KR20120105572A - Photosensitive resin composition and reflector using the same - Google Patents

Abstract

PURPOSE: A photo-sensitive resin composition and a reflector using the same are provided to improve pattern characteristic, development characteristic, heat resistance characteristic, and light resistance characteristic. CONSTITUTION: A photo-sensitive resin composition includes a pigment, an acryl-based binder resin, a photopolymerizable monomer, a photo-polymerization initiator, and a solvent. The pigment includes titanium dioxide of the average diameter in a range between 200 and 450 nm. The content of the pigment is in a range between 5 and 20 weight% based on the total weight of the composition. The composition further includes an additive which is a silane-based coupling agent based on malonic acid, 3-amino-1,2-propanediol vinyl group, (meth)acryloxy group, a radical polymerization initiator, or the combination of the same.

Description

PHOTOSENSITIVE RESIN COMPOSITION AND REFLECTOR USING THE SAME}

The present substrate relates to a photosensitive resin composition and a reflecting plate using the same.

In general, the reflection type liquid crystal display device is a liquid crystal display device of a type that does not require a separate light source is provided to reflect the light introduced to the reflection plate provided inside the liquid crystal display using the incident light from the outside as a light source for display. Accordingly, low power consumption can be driven and a thin film can be realized.

Such a reflective liquid crystal display device includes a lower substrate, a reflective plate, a lower alignment layer, a liquid crystal layer, an upper alignment layer, an upper substrate, a retardation plate, a polarizing plate, and the like.

The reflector is required to have a high reflectance, and for this purpose, development of a photosensitive resin composition required for coating a photoresist in a photolithography process is being performed.

One aspect of the present invention is to provide a photosensitive resin composition that is excellent in patternability, developability, flushing ability, heat resistance, and light resistance, as well as high reflectance.

Another aspect of the present invention is to provide a reflector plate manufactured using the photosensitive resin composition.

One aspect of the invention (A) a pigment comprising titanium dioxide (TiO ₂ ) having an average particle diameter of 200 to 450 nm; (B) acrylic binder resin; (C) photopolymerizable monomer; (D) photoinitiator; And (E) provides a photosensitive resin composition comprising a solvent.

The pigment may be included in 5 to 20% by weight based on the total amount of the photosensitive resin composition.

The photosensitive resin composition is 5 to 20% by weight of the pigment (A); 1 to 20% by weight of the acrylic binder resin (B); 1 to 15% by weight of the photopolymerizable monomer (C); 0.1 to 10% by weight of the photopolymerization initiator (D); And the residual amount of the solvent (E).

The acrylic binder resin may include a first ethylenically unsaturated monomer including (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof; And styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethylether, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylic Copolymers of second ethylenically unsaturated monomers comprising laterate, vinyl acetate, vinyl benzoate, glycidyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, or combinations thereof. .

The photopolymerizable monomer is ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth Ta) acrylate, trimethylol propane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate or combinations thereof.

The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; Radical polymerization initiators; Or an additive of a combination thereof.

Another aspect of the invention provides a reflector plate manufactured using the photosensitive resin composition.

The reflective plate may include a substrate and the photosensitive resin composition coated on the substrate.

The substrate may include a glass substrate, an aluminum (Al) glass substrate, an aluminum (Al) organic glass substrate, or a combination thereof.

The photosensitive resin composition may be coated with a thickness of 1 μm to 8 μm.

The reflectance of the reflector may be 20 kW to 85 kW%.

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

By using the photosensitive resin composition, not only the pattern, developability, water resistance, heat resistance, and light resistance can be obtained, but also a high reflectance reflector can be obtained. It can be usefully used.

1 is a scanning electron microscope (SEM) photograph showing the end portion of the coating pattern according to Example 4;

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

Unless stated otherwise in the present specification, "substituted" means that at least one hydrogen atom is a halogen atom (F, Cl, Br, I), hydroxy group, C1 to C20 alkoxy group, nitro group, cyano group, amine group, imino group , Azido groups, amidino groups, hydrazino groups, hydrazono groups, carbonyl groups, carbamyl groups, thiol groups, ester groups, ether groups, carboxyl groups or salts thereof, sulfonic acid groups or salts thereof, phosphoric acid or salts thereof, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C3 to C20 cycloalkyl group, C3 to C20 cycloalkenyl group, C3 to C20 cycloalkynyl group, It means substituted with a substituent of C2 to C20 heterocycloalkyl group, C2 to C20 heterocycloalkenyl group, C2 to C20 heterocycloalkynyl group, C3 to C30 heteroaryl group or a combination thereof.

In addition, "hetero" means at least one hetero atom of at least one of N, O, S and P in the ring group unless otherwise specified in the present specification.

Also, unless stated otherwise in the present specification, "(meth) acrylate" means that both "acrylate" and "methacrylate" are possible, and "(meth) acrylic acid" means "acrylic acid" and "methacrylic acid". "Both mean it's possible.

The photosensitive resin composition according to one embodiment may include (A) a pigment, (B) an acrylic binder resin, (C) a photopolymerizable monomer, a (D) photopolymerization initiator, and (E) a solvent.

Each component is demonstrated concretely below.

(A) pigment

The pigment may be an inorganic pigment, and specifically, titanium dioxide (TiO ₂ ) may be used.

The titanium dioxide (TiO ₂ ) may have an average particle diameter of 200 to 450 nm, specifically 250 to 350 nm. When the average particle diameter of titanium dioxide (TiO ₂ ) is within the above range, excellent reflectance can be obtained.

The pigment may be used by mixing zinc oxide, zirconium oxide, alumina, etc. together with the titanium dioxide (TiO ₂ ).

A dispersant may be used together to disperse the pigment in the photosensitive resin composition.

Specifically, the pigment may be used after surface treatment with a dispersant in advance, or a dispersant may be added together with the pigment in preparing the photosensitive resin composition.

As the dispersant, a nonionic dispersant, an anionic dispersant, a cationic dispersant, or the like may be used. Specific examples of the dispersant include polyalkylene glycols and esters thereof, polyoxyalkylenes, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts, sulfonic acid esters, sulfonic acid salts, carboxylic acid esters, and carboxylic acids. Salts, alkylamide alkylene oxide adducts, alkyl amines, and the like, and these may be used alone or in combination of two or more thereof.

Examples of commercially available products of the dispersant include, for example, DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, and DISPERBYK. -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001, and the like; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450, etc. of EFKA Chemical Co., Ltd .; Zenspera Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000, and the like; Or PB711, PB821 from Ajinomoto.

The dispersant may be included in 0.1 to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersant is included in the above range, as the dispersibility of the photosensitive resin composition is excellent, it is excellent in stability, developability and patternability in manufacturing the light shielding layer.

The pigment may be included in 5 to 20% by weight, specifically, 7 to 15% by weight based on the total amount of the photosensitive resin composition. When the pigment is included in the above range may have a good reflectance, it is possible to implement a reflective plate excellent in pattern formation.

(B) acrylic binder resin

The acrylic binder resin may be a polymer of the first ethylenically unsaturated monomer and the second ethylenically unsaturated monomer.

The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing one or more carboxyl groups, and specific examples thereof include (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid, and combinations thereof.

The first ethylenically unsaturated monomer may be included in the amount of 5 to 50% by weight relative to the total amount of the acrylic binder resin (), specifically, may be included in 10 to 40% by weight.

The second ethylenically unsaturated monomer is an aromatic vinyl compound such as styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethyl ether, etc .; Methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid amino alkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds, such as vinyl acetate and a vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; Vinyl cyanide compounds such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These etc. can be mentioned, These can be used individually or in mixture of 2 or more.

Specific examples of the acrylic binder resin, acrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate / 2-hydroxyethyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, and the like, but is not limited to these, these alone or two You may mix and use the above.

The weight average molecular weight of the acrylic binder resin may be 3,000 to 150,000 μg / mol, specifically 3,000 to 40,000 g / mol, and more specifically 5,000 to 30,000 g / mol. When the weight average molecular weight of the acrylic binder resin is within the above range, the physical and chemical properties of the photosensitive resin composition and the viscosity is appropriate, can maintain an appropriate level of developability and sensitivity, and when manufacturing a light shielding layer and Excellent adhesion.

The acid value of the acrylic binder resin may be 20 kPa to 200 kPa / gK, specifically, 50 kPa to 150 kPa / mgKOH / g. When the acid value of the acrylic binder resin is within the above range, developability can be maintained, and the resolution of the pixel pattern is excellent.

The acrylic binder resin may be included in the amount of 1 to 20% by weight, specifically, 5 to 15% by weight based on the total amount of the photosensitive resin composition. When the acrylic binder resin is included in the above range, it is excellent in developability and crosslinkability is improved to obtain excellent surface smoothness.

The said photosensitive resin composition can also mix and use cardo-type binder resin with the said acrylic binder resin.

(C) Photopolymerization  Monomer

As the photopolymerizable monomer, a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond may be used.

Since the photopolymerizable monomer has the ethylenically unsaturated double bond, the photopolymerizable monomer may form a pattern having excellent heat resistance, light resistance, and chemical resistance by causing sufficient polymerization during exposure in the pattern forming process.

Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol Di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate , Pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol There may be mentioned furnace methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, and the like.

Examples of commercially available products of the photopolymerizable monomer are as follows. Examples of the monofunctional ester of (meth) acrylic acid include Aronix M-101 ^® , M-111 ^® , M-114 ^®, and the like manufactured by Toagosei Kagaku Kogyo Co., Ltd .; Nihon Kayaku Co., Ltd. KAYARAD TC-110S ^® , TC-120S ^®, etc .; The V-158 ^® and V-2311 ^{® of} Osaka Yuki Chemical Co., Ltd. are mentioned. Examples of the difunctional ester of the (meth) acrylic acid include, but are not limited to, Aronix M-210 ^® , M-240 ^® , M-6200 ^®, etc. manufactured by Toagosei Chemical Industries, Ltd .; Nihon Kayaku Co., Ltd. KAYARAD HDDA ^® , HX-220 ^® , R-604 ^®, etc .; And V-260 ^® , V-312 ^® and V-335 HP ^{® from} Osaka Yuki Kagaku Kogyo Co., Ltd. Examples of the trifunctional ester of (meth) acrylic acid include Aronix M-309 ^® , M-400 ^® , M-405 ^® , M-450 ^® , M-450 ^{® from} Toagosei Kagaku Kogyo Co., Ltd. -7100 ^® , M-8030 ^® , M-8060 ^®, etc .; Nihon Kayaku Co., Ltd., KAYARAD TMPTA ^® , DPCA-20 ^® , East-30 ^® , East-60 ^® , East-120 ^®, etc .; Osaka yukki Kayaku high (primary)社of V-295 ^®, copper ^® -300, -360 ^® copper, copper -GPT ^®, copper -3PA ^®, and the like copper -400 ^®. These products may be used alone or in combination of two or more.

The photopolymerizable monomer may be used by treating with an acid anhydride in order to impart better developability.

The photopolymerizable monomer may be included in an amount of 1 to 15% by weight, specifically 3 to 10% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerizable monomer is included in the above range, curing occurs at the time of exposure in the pattern forming step, thereby providing excellent sensitivity in the presence of oxygen, and excellent compatibility with the acrylic binder resin.

(D) Light curing Initiator

The photopolymerization initiator may be an acetophenone compound, a benzophenone compound, a thioxanthone compound, a benzoin compound, a triazine compound, an oxime compound, or the like.

Examples of the acetophenone-based compound include 2,2'-diethoxy acetophenone, 2,2'-dibutoxy acetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloro acetophenone, pt-butyldichloro acetophenone, 4-chloro acetophenone, 2,2'-dichloro-4-phenoxy acetophenone, 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-based compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxy benzophenone, acrylated benzophenone, 4,4'-bis (dimethyl amino) benzophenone, 4,4 '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'-dimethyl-2-methoxybenzophenone and the like.

Examples of the thioxanthone-based compound include thioxanthone, 2-chloro thioxanthone, 2-methyl thioxanthone, isopropyl thioxanthone, 2,4-diethyl thioxanthone, and 2,4-diiso Propyl thioxanthone, 2-chloro thioxanthone, etc. are mentioned.

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

Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl 4,6-bis (trichloromethyl) -s-triazine and 2- (3 ', 4'- Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-biphenyl 4,6-bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho1-yl) -4,6 -Bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2-4-tri chloromethyl (Piperonyl) -6-triazine, 2-4-trichloromethyl (4'-methoxystyryl) -6-triazine, etc. are mentioned.

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 and the like.

In addition to the compound, the photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, a biimidazole compound, or the like.

The photopolymerization initiator may be included in an amount of 0.1 to 10% by weight, specifically 0.5 to 5% by weight, based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is included in the above range, photopolymerization occurs sufficiently during exposure in the pattern forming process, and it is possible to prevent a decrease in transmittance due to the unreacted initiator.

(E) solvent

The solvent may be a material that has compatibility with the pigment, the acrylic binder resin, the photopolymerizable monomer, and the photopolymerization initiator but does not react.

Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol methyl ether, ethylene glycol ethyl ether, and propylene glycol methyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Methylethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methylethyl ether, diethylene glycol ethylmethyl ether, diethylene glycol diethyl ether Carbitols such as these; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl-n-butylkenone, methyl-n-amyl ketone and 2-heptanone ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid alkyl esters such as methyl lactate and ethyl lactate; Hydroxyacetic acid alkyl esters such as methyl hydroxyacetate, ethyl hydroxyacetate and butyl hydroxyacetate; Acetate alkoxyalkyl esters, such as methoxymethyl acetate, methoxyethyl acetate, methoxybutyl acetate, ethoxymethyl acetate, ethoxyethyl acetate; 3-hydroxypropionic acid alkyl esters such as methyl 3-hydroxypropionate and ethyl 3-hydroxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-hydroxypropionic acid alkyl esters such as methyl 2-hydroxypropionate, ethyl 2-hydroxypropionate, and propyl 2-hydroxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-hydroxy-2-methylpropionic acid alkyl esters such as methyl 2-hydroxy-2-methylpropionate and ethyl 2-hydroxy-2-methylpropionate; 2-alkoxy-2-methylpropionic acid alkyl esters such as methyl 2-methoxy-2-methylpropionate and ethyl 2-ethoxy-2-methylpropionate; Esters such as 2-hydroxyethyl propionate, 2-hydroxy-2-methylethyl propionate, hydroxyethyl acetate and methyl 2-hydroxy-3-methylbutanoate; Or ketone acid esters such as ethyl pyruvate, and N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, Ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like, and these may be used alone or in combination of two or more thereof.

Considering miscibility and reactivity in the solvent, glycol ethers such as ethylene glycol monoethyl ether; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as 2-hydroxyethyl propionate; Diethylene glycol such as diethylene glycol monomethyl ether; Propylene glycol alkylether acetates such as propylene glycol monomethylether acetate and propylene glycol propylether acetate can be used.

The solvent may be included in the remaining amount relative to the total amount of the photosensitive resin composition, specifically, may be included in 50 to 90% by weight. When the solvent is included in the above range, as the photosensitive resin composition has an appropriate viscosity, processability in manufacturing a reflector is excellent.

(F) Other additives

The photosensitive resin composition includes malonic acid to prevent spots and spots upon application, to improve leveling performance, and to prevent generation of residue by undeveloped; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; It may further include other additives such as radical polymerization initiators.

Examples of the silane coupling agent include trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxysilane, aminopropyl trimethoxysilane, vinyl triacetoxysilane, vinyl trimethoxysilane and γ-isocyanate. Propyl triethoxysilane, γ-glycidoxy propyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. can be mentioned, These can be used individually or in mixture of 2 or more types. .

Examples of the fluorine-based surfactants include BM-1000 ^® , BM-1100 ^® , and the like by BM Chemie; Mecha Pack F 142D ^® , F 172 ^® , F 173 ^® , F 183 ^®, etc. by Dai Nippon Inky Chemical Co., Ltd .; Prorad FC-135 ^® , FC-170C ^® , FC-430 ^® , FC-431 ^®, etc. of Sumitomo 3M Corporation; Asahi Grass Co., Ltd. Saffron S-112 ^® , S-113 ^® , S-131 ^® , S-141 ^® , S-145 ^®, etc .; Toray Silicone Co., Ltd.'s SH-28PA ^{®, ®} -190 copper, may be a commercially available product such as copper ^{-193 ®, SZ-6032 ®,} SF-8428 ®.

The content of the additive can be easily adjusted according to the desired physical properties.

The photosensitive resin composition may further include an epoxy compound in order to improve adhesion to a substrate.

As an example of the said epoxy compound, a phenol novolak epoxy compound, a tetramethyl biphenyl epoxy compound, a bisphenol-A epoxy compound, an alicyclic epoxy compound, or a combination thereof is mentioned.

The epoxy compound may be included in an amount of 0.01 to 5 parts by weight, and specifically 0.1 to 5 parts by weight, based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is included in the above range, it is excellent in adhesion, heat resistance and chemical resistance.

Another embodiment provides a reflector plate manufactured using the photosensitive resin composition described above. The reflective plate may include a substrate and the photosensitive resin composition coated on the substrate. The pattern manufacturing method of the coating film for forming the said reflecting plate is as follows.

(1) application and coating film forming step

The photosensitive resin composition described above is applied to a substrate having a predetermined pretreatment at a desired thickness, for example, 0.5 to 25 μm, using a method such as spin or slit coating, roll coating, screen printing, or applicator. After that, the coating film is formed by heating at a temperature of 70 to 110 ° C. for 1 to 10 minutes to remove the solvent.

The applied thickness may be specifically 1 to 8 μm, more specifically 3 to 6 μm. When applied within the thickness range it is possible to obtain a high reflectance.

The substrate may be a glass substrate, an aluminum (Al) glass substrate, an aluminum (Al) organic glass substrate, or a combination thereof. Among these, an aluminum (Al) glass substrate, an aluminum (Al) organic glass substrate, or a combination thereof may be used to obtain high reflectance. More preferably, an aluminum (Al) organic glass substrate may be used.

(2) Exposure step

In order to form the pattern required for the obtained coating film, a mask of a predetermined form is interposed therebetween, and active rays of 190 to 500 nm are irradiated. As a light source used for irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. can be used, and X-rays, an electron beam, etc. can also be used in some cases.

The exposure amount depends on the type, compounding amount, and dry film thickness of each component of the photosensitive resin composition, but, for example, when using a high pressure mercury lamp, 500 mJ / cm ² (Based on a 365 nm sensor).

(3) developing stage

Subsequent to the above exposure step, an alkaline aqueous solution is used as a developer to dissolve and remove unnecessary portions, thereby remaining only the exposed portions to form an image pattern.

(4) post-processing steps

The image pattern obtained by the above development can be cured by heating again or by actinic radiation irradiation in order to obtain an excellent pattern in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength, storage stability and the like.

By using the photosensitive resin composition mentioned above, the high reflectance calculated | required by the reflecting plate can be obtained.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only preferred embodiments of the present invention, and the present invention is not limited by the following examples.

Example  1 to 3 and Comparative example  1 to 6: photosensitive resin composition

The photosensitive resin compositions according to Examples 1 to 3 and Comparative Examples 1 to 6 were prepared in the compositions shown in Table 1 below using the components mentioned below.

Specifically, after dissolving CGI-124 of Ciba-Geigi Co., Ltd. and IRG-907 of Ciba-Geigi Co., Ltd., a photopolymerization initiator in propylene glycol methyl ether acetate as a solvent, the mixture was stirred at room temperature for 2 hours, and then acrylic binder resin was added thereto. Wako's CR-61 and photopolymerizable monomer dipentaerythritol hexaacrylate were added and stirred at room temperature for 2 hours. Subsequently, the obtained reaction product was charged with a pigment dispersion and γ-glycidoxy propyl trimethoxysilane (S-510 manufactured by Chisso Co., Ltd.) as a silane coupling agent, and stirred at room temperature for 1 hour. The product was then filtered three times to remove impurities, thereby preparing a photosensitive resin composition.

At this time, the pigment dispersion is titanium dioxide (TiO ₂ ) 6.23g, acrylic binder resin (Wako, CR-61) 0.63g, dispersant (BYK Chem, BYK-2163) 1.26g, propylene glycol methyl ether acetate 23.37g and 0.5 mm zirconium beads were placed in a hand shaker and milled for 13 hours.

Acrylic
Binder Resin (g) Photopolymerizable monomer (g) Photopolymerization initiator Solvent (g) Pigment Dispersion (g)
(TiO ₂ average particle diameter) Silane
Coupling Agent (g) IRGACURE OXE01 (g) IRG-907 (g) Example 1 10.55 7.75 0.97 0.58 48.06 31.58
(280 nm) 0.51 Example 2 8.14 5.99 0.75 0.45 41.43 42.75
(300 nm) 0.49 Example 3 5.96 4.38 0.55 0.33 35.44 52.88
(330 nm) 0.46 Comparative Example 1 5.96 4.38 0.55 0.33 35.44 52.88
(50 nm) 0.46 Comparative Example 2 5.96 4.38 0.55 0.33 35.44 52.88
(90 nm) 0.46 Comparative Example 3 5.96 4.38 0.55 0.33 35.44 52.88
(130 nm) 0.46 Comparative Example 4 5.96 4.38 0.55 0.33 35.44 52.88
(50 nm) 0.46 Comparative Example 5 5.96 4.38 0.55 0.33 35.44 52.88
(90 nm) 0.46 Comparative Example 6 5.96 4.38 0.55 0.33 35.44 52.88
(130 nm) 0.46

Example  4 to 11 and Comparative example  7 to 12: pattern production of the coating film

Using a spin coating machine (KDNS, K-Spin8) on each substrate having a thickness of 1 mm degreasing washed using the respective photosensitive resin compositions prepared in Examples 1 to 3 and Comparative Examples 1 to 6, respectively, a predetermined thickness After coating with, a soft-baking was carried out at 90 ° C. for 90 seconds on a hot plate to obtain a coating film. At this time, the coating films according to Examples 4 and 5 were prepared from the photosensitive resin compositions of Examples 1 and 2, respectively, and the coating films according to Examples 6 to 11 were prepared from the photosensitive resin compositions of Example 3. Further, the coating films according to Comparative Examples 7 to 12 are produced from the photosensitive resin compositions of Comparative Examples 1 to 6, respectively.

Subsequently, a photomask was placed on the obtained coating film and exposed at a power of 60 mJ. Subsequently, an aqueous solution of potassium hydroxide (KOH) at a concentration of 1% by weight was used as a developer, and developed at 25 ° C. and atmospheric pressure for 60 seconds using a developer, followed by washing for 60 seconds, followed by spin dry for 25 seconds. It was. Subsequently, a hard bake was performed at 180 to 230 ° C. for 30 minutes in a hot air circulation drying oven to prepare a pattern.

Evaluation 1: Coating Pattern Formability  Measure

1 is a scanning electron microscope (SEM) photograph showing the end portion of the coating pattern according to Example 4; Referring to Figure 1, it can be seen that the coating film prepared from the photosensitive resin composition according to one embodiment has excellent pattern formability.

Evaluation 2: Coating Thickness Measurement

The coating thickness of the produced pattern was measured using Tencor, the results are shown in Table 2 below.

Evaluation 3: reflectance measurement

The reflectance of the produced pattern was observed using X-1 basic (X-rite, Inc.), and the results are shown in Table 2 below.

Board Type Coating Thickness (탆) reflectivity(%) Example 4 Glass 3 27.53 Example 5 Glass 3 41.11 Example 6 Glass 3 53.25 Example 7 Al glass 3 68.68 Example 8 Al organic glass 3 75.43 Example 9 Glass 6 68.01 Example 10 Al glass 6 75.40 Example 11 Al organic glass 6 79.33 Comparative Example 7 Glass 3 4.08 Comparative Example 8 Glass 3 4.96 Comparative Example 9 Glass 3 10.62 Comparative Example 10 Al glass 3 6.54 Comparative Example 11 Al glass 3 12.90 Comparative Example 12 Al organic glass 3 16.87

Through Tables 1 and 2, in the case of Examples 4 to 11 using titanium dioxide (TiO ₂ ) having an average particle diameter of 200 to 450 nm according to one embodiment, titanium dioxide (TiO ₂ ) outside the average particle diameter range was obtained. It can be confirmed that the reflectance is more excellent as compared with the case of Comparative Examples 7 to 12 used.

In addition, referring to Examples 1 to 3, it can be seen that the reflectance increases as the content of the pigment increases. In addition, referring to Examples 6 to 8, it can be seen that the reflectance is changed according to the type of substrate, and referring to Examples 6 to 11, it can be seen that the reflectance increases as the thickness of the coating increases.

The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

Claims (11)

(A) a pigment containing titanium dioxide (TiO ₂ ) having an average particle diameter of 200 to 450 nm;
(B) acrylic binder resin;
(C) photopolymerizable monomer;
(D) photoinitiator; And
(E) solvent
Photosensitive resin composition comprising a.
The method of claim 1,
The pigment is a photosensitive resin composition is contained in 5 to 20% by weight based on the total amount of the photosensitive resin composition.
The method of claim 1,
The photosensitive resin composition
5 to 20% by weight of the pigment (A);
1 to 20% by weight of the acrylic binder resin (B);
1 to 15% by weight of the photopolymerizable monomer (C);
0.1 to 10% by weight of the photopolymerization initiator (D); And
Residual amount of the solvent (E)
Photosensitive resin composition comprising a.
The method of claim 1,
The acrylic binder resin may include a first ethylenically unsaturated monomer including (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof; And styrene, α-methylstyrene, vinyltoluene, vinylbenzylmethylether, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2- Hydroxy butyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenyl (meth) acrylate, 2-aminoethyl (meth) acrylate, 2-dimethylaminoethyl (meth) acrylic A copolymer of a second ethylenically unsaturated monomer comprising a latex, vinyl acetate, vinyl benzoate, glycidyl (meth) acrylate, (meth) acrylonitrile, (meth) acrylamide, or a combination thereof Photosensitive resin composition.
The method of claim 1,
The photopolymerizable monomer is ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol Tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di (meth) acrylate, dipentaerythritol tri (meth) acrylate, di Pentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethyl ether (meth ) Acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, or the photosensitive resin composition comprises a combination of the two.
The method of claim 1,
The photosensitive resin composition is malonic acid; 3-amino-1,2-propanediol; Silane coupling agent containing a vinyl group or a (meth) acryloxy group; Leveling agents; Fluorine-based surfactants; Radical polymerization initiators; Or an additive of a combination thereof.
The reflecting plate manufactured using the photosensitive resin composition of any one of Claims 1-6.
The method of claim 7, wherein
The reflecting plate comprises a substrate, and the photosensitive resin composition coated on the substrate.
9. The method of claim 8,
The substrate comprises a glass substrate, an aluminum (Al) glass substrate, an aluminum (Al) organic glass substrate, or a combination thereof.
9. The method of claim 8,
The photosensitive resin composition is a reflection plate that is coated with a thickness of 1 to 8㎛.
The method of claim 7, wherein
Reflector of the reflector is a reflector of 20 to 85%.

Images