleaned degreasing, and it dried at 80 degreeC for 1 minute on a hotplate, and obtained the coating film. Subsequently, a photomask having a pixel structure 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 an aqueous 1% potassium hydroxide solution. After development, the pattern was obtained by drying at 220 ° C. for 40 minutes in a hot air circulation drying furnace, and a drop of ink (green) was printed on the pixel with a printing equipment.

 ○: When ink spreads to 50% or more of the pixel area

 Δ: ink spreads to a level of 20 to 50% of the pixel area

 ×: ink spreads to a level of 20% or less of the pixel area

(6) repulsive

The photosensitive resin composition was apply | coated to the thickness of 2 micrometers on the chromium-coated glass substrate of the thickness which wash | cleaned degreasing, and it dried at 80 degreeC for 1 minute on a hotplate, and obtained the coating film. Subsequently, a photomask having a pixel structure was placed on the coating film and exposed using a high pressure mercury lamp having a wavelength of 365 nm, followed by development for 100 seconds at 30 ° C. and atmospheric pressure using a 1% aqueous potassium hydroxide solution. After development, the pattern was obtained by drying at 220 ° C. for 40 minutes in a hot air circulation drying furnace, and ink (green) was printed on the pixels at 10 drop intervals with a printing equipment. At this time, the point in time where the ink does not overflow to the pixel next to the printing pixel is regarded as a good level.

 TABLE 1

Membrane uniformity Developability Surface roughness Contact angle (°) Spreadability Repulsive (drop number) Distilled water ink Example 1 ○ ○ 70 110 55 ○ 120 Example 2 ○ ○ 75 105 53 ○ 110 Comparative Example 1 × △ 73 45 14 ○ 20

Referring to Table 1, the patterns made of the photosensitive resin compositions of Examples 1 and 2 were all excellent in film uniformity, developability, spreadability, and resilience. In particular, it could be confirmed that the surface roughness of 70 (Å) or more, and the contact angle to the water was more than 100˚.

On the other hand, the pattern made from the photosensitive resin composition of Comparative Example 1 was significantly inferior in film uniformity, developability, and resilience as compared with Examples 1 and 2, in particular, the contact angle was significantly lower than those in Examples 1 and 2. I could confirm that.

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 (6)

 (A) acrylic binder resin; (B) photopolymerizable monomer; (C) photoinitiator; (D) pigments; (E) a leveling agent selected from the group consisting of a silicone compound of formula 1, a fluorine compound of formula 2, and a mixture thereof; And (F) a solvent. [Formula 1]

(In Formula 1, n is an integer from 1 to 5, R ₁ , R ₂ , R ₃ , and R ₄ are the same or independently selected from the group consisting of a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group.) [Formula 2]

(In Formula 2, p is an integer from 1 to 10, q is an integer from 0 to 30, m is an integer from 0 to 2, R ₅ is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, and halogen, R ₆ is selected from the group consisting of hydrogen, a substituted or unsubstituted alkyl group, a halogen, an epoxy group, and a (meth) acrylate group.) The method of claim 1, The photosensitive resin composition, (A) 1 to 40% by weight of the acrylic binder resin (B) 1 to 20% by weight of acrylic photopolymerizable monomer (C) 0.1 to 10% by weight of photopolymerization initiator (D) 5 to 40% by weight of pigment (E) 0.03 to 0.5% by weight of a leveling agent selected from the group consisting of silicone compounds, fluorine compounds, and combinations thereof (F) Solvent Residue Photosensitive resin composition comprising a. The method of claim 1, The surface roughness of the light shielding layer manufactured from the said photosensitive resin composition is 50 GPa or more. The method of claim 1, The photosensitive resin composition of the contact angle between the surface of the light-shielding layer made of the photosensitive resin composition and water is 100 ° or more. The light shielding layer for display devices manufactured from the photosensitive resin composition of any one of Claims 1-4. A display device comprising the light blocking layer of claim 5.