KR102017246B1 - Polyfunctional acrylate compounds, a colored photosensitive resin, color filter and display device comprising the same - Google Patents
Polyfunctional acrylate compounds, a colored photosensitive resin, color filter and display device comprising the same Download PDFInfo
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- KR102017246B1 KR102017246B1 KR1020130081457A KR20130081457A KR102017246B1 KR 102017246 B1 KR102017246 B1 KR 102017246B1 KR 1020130081457 A KR1020130081457 A KR 1020130081457A KR 20130081457 A KR20130081457 A KR 20130081457A KR 102017246 B1 KR102017246 B1 KR 102017246B1
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- 0 O=C(c1ccc(*c(cc2)cc(C(O3)=O)c2C3=O)cc11)OC1=O Chemical compound O=C(c1ccc(*c(cc2)cc(C(O3)=O)c2C3=O)cc11)OC1=O 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
- G02B1/041—Lenses
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
Abstract
This invention manufactures a novel polyfunctional (meth) acrylate type compound, the said polyfunctional (meth) acrylate type compound (A), alkali-soluble resin (B), a photopolymerizable compound (C), and a photoinitiator (D) ) And a colored photosensitive resin composition having excellent sensitivity and film hardness without a residue occurring in a colored photosensitive resin composition containing a coloring material (E) and a solvent (F).
Description
The present invention relates to a polyfunctional (meth) acrylic compound, a colored photosensitive resin composition, a color filter, and a display device including the same.
Color filters are widely used in imaging devices, liquid crystal displays (LCDs), and the like, and their application ranges are rapidly expanding. The color filter used for a color liquid crystal display device, an image pick-up element, etc. spin-coats the colored photosensitive resin composition containing the pigment corresponding to each color of red, green, and blue normally on the board | substrate with a black matrix patterned. After coating uniformly, an operation of exposing and developing a coating film formed by heating and drying (hereinafter sometimes referred to as preliminary firing) and further curing by heat (hereinafter sometimes referred to as postfiring) as necessary is performed for each color. It is manufactured by forming the pixel of each color repeatedly.
As such colored photosensitive resin composition, the composition containing a photopolymerizable compound and a photoinitiator together with a pigment and binder resin is used abundantly, and the photosensitive resin composition containing a black pigment is used also for black matrix formation.
In recent years, in order to improve the yield in process, the coloring photosensitive resin composition is calculated | required the coloring photosensitive resin composition which has the same sensitivity and adhesiveness even with a small exposure amount.
In addition, recently, the coloring material of the coloring photosensitive resin composition has been further atomized in order to satisfy the required performance such as high color purity and high brightness. Therefore, when the pixel is formed using the colored layer formed on the background, there is a problem of developing residue that is not removed during development. Conventional techniques for solving this problem include the method of adjusting the acid value and molecular weight of the binder resin or the acid value of the binder resin and the composition, but the application range is limited, so when the acid value is excessively increased, adhesiveness or surface defect may be caused. In addition, there is a limitation that it is difficult to solve the remaining residues on the metal oxide film or the silicon nitride film.
The present invention provides a color filter and a display device for producing a novel multifunctional (meth) acrylate-based compound, to produce a colored photosensitive resin containing the compound to improve sensitivity and developability, and to improve film hardness. For the purpose of
The present invention to achieve the above object,
It provides a polyfunctional (meth) acrylate compound of the formula (1).
[Formula 1]
R is an alicyclic or aromatic hydrocarbon having 4 to 20 carbon atoms that may have O, CO, CR 3 R 4 , S or SO 2 groups,
R 3 and R 4 are each independently hydrogen, an aliphatic hydrocarbon of 1 to 12 carbon atoms or an aromatic hydrocarbon of 6 to 12 carbon atoms, wherein R 3 and R 4 may be connected to form an alicyclic hydrocarbon,
R 1 is a branched hydrocarbon or alicyclic hydrocarbon having 3 to 12 carbon atoms with or without heteroatoms,
R 2 is hydrogen or methyl,
N is a natural number of 2 to 6.
In addition, the present invention is a polyfunctional (meth) acrylate compound (A), alkali-soluble resin (B), photopolymerizable compound (C), photoinitiator (D), coloring material (E) and solvent ( It provides the coloring photosensitive resin composition containing F).
Furthermore, this invention provides the color filter manufactured with the said coloring photosensitive resin composition.
In addition, the present invention provides a display device including the color filter.
The coloring photosensitive resin composition containing the novel polyfunctional (meth) acrylate type compound of this invention does not generate | occur | produce a residue, and is good in developability, it is excellent in film hardness, and has the advantage of having high sensitivity.
Hereinafter, the present invention will be described in more detail.
The present invention relates to a novel multifunctional (meth) acrylate-based compound, the compound is represented by the following formula (1).
[Formula 1]
R is an alicyclic or aromatic hydrocarbon having 4 to 20 carbon atoms that may have O, CO, CR 3 R 4 , S or SO 2 groups,
R 3 and R 4 are each independently hydrogen, an aliphatic hydrocarbon of 1 to 12 carbon atoms or an aromatic hydrocarbon of 6 to 12 carbon atoms, wherein R 3 and R 4 may be connected to form an alicyclic hydrocarbon,
R 1 is a branched hydrocarbon or alicyclic hydrocarbon having 3 to 12 carbon atoms with or without heteroatoms,
R 2 is hydrogen or methyl,
N is a natural number of 2 to 6.
Formula 1 should contain at least two aliphatic or aromatic structures and carboxyl groups in the core structure, and at least six (meth) acryl groups.
In addition, Chemical Formula 1 is prepared by the ring-opening reaction of the following Chemical Formula 2 and Chemical Formula 3.
[Formula 2]
R 1 is a branched hydrocarbon or alicyclic hydrocarbon having 3 to 12 carbon atoms with or without heteroatoms,
R 2 is hydrogen or methyl,
N is a natural number of 2 to 6.
[Formula 3]
R is an alicyclic or aromatic hydrocarbon having 4 to 20 carbon atoms that may have O, CO, CR 3 R 4 , S or SO 2 groups,
R 3 and R 4 are each independently hydrogen, an aliphatic hydrocarbon having 1 to 12 carbon atoms or an aromatic hydrocarbon having 6 to 12 carbon atoms, wherein R 3 and R 4 may be connected to form an alicyclic hydrocarbon.
Formula 2 may be the following Formula 4 or 5.
[Formula 4]
[Formula 5]
In addition, Chemical Formula 3 is at least one monomer selected from the group consisting of the following Chemical Formulas 6 to 15.
[Formula 6]
[Formula 7]
[Formula 8]
X in Chemical Formulas 7 and 8 is a direct connection, CO, CR 3 R 4 , O, S or SO 2 ,
R 3 and R 4 are each independently hydrogen, an aliphatic hydrocarbon having 1 to 12 carbon atoms or an aromatic hydrocarbon having 6 to 12 carbon atoms, wherein R 3 and R 4 may be linked to form an alicyclic hydrocarbon.
[Formula 9]
[Formula 10]
[Formula 11]
[Formula 12]
[Formula 13]
[Formula 14]
[Formula 15]
In embodiment of this invention, as a specific example of the compound which has an unsaturated bond and an epoxy group in the said 1 molecule, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl (meth) acrylate, 3, 4- epoxy Cyclohexyl methyl (meth) acrylate, methylglycidyl (meth) acrylate, etc. are mentioned.
Alternatively, all compounds containing glycidyl groups such as glycidyl neodecanoate can be used. Among these, glycidyl (meth) acrylate is preferably used.
In the present invention, (meth) acrylate means acrylate or / and methacrylate.
In addition, the acid anhydride may be used without limitation as an acid anhydride capable of reacting with a polyfunctional alcohol, and specific examples thereof include maleic anhydride, trimellitic anhydride, phthalic acid, terephthalic acid, and isode Tephthalic acid, phthalic anhydride, hexahydrophthalic anhydride, etc. are mentioned.
In addition, the present invention is a polyfunctional (meth) acrylate compound (A), alkali-soluble resin (B), photopolymerizable compound (C), photoinitiator (D), coloring material (E) and solvent ( It provides the coloring photosensitive resin composition containing F). Moreover, although it is not restrict | limited, It is preferable that the other additive (G) is melt | dissolved or disperse | distributed to the solvent (F).
(A) of Formula 1 Multifunctional ( Meta ) Acrylate compound
The polyfunctional (meth) acrylate-based compound (A) of Formula 1 is the same as described above, it is contained in 0.01 to 5% by weight relative to the total weight of the colored photosensitive resin composition, preferably 0.05 to 4% by weight to be. It does not affect the sensitivity and adhesiveness of the coloring photosensitive resin composition in the above range, there is an advantage that the development speed is excellent and that little residue after development remains. On the other hand, when out of the above range, the sensitivity and adhesion may be lowered, which may inhibit the performance of the colored photosensitive resin composition.
(B) alkali-soluble resin
The alkali-soluble resin (B) is an acrylic copolymer which can be dissolved in the solvent of the present invention, has reactivity to the action of light or heat, functions as a binder resin for the colorant, and can be dissolved in an alkaline developer. It can use without a restriction | limiting in particular. As said alkali-soluble resin, the copolymer etc. with a carboxyl group-containing monomer and the other monomer copolymerizable with the said monomer are mentioned, for example. As said carboxyl group-containing monomer, For example, unsaturated carboxylic acids, such as unsaturated polyhydric carboxylic acid which has 1 or more carboxyl groups in molecules, such as unsaturated monocarboxylic acid, unsaturated dicarboxylic acid, or unsaturated tricarboxylic acid, are mentioned. Can be. As said unsaturated monocarboxylic acid, acrylic acid, methacrylic acid, crotonic acid, (alpha)-chloroacrylic acid, cinnamic acid etc. are mentioned, for example. As said unsaturated dicarboxylic acid, a maleic acid, a fumaric acid, itaconic acid, a citraconic acid, a mesaconic acid, etc. are mentioned, for example. The unsaturated polyhydric carboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride and citraconic anhydride. In addition, the unsaturated polyhydric carboxylic acid may be a mono (2-methacryloyloxyalkyl) ester thereof, for example, monosuccinate mono (2-acryloyloxyethyl), monosuccinate mono (2-methacryloyloxy Ethyl), mono phthalate (2-acryloyloxyethyl), mono phthalate (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of the sock end dicarboxy polymer, for example, ω-carboxypolycaprolactone monoacrylate, ω-carboxypolycaprolactone monomethacrylate, or the like. Can be mentioned. The said carboxyl group-containing monomer can be used individually or in mixture of 2 or more types, respectively. Specific examples of other monomers copolymerizable with the carboxyl group-containing monomers include styrene, α-methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, and m-meth Oxy styrene, p-methoxy styrene, o-vinyl benzyl methyl ether, m-vinyl benzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p- Aromatic vinyl compounds such as vinyl benzyl glycidyl ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, 2-hydroxy Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxy Hydroxybutyl acrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, allyl Relate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxydiethylene glycol acrylate, methoxydiethylene glycol methacrylate, methoxytriethylene glycol acrylate, methoxytriethylene glycol meth Methacrylate, methoxy propylene glycol acrylate, methoxy propylene glycol methacrylate, methoxy dipropylene glycol acrylate, methoxy dipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadier Nylacrylate, dicyclopentadienyl methacrylate, 2-hydroxy-3-phenoxy Acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, unsaturated carboxylic acid esters such as glycerol monoacrylate, glycerol monomethacrylate; 2-aminoethyl acrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2-dimethyl Unsaturated carboxyl such as aminopropyl acrylate, 2-dimethylaminopropyl methacrylate, 3-aminopropyl acrylate, 3-aminopropyl methacrylate, 3-dimethylaminopropyl acrylate and 3-dimethylaminopropyl methacrylate Acid aminoalkyl esters; Unsaturated carboxylic acid glycidyl esters such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide, α-chloroacrylamide, N-2-hydroxyethylacrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, N-phenylmaleimide. Unsaturated imides such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; Polystyrene, polymethylacrylate, polymethylmethacrylate, poly-n-butylacrylate, poly-n-butylmethacrylate, having a monoacryloyl group or a monomethacryloyl group at the terminal of the polymer molecular chain of polysiloxane Macromonomers; and the like. These monomers can be used individually or in mixture of 2 or more types, respectively.
The said alkali-soluble resin is a (meth) acrylic acid / methyl (meth) acrylate copolymer, the (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth), for example. Acrylate / benzyl (meth) acrylate copolymer, (meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl (meth) acrylate macro Monomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / benzyl (meth) acrylate / polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / Polymethyl (meth) acrylate macromonomer copolymer, (meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / mono (2-acryloyloxy) / Styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / mono succinate mono (2-acryloyloxyethyl) / styrene / allyl (meth) acrylate / N-phenylmaleimide aerial A copolymer, a (meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer, etc. are mentioned. Here (meth) acrylate means acrylate or methacrylate.
Among these, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, (meth) acrylic acid / methyl (meth) acrylate copolymer, (meth) acrylic acid / Methyl (meth) acrylate / styrene copolymer is preferably used.
The alkali-soluble resin has a polystyrene reduced weight average molecular weight (hereinafter, simply referred to as "weight average molecular weight") measured by gel permeation chromatography (GPC) using tetrahydrofuran as an eluting solvent, preferably 5,000 to 50,000. 10,000 to 35,000, more preferably 10,000 to 30,000. When the weight average molecular weight of the alkali-soluble resin is 5,000 to 50,000, the coating film hardness is improved, the residual film ratio is high, the solubility in the developer of the unexposed part is good, and the resolution is improved.
The said alkali-soluble resin has an acid value of 50-150 (mgKOH / g), Preferably it is 60-140 (mgKOH / g), More preferably, it is 80-130 (mgKOH / g). When the acid value of the alkali-soluble resin is 50 to 150 (mgKOH / g), the solubility in the developer is improved, so that the unexposed portion is easily dissolved, and the sensitivity is increased, so that the pattern of the exposed portion at the time of development remains to improve the residual film ratio. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the acrylic polymer, and can be determined by titration using an aqueous potassium hydroxide solution.
The alkali-soluble resin may be included in 5 to 85% by weight based on the total weight of solids in the colored photosensitive resin composition, it is preferably included in 5 to 70% by weight. When the alkali-soluble resin is included in the above range, it is advantageous for suppressing residue and forming a coating film.
(C) Photopolymerizable compound
The photopolymerizable compound is a compound which can be polymerized by an active radical, an acid, etc. generated from a photopolymerization initiator by irradiation of light, and examples thereof include monofunctional, bifunctional and trifunctional polymerizable compounds depending on the number of functional groups. Specific examples of the monofunctional polymerizable compound include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, and N-. Vinylpyrrolidone, etc. are mentioned. Specific examples of the bifunctional polymerizable compound include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, and triethylene glycol di (meth). Acrylate, bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, butylene glycol dimethacrylate, hexanediol di (meth) acrylate, diethylene glycol di ( Meta) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxy The late neopentyl glycol diacrylate, the propyl oxylate neopentyl glycol diacrylate, etc. are mentioned. Specific examples of the trifunctional polymerizable compound include trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ethoxylate trimethylolpropane tri (meth) acrylate, and propyloxylate trimethylolpropane Tri (meth) acrylate, glycerylpropyl oxylate triacrylate, isocyanurate triarylate and the like. Specific examples of the tetrafunctional polymerizable compound include pentaerythritol tetra (meth) acrylate, dimethylolpropane tetra (methyl) acrylate, and the like.
In addition, specific examples of the 5-functional polymerizable compound include dipentaerythritol penta (meth) acrylate, and specific examples of the six-functional photopolymerizable compound include dipentaerythritol hexa (meth) acrylate.
Among these, as the photopolymerizable compound, a bifunctional or higher polyfunctional polymerizable compound can be preferably used, and in particular, a polyfunctional or higher polyfunctional polymerizable compound can be preferably used. The photopolymerizable compound is preferably contained in 5 to 50% by weight, more preferably in 7 to 45% by weight relative to the total weight of solids in the colored photosensitive resin composition. When the photopolymerizable compound is included in the above range, the strength and smoothness of the pixel portion are good.
(D) Photopolymerization Initiator
The photoinitiator (D) can be used without particular limitation as long as it can polymerize the photopolymerizable compound (C).
In particular, the photopolymerization initiator (D) is an acetophenone compound, a benzophenone compound, a triazine compound, a biimidazole compound, an oxime compound and a tee from the viewpoint of polymerization characteristics, initiation efficiency, absorption wavelength, availability, or price. It is preferable to use at least one compound selected from the group consisting of oxatone compounds.
Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyl dimethyl ketal, 2-hydroxy-1- [4- (2-hydroxy Hydroxyethoxy) phenyl] -2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one, 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propane-1 -One or 2- (4-methylbenzyl) -2- (dimethylamino) -1- (4-morpholinophenyl) butan-1-one, and the like.
As said benzophenone type compound, benzophenone, methyl 0- benzoyl benzoate, 4-phenylbenzo phenone, 4-benzoyl-4'- methyl diphenyl sulfide, 3,3 ', 4, 4'- tetra ( tert-butylperoxycarbonyl) benzophenone or 2,4,6-trimethylbenzophenone.
Specific examples of the triazine-based compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine and 2,4-bis (trichloromethyl) -6 -(4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- (4-methoxystyryl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (5-methylfuran-2- Yl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] -1,3,5-triazine , 2,4-bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine or 2,4-bis (trichloromethyl ) -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine and the like.
Specific examples of the biimidazole compound include 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichloro Phenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2-chlorophenyl) -4,4', 5,5'-tetra (alkoxyphenyl) biimidazole , 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetra (trialkoxyphenyl) biimidazole, 2,2-bis (2,6-dichlorophenyl) -4, The imidazole compound etc. which the phenyl group of a 4 ', 5,5'- tetraphenyl- 1,2'-biimidazole or a 4,4', 5,5 'position are substituted by the carboalkoxy group are mentioned. Among them, 2,2'-bis (2-chlorophenyl) -4,4 ', 5,5'-tetraphenylbiimidazole, 2,2'-bis (2,3-dichlorophenyl) -4,4' , 5,5'-tetraphenylbiimidazole or 2,2-bis (2,6-dichlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'-biimidazole is preferably Used.
Specific examples of the oxime compound include o-ethoxycarbonyl-α-oxyimino-1-phenylpropan-1-one and the like, and OXE01 and OXE02 manufactured by BASF Corporation are typical examples.
As said thioxanthone type compound, 2-isopropyl thioxanthone, 2, 4- diethyl thioxanthone, 2, 4- dichloro thioxanthone, 1-chloro-4- propoxy thioxanthone, etc. are mentioned, for example. There is this.
Moreover, the photoinitiator etc. of that excepting the above can also be used together in the range which does not impair the effect of this invention. For example, a benzoin type compound, an anthracene type compound, etc. are mentioned, These can be used individually or in combination of 2 or more types, respectively.
Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and the like.
Examples of the anthracene-based compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, and the like. have.
Other 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 10-butyl-2-chloroacridone, 2-ethylanthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, phenylclioxylic acid A methyl or titanocene compound and the like can be further used in combination as a photopolymerization initiator.
In addition, the photoinitiator (D) may further include a photopolymerization initiation aid (D-1) in order to improve the sensitivity of the colored photosensitive resin composition of the present invention. The coloring photosensitive resin composition which concerns on this invention contains a photoinitiation adjuvant (D-1), and can raise a sensitivity further and can improve productivity.
As the photopolymerization initiation assistant (D-1), for example, one or more compounds selected from the group consisting of amine compounds, carboxylic acid compounds and organic sulfur compounds having thiol groups can be preferably used.
It is preferable to use an aromatic amine compound as the amine compound, and specifically, aliphatic amine compounds such as triethanolamine, methyl diethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4- Dimethylaminobenzoic acid isoamyl, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethylaminoethyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (common name: Michler's ketone ) Or 4,4'-bis (diethylamino) benzophenone can be used.
The carboxylic acid compound is preferably an aromatic heteroacetic acid, specifically, phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthio Acetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine or naphthoxyacetic acid, and the like.
Specific examples of the organic sulfur compound having the thiol group include 2-mercaptobenzothiazole, 1,4-bis (3-mercaptobutyryloxy) butane, 1,3,5-tris (3-mercaptobutyloxyethyl)- 1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, trimethylolpropanetris (3-mergaptopropionate), pentaerythritol tetrakis (3-mercaptobutyl Late), pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), tetraethylene glycol bis (3-mercaptopropionate), etc. are mentioned. Can be.
The photopolymerization initiator (D) may be included in an amount of 0.02 to 10% by weight, preferably 0.5 to 5% by weight, based on the total weight of solids in the colored photosensitive resin composition of the present invention. When the said photoinitiator (D) exists in the said range, since a coloring photosensitive resin composition becomes high sensitivity and an exposure time is shortened, productivity may improve and a high resolution can be maintained. In addition, the strength of the pixel portion formed using the composition and smoothness on the surface of the pixel portion may be improved.
In addition, when the photopolymerization initiation aid (D-1) is further used, it is preferable to use the same content range as the photopolymerization initiator (D), and when used in the content, the sensitivity of the colored photosensitive resin composition is further improved, The productivity of the color filter formed using the composition can be exhibited.
(E) coloring materials
The coloring material (E) may be used an organic pigment, an inorganic pigment or a dye generally used in the art.
The organic pigment may be used a variety of pigments used in printing inks, inkjet inks, and the like, specifically, phthalocyanine water-soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments , Isoindolin pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, ananthrone pigments, indanthrone pigments, pravantrons Pigments, pyranthrone pigments or diketopyrrolopyrrole pigments and the like.
If necessary, the pigment may be a resin treatment, a surface treatment using a pigment derivative having an acidic group or a basic group introduced therein, a graft treatment on the surface of the pigment with a high molecular compound or the like, an atomization treatment by a sulfate atomization method or the like to remove impurities. Washing treatment with an organic solvent, water, or the like, removing ionic impurities by an ion exchange method, or the like can also be performed.
Examples of the inorganic pigment include metal compounds such as metal oxides and metal complex salts. Specifically, oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony or carbon black Or a composite metal oxide.
As the pigment used in the pigment dispersion composition of the present invention, an organic pigment or an inorganic pigment generally used in the art may be used, and these may be used alone or in combination of two or more kinds.
In particular, the pigment may be a compound that is specifically classified as a pigment in the color index (Published by The society of Dyers and Colourists), more specifically, a pigment having the following color index (CI) number can be used It is not necessarily limited to these.
C.I. Pigment Yellow 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 180, 185 And 242
C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, and 71
C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 215, 216, 224, 242, 254, 255, 264 and 277
C.I. Pigment Violet 14, 19, 23, 29, 32, 33, 36, 37 and 38
C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.), 21, 28, 60, 64, and 76
C.I. Pigment Green 7, 10, 15, 25, 36, 47 and 58
C.I Pigment Brown 28
C.I pigment black 1 and 7, etc.
C.I. exemplified above. Among pigment pigments, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, C.I. Pigment Yellow 185, C.I. Pigment Orange 38, C.I. Pigment Red 166, C.I. Pigment Red 177, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Violet 23, C.I. Pigment Blue 15: 6, C.I. Pigment Green 7, C.I. Pigment Green 36 or C.I. Pigments selected from Pigment Green 58 may be preferably used.
It is preferable to use the pigment dispersion liquid which the said particle size disperse | distributed uniformly. As an example of the method for uniformly dispersing the particle size of the pigment, a method of containing and dispersing the pigment dispersant may be used. According to this method, a pigment dispersion in which the pigment is uniformly dispersed in a solution can be obtained.
As said pigment dispersant, surfactant, such as cationic, anionic, nonionic, amphoteric, polyester, and polyamine type, etc. are mentioned, for example, These can be used individually or in combination of 2 or more types, respectively. have.
Specific examples of the surfactant include polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyethylene glycol diesters, sorbitan fatty acid esters, fatty acid modified polyesters, tertiary amine modified polyurethanes, and polyethyleneimines. And KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Mega Pack (MEGAFAC) (manufactured by Dainippon Ink & Chemicals Co., Ltd.), Florard (manufactured by Sumitomo 3M Inc.), Asahi guard, Suflon (manufactured by Asahi Glass Co., Ltd.), SOLSPERSE ) (Manufactured by Genca Corp.), EFKA (manufactured by EFKA Chemicals Co., Ltd.), PB 821 (manufactured by Ajinomoto Co., Ltd.), and the like.
The pigment dispersant is usually used in an amount of 1 part by weight or less, preferably 0.05 to 0.5 parts by weight, based on 1 part by weight of a solid content of the pigment. When the pigment dispersant is used in such a content, it is preferable because a dispersed pigment of uniform particle size can be obtained.
The dye can be used without limitation so long as it has solubility in an organic solvent. Preferably, it is preferable to use a dye which has solubility in an organic solvent and can ensure reliability such as solubility, heat resistance and solvent resistance in an alkaline developer.
The dye may be selected from acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salts of acid dyes and nitrogen-containing compounds, sulfonamides of acid dyes, and derivatives thereof, and azo, xanthene, and phthalocyanines. Acid dyes and derivatives thereof can also be selected.
Preferably, the dye may be a compound classified as a dye in the color index (Published by The Society of Dyers and Colourists), or a known dye described in a dyeing note (color dyed yarn).
Specific examples of the dye include C.I. As solvent dyes,
C.I. Yellow dyes such as solvent yellow 4, 14, 15, 21, 23, 24, 38, 62, 63, 68, 82, 94, 98, 99, 162;
C.I. Red dyes such as solvent red 8, 45, 49, 122, 125 and 130;
C.I. Orange dyes such as solvent orange 2, 7, 11, 15, 26, 56 and the like;
C.I. Blue dyes such as solvent blue 35, 37, 59, 67 and the like;
C.I. Green dyes, such as solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc. are mentioned.
See also C.I. As an acid dye
CI acid yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112 , 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184 Yellow dyes such as, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251 ;
CI acid red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 34, 35, 37, 42, 44, 50, 51, 52, 57, 66, 73, 80, 87, 88 , 91, 92, 94, 97, 103, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 158, 176, 182, 183, 198, 206, 211, 215, 216, 217 , 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 195, 308, 312, 315, 316, 339, 341, 345, 346, 349 Red dyes such as, 382, 383, 394, 401, 412, 417, 418, 422, 426;
Orange dyes such as C.I. acid orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 169, 173;
CI acid blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92, 96, 103 , 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315, 324: 1 Blue dyes such as, 335 and 340;
Violet dyes such as C.I. acid violet 6B, 7, 9, 17, 19 and the like;
Green dyes, such as C.I. acid green 1, 3, 5, 9, 16, 25, 27, 50, 58, 63, 65, 80, 104, 105, 106, 109, etc. are mentioned.
Also as a C.I. direct dye
CI direct yellow 2, 33, 34, 35, 38, 39, 43, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129 Yellow dyes such as, 136, 138, and 141;
CI Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211 Red dyes such as, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246 and 250;
Orange dyes such as C.I.direct orange 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;
CI direct blue 38, 44, 57, 70, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113 , 114, 115, 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, 189 , 190, 192, 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248 Blue dyes such as, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293, etc .;
Violet dyes such as C.I. direct violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104 and the like;
Green dyes, such as C.I. direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 77, 79, 82, etc. are mentioned.
In addition, C.I. As modanto dye
Yellow dyes such as C.I. modanto yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;
CI Modanto Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 30, 32, 33, 36, 37, 38, 39, Red dyes such as 41, 43, 45, 46, 48, 53, 56, 63, 71, 74, 85, 86, 88, 90, 94, 95 and the like;
CI Modanto Orange Orange such as 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48, etc. dyes;
CI Modanto Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, Blue dyes such as 43, 44, 48, 49, 53, 61, 74, 77, 83, 84 and the like;
Violet dyes such as C.I. modanto violet 1, 2, 4, 5, 7, 14, 22, 24, 30, 31, 32, 37, 40, 41, 44, 45, 47, 48, 53, 58 and the like;
Green dyes, such as C.I. modanto green 1, 3, 4, 5, 10, 15, 19, 26, 29, 33, 34, 35, 41, 43, 53, etc. are mentioned.
Each of the pigments and dyes may be used in combination of one or more kinds.
The coloring material of the present invention comprises 2 to 15% by weight based on the total weight of the coloring photosensitive resin composition, and the pigment is 20 to 90% by weight, preferably 30 to 70% by weight, based on the total solids in the pigment to dye dispersion composition. It can be included as a range. When the content of the pigment is outside the above range, the viscosity is high, the storage stability is bad, and the dispersion efficiency is low, which adversely affects the contrast ratio.
(F) solvent
If the solvent (F) is effective to dissolve the other components included in the colored photosensitive resin composition, it can be used without particular limitation to the solvent used in the usual colored photosensitive resin composition, especially ethers, aromatic hydrocarbons, ketones, Alcohols, esters or amides are preferable.
Specifically, the solvent (F) is ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl Ether, diethylene glycol dibutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, dipropylene glycol di Ethers such as propyl ether and dipropylene glycol dibutyl ether; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin; Ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl cellosolve acetate, ethyl cellosolve acetate, ethyl acetate, butyl acetate, amyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3-meth Methoxybutyl acetate, 3-methyl-3-methoxy-1-butyl acetate, methoxypentyl acetate, ethylene glycol monoacetate, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol Monoacetate, diethylene glycol diacetate, diethylene glycol monobutyl ether acetate, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene carbonate, propylene carbonate or γ-buty Rockactone, etc. And esters thereof.
The solvent (F) is preferably an organic solvent having a boiling point of 100 ℃ to 200 ℃ in terms of applicability and drying properties, more preferably propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate , Butalactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate and the like can be used.
Solvent (F) mentioned above can be used individually or in mixture of 2 or more types, respectively.
The solvent may be included 60 to 90% by weight, preferably 70 to 85% by weight relative to the total weight of the colored photosensitive resin composition of the present invention. When the solvent (F) is in the above range, the coating property is improved when applied with a coating device such as a roll coater, spin coater, slit and spin coater, slit coater (sometimes referred to as die coater) or inkjet. do.
(G) additive
In the coloring photosensitive resin composition of this invention, it is also possible to add additives (G), such as a filler, another high molecular compound, a pigment dispersing agent, an adhesion promoter, antioxidant, a ultraviolet absorber, and an aggregation inhibitor, as needed.
Specific examples of the filler include glass, silica, alumina and the like.
Specific examples of other high molecular compounds include curable resins such as epoxy resins and maleimide resins, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ethers, polyfluoroalkyl acrylates, polyesters, polyurethanes, and the like. have.
Commercially available surfactants can be used as the pigment dispersant, and examples thereof include surfactants such as silicone, fluorine, ester, cationic, anionic, nonionic and amphoteric. These can be used individually or in combination of 2 types or more, respectively. As said surfactant, For example, polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, polyethylene glycol diester, sorbitan fatty acid ester, fatty acid modified polyester, tertiary amine modified polyurethane, Polyethyleneimines and the like, and other trade names include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), POLYFLOW (manufactured by Kyoeisha Chemical Co., Ltd.), EFTOP (manufactured by Tochem Products), Mega MEGAFAC (made by Dainippon Ink & Chemicals Co., Ltd.), Florad (made by Sumitomo 3M Co., Ltd.), Asahi guard, Suflon (above, manufactured by Asahi Glass Co., Ltd.), Sol SLSPERSE (made by Genka Corporation), EFKA (made by EFKA Chemicals), PB 821 (made by Ajinomoto Co., Ltd.), etc. are mentioned.
As the adhesion promoter, for example, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N -(2-aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltri Methoxysilane, etc. are mentioned.
Specific examples of the antioxidant include 2,2'-thiobis (4-methyl-6-t-butylphenol), 2,6-di-t-butyl-4-methylphenol, and the like.
Specific examples of the ultraviolet absorber include 2- (3-tert-butyl-2-hydroxy-5-methylphenyl) -5-chlorobenzothiazole, alkoxybenzophenone and the like.
Specific examples of the aggregation inhibitor include sodium polyacrylate and the like.
The present invention provides a color filter made of a colored photosensitive resin composition and a display device having the same.
It can manufacture by apply | coating the said coloring photosensitive resin composition on a base material as follows, photocuring and developing, and forming a pattern.
First, the photosensitive resin composition is apply | coated on the board | substrate (usually glass) or the layer which consists of solid content of the coloring photosensitive resin composition formed first, and heat-drying removes volatile components, such as a solvent, and obtains a smooth coating film.
As a coating method, it can carry out by a spin coat, cast coating method, the roll coating method, the slit and spin coat, the slit coat method, etc., for example. It heats after application | coating and heat-drying (prebaking) or drying under reduced pressure, and volatilizes volatile components, such as a solvent. Here, heating temperature is 70-200 degreeC normally, Preferably it is 80-130 degreeC. The coating film thickness after heat drying is about 1-8 micrometers normally. The coating film thus obtained is irradiated with ultraviolet rays through a mask for forming a target pattern. At this time, it is preferable to use apparatuses, such as a mask aligner and a stepper, so that the parallel light beam may be irradiated uniformly to the whole exposure part, and the exact alignment of a mask and a board | substrate is performed. When ultraviolet light is irradiated, the site to which ultraviolet light is irradiated is hardened.
G-rays (wavelength: 436 nm), h-rays, i-rays (wavelength: 365 nm) and the like can be used as the ultraviolet rays. The irradiation dose of ultraviolet rays may be appropriately selected as necessary, and the present invention is not limited thereto. When the coating film after hardening is contacted with a developing solution and the non-exposed part is melted and developed, the spacer which has a target pattern shape can be obtained.
The developing method may be any of a liquid addition method, a dipping method, a spray method and the like. In addition, during development, the substrate may be tilted at an arbitrary angle. The developer is usually an aqueous solution containing an alkaline compound and a surfactant. The alkaline compound may be either an inorganic or organic alkaline compound. Specific examples of the inorganic alkaline compound include sodium hydroxide, potassium hydroxide, sodium hydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium dihydrogen phosphate, sodium silicate, potassium silicate, sodium carbonate, potassium carbonate And sodium hydrogen carbonate, potassium hydrogen carbonate, sodium borate, potassium borate, ammonia and the like. Specific examples of the organic alkaline compound include tetramethylammonium hydroxide, 2-hydroxyethyltrimethylammonium hydroxide, monomethylamine, dimethylamine, trimethylamine, monoethylamine, diethylamine, triethylamine, Monoisopropylamine, diisopropylamine, ethanolamine and the like.
These inorganic and organic alkaline compounds can be used individually or in combination of 2 or more types, respectively. The concentration of the alkaline compound in the alkaline developer is preferably 0.01 to 10% by weight, more preferably 0.03 to 5% by weight.
The surfactant in the alkaline developer may be at least one selected from the group consisting of nonionic surfactants, anionic surfactants or cationic surfactants.
Specific examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene aryl ether, polyoxyethylene alkyl aryl ether, other polyoxyethylene derivatives, oxyethylene / oxypropylene block copolymers, sorbitan fatty acid esters, Polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and the like.
Specific examples of the anionic surfactants include higher alcohol sulfate ester salts such as sodium lauryl alcohol sulfate and sodium oleyl alcohol sulfate, alkyl sulfates such as sodium lauryl sulfate and ammonium lauryl sulfate, sodium dodecylbenzene sulfonate, Alkyl aryl sulfonates, such as sodium dodecyl naphthalene sulfonate, etc. are mentioned.
Specific examples of the cationic surfactant include amine salts such as stearylamine hydrochloride and lauryl trimethylammonium chloride, or quaternary ammonium salts. These surfactant can be used individually or in combination of 2 or more types, respectively.
The concentration of the surfactant in the developer is usually 0.01 to 10% by weight, preferably 0.05 to 8% by weight, more preferably 0.1 to 5% by weight. After image development, it is washed with water and also 10-60 minutes post-baking may be performed at 150-230 degreeC as needed.
Using the coloring photosensitive resin composition of this invention, a specific pattern can be formed on a board | substrate through each process as mentioned above.
Therefore, the pattern thus obtained can be usefully used in image display devices such as liquid crystal displays, and has excellent visible light shielding properties, high crosslinking density even at low exposure amounts, and excellent adhesion to substrates, thereby providing excellent heat resistance and chemical stability (contents). Attractive)
Hereinafter, the present invention will be described in detail with reference to Examples. However, embodiments according to the present invention can be modified in many different forms, and the scope of the present invention should not be construed as being limited to the embodiments described below. The embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.
Production Example One. Multifunctional ( Meta ) Acrylate (A) manufacturing
Pentaerythritol tetra / tri (50/50 weight ratio) acrylate (650 g) and pyromellitic anhydride (120 g) were placed in a 1 L reactor and heated to 60 ° C. under a nitrogen atmosphere. Thereafter, 10 g of a triethylamine catalyst was added, and after stirring at the same temperature for 5 hours, the temperature was lowered to room temperature to synthesize a polyfunctional acrylate compound (Scheme 1, Formula 16).
A certain amount of the synthesized compound was taken as a sample and analyzed by LC / MS to confirm the product of the reaction scheme (LC chromatogram peak area ratio, A: B: C = 40: 10: 50), and A ( M +; 814), B (M +; 534) and C (M +; 352).
Scheme 1
[Formula 16]
Production Example 2. Alkali-soluble resin (B-1) manufacture
200 g of propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from air to nitrogen, and then heated to 100 ° C., and then benzyl methacrylate. Azobisisobutyronitrile 3.6 The solution to which g was added was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 100 degreeC for 5 hours. Thereafter, the atmosphere in the flask was switched from nitrogen to air, and 0.2 mol of glycidyl methacrylate (50 mol% relative to the carboxyl group of methacrylic acid used in the reaction), 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone Was added to a flask and the reaction was continued at 110 ° C for 6 hours to obtain an alkali-soluble resin B-1 having a solid acid value of 94 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 30,000, and molecular weight distribution (Mw / Mn) was 2.1.
Production Example 3. Alkali-soluble resin (B-2) manufacture
200 g of propylene propylene glycol monomethyl ether acetate was introduced into a flask equipped with a stirrer, a thermometer reflux condenser, a dropping lot, and a nitrogen inlet tube, and the atmosphere in the flask was changed from air to nitrogen. Azobisisobutyronitrile 3.6 to a mixture containing 0.40 mol, methacrylic acid 0.6 mol, 0.10 mol of monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) of tricyclodecane skeleton and 150 g of propylene glycol monomethyl ether acetate. The solution to which g was added was dripped at the flask over 2 hours from the dropping lot, and stirring was continued at 100 degreeC for 5 hours. Thereafter, the atmosphere in the flask was switched from nitrogen to air, and 0.2 mol of glycidyl methacrylate (50 mol% relative to the carboxyl group of methacrylic acid used in the reaction), 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone Was added into a flask and the reaction was continued at 110 ° C. for 6 hours to obtain an alkali-soluble resin B-2 having a solid acid value of 120 mgKOH / g. The weight average molecular weight of polystyrene conversion measured by GPC was 12,000, and molecular weight distribution (Mw / Mn) was 2.2.
The measurement of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the alkali-soluble resins of Preparation Examples 2 and 3 was carried out under the following conditions using the GPC method.
Equipment: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG4000HXL + TSK-GELG2000HXL (Serial Connection)
Column temperature: 40 ℃
Mobile phase solvent: tetrahydrofuran
Flow rate: 1.0 ml / min
Injection volume: 50 μl
Detector: RI
Measurement sample concentration: 0.6 mass% (solvent = tetrahydrofuran)
Calibration standard: TSK STANDARD POLYSTYRENE F-40, F-4, F-1, A-2500, A-500 (manufactured by Tosoh Corporation)
The ratio of the weight average molecular weight and number average molecular weight obtained above was made into molecular weight distribution (Mw / Mn).
Example 1. Preparation of colored photosensitive resin composition
Of the components shown in Table 1 below, the total amount of the pigment, which is the composition of the coloring material (E), and the pigment dispersant, which is the additive (G), is 20% by weight relative to the mixture of the pigment, the pigment dispersant, and the propylene glycol monomethyl ether acetate. After mixing and sufficiently dispersing the pigment using the bead mill, the bead mill is separated, and the remaining components including the remaining amount (10.2 wt%) of propylene glycol monomethyl ether acetate are further added and mixed to color the photosensitive resin in a conventional manner. The composition was prepared.
Benzophenone
Experimental Example 1. color filter manufacturer
A 2 square inch glass substrate (# 1737, manufactured by Corning) was washed sequentially with a neutral detergent, water, and alcohol and dried. Film thickness after post-firing when the colored photosensitive resin composition of Examples 1-3 and Comparative Examples 1-2 of Table 1 was exposed on this glass substrate by 100 mJ / cm <2> of exposure amount (365 nm), and the image development process was skipped. Was spin-coated to 1.9 µm and pre-dried at 100 ° C. for 3 minutes in a clean oven. After cooling, the gap between the substrate coated with the colored photosensitive resin composition and a quartz glass photomask (having a pattern for changing the transmittance stepwise in the range of 1 to 100% and a line / space pattern from 1 µm to 50 µm) Was made into 100 micrometers, and it irradiated with the exposure amount (365 nm) of 100 mJ / cm <2> in air | atmosphere using the ultrahigh pressure mercury lamp (brand name USH-250D) by Ushio Denki Corporation. Thereafter, the coating film was immersed at 26 ° C. for a predetermined time in an aqueous developer containing 0.12% of nonionic surfactant and 0.06% of potassium hydroxide, and then dried at 220 ° C. for 30 minutes after washing with water. No surface roughness was found in the obtained pixel portion. In addition, in the non-pixel portion, no developing residue was generated on the substrate. The minimum required exposure amount required to form a thin film free from pattern errors (line tearing) even after development was measured at 50 mJ / cm 2.
Experimental Example 2. Measurement of color filter characteristics
The development residue, cross-sectional shape, straightness and pencil hardness of the color filter prepared in Experimental Example 1 were measured. The measurement results are shown in Table 2 below.
* 1: ○: no development residue on substrate, ×: development residue on substrate
* 2: The cross-sectional shape of the pixel edge part was observed using SEM.
○: Forward tapered, ×: Reverse tapered
* 3: When the generated pattern was evaluated through an optical microscope,
○: If there is no error in the pattern
△: 1-3 errors in pattern
×: 4 or more errors in pattern
In the above results, the color filters prepared according to Examples 1 to 3 including Chemical Formula 1 did not have development residues on the substrate, the cross-sectional shape was observed on the forward tape, and an excellent color filter was not produced. It became. On the other hand, the color filters prepared in Comparative Examples 1 and 2, which do not include Formula 1, had development residues on the substrate, and both the cross-sectional shape and the straightness were not excellent.
Claims (9)
The said alkali-soluble resin (B) has an acid value of 50-150 (mgKOH / g), The polystyrene reduced weight average molecular weight is 5,000-50,000, The coloring photosensitive resin composition characterized by the above-mentioned.
[Formula 1]
R is an alicyclic or aromatic hydrocarbon having 4 to 24 carbon atoms, with or without O, CO, CR 3 R 4 , S or SO 2 groups,
R 3 and R 4 are each independently hydrogen, an aliphatic hydrocarbon of 1 to 12 carbon atoms or an aromatic hydrocarbon of 6 to 12 carbon atoms, wherein R 3 and R 4 may be connected to form an alicyclic hydrocarbon,
R 1 is a branched hydrocarbon or alicyclic hydrocarbon having 3 to 12 carbon atoms with or without heteroatoms,
R 2 is hydrogen or methyl,
N is a natural number of 2 to 6.
[Formula 2]
R 1 is a branched hydrocarbon or alicyclic hydrocarbon having 3 to 12 carbon atoms with or without heteroatoms,
R 2 is hydrogen or methyl,
N is a natural number of 2 to 6.
[Formula 3]
R is an alicyclic or aromatic hydrocarbon having 4 to 24 carbon atoms, with or without O, CO, CR 3 R 4 , S or SO 2 groups,
R 3 and R 4 are each independently hydrogen, an aliphatic hydrocarbon having 1 to 12 carbon atoms or an aromatic hydrocarbon having 6 to 12 carbon atoms, wherein R 3 and R 4 may be connected to form an alicyclic hydrocarbon.
[Formula 4]
[Formula 5]
[Formula 6]
[Formula 7]
[Formula 8]
X in Chemical Formulas 7 and 8 is a direct connection, CO, CR 3 R 4 , O, S or SO 2 ,
R 3 and R 4 are each independently hydrogen, an aliphatic hydrocarbon having 1 to 12 carbon atoms or an aromatic hydrocarbon having 6 to 12 carbon atoms, wherein R 3 and R 4 may be connected to form an alicyclic hydrocarbon.
[Formula 9]
[Formula 10]
[Formula 11]
[Formula 12]
[Formula 13]
[Formula 14]
[Formula 15]
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020130081457A KR102017246B1 (en) | 2013-07-11 | 2013-07-11 | Polyfunctional acrylate compounds, a colored photosensitive resin, color filter and display device comprising the same |
Applications Claiming Priority (1)
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| KR1020130081457A KR102017246B1 (en) | 2013-07-11 | 2013-07-11 | Polyfunctional acrylate compounds, a colored photosensitive resin, color filter and display device comprising the same |
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| JP2006243493A (en) * | 2005-03-04 | 2006-09-14 | Fuji Photo Film Co Ltd | Photosensitive lithographic printing plate |
| CN101082771A (en) * | 2006-05-30 | 2007-12-05 | 奇美实业股份有限公司 | Photosensitive resin composition for colorful color filter |
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| US5320886A (en) * | 1991-11-14 | 1994-06-14 | American Dental Association Health Foundation | Hydrophilic crosslinking monomers and polymers made therefrom |
| JPH05202332A (en) * | 1992-01-27 | 1993-08-10 | Taiyo Ink Seizo Kk | Liquid photo-solder resist ink composition |
| KR100678958B1 (en) | 2005-07-29 | 2007-02-06 | 삼성전자주식회사 | Deblocking filtering method considering intra BL mode, and video encoder/decoder based on multi-layer using the method |
| JP5396833B2 (en) | 2008-11-28 | 2014-01-22 | Ｊｓｒ株式会社 | Radiation-sensitive resin composition, spacer and protective film for liquid crystal display element, and method for forming them |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2006243493A (en) * | 2005-03-04 | 2006-09-14 | Fuji Photo Film Co Ltd | Photosensitive lithographic printing plate |
| CN101082771A (en) * | 2006-05-30 | 2007-12-05 | 奇美实业股份有限公司 | Photosensitive resin composition for colorful color filter |
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