KR101710409B1 - Photosensitive phosphorus-containing unsaturated acrylic compositions and the method of manufacturing the same - Google Patents
Photosensitive phosphorus-containing unsaturated acrylic compositions and the method of manufacturing the same Download PDFInfo
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- KR101710409B1 KR101710409B1 KR1020150144403A KR20150144403A KR101710409B1 KR 101710409 B1 KR101710409 B1 KR 101710409B1 KR 1020150144403 A KR1020150144403 A KR 1020150144403A KR 20150144403 A KR20150144403 A KR 20150144403A KR 101710409 B1 KR101710409 B1 KR 101710409B1
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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
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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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
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Abstract
Description
The present invention relates to a photosensitive phosphorus-containing unsaturated acrylic resin composition for use in a photosensitive resin composition for the production of color filters and a method of preparing the same. More particularly, And more particularly to a photosensitive phosphorus containing unsaturated acrylic composition which provides less outgassing in a high temperature process of at least 200 < 0 > C, and a method of making the same.
A color filter used in an LCD (liquid crystal display) is formed by forming fine pixels such as red, green, and blue on a transparent substrate such as glass by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method or the like.
Of these various production methods, a production method (pigment dispersion method) in which pigments are dispersed in a photosensitive resin composition is the mainstream in recent years in the production of color filters for LCDs because of high productivity and fine workability, An alkaline developing photosensitive binder, a photopolymerizable monomer, a photoinitiator, a solvent, and other additives.
In the pigment dispersion method, for example, a composition in which a pigment is dispersed in a photosensitive binder is coated on a transparent substrate such as glass provided with a black matrix, the formed coating film is exposed to light by UV irradiation through a photomask, And then the pattern is formed by repeating a series of steps of removing it by development processing and postbaking it.
Such a pigment dispersion method can improve the heat resistance and durability, which are the most important properties of the color filter, and has an advantage that the thickness of the film can be uniformly maintained.
However, in recent years, the use of LCD has been expanded to a large area such as a desktop monitor, an LCD TV, etc., away from conventional notebook computers. Therefore, in order to realize high quality color, the pigment concentration in the photosensitive resin composition is increased, It is required to improve the performance.
Also, since the fine patterns of red, green and blue formed are exposed to a high temperature of 200 ° C or higher in the process of manufacturing a color filter, a characteristic of out gas generated in a high temperature process is required to be small.
This is because when an out gas is generated in a large amount, an out gas is excessively present in the liquid crystal during a color filter manufacturing process, and a pixel defect may occur due to a malfunction of the liquid crystal.
On the other hand, Japanese Patent Application Laid-Open No. 2004-302293 discloses a process for producing a resin capable of improving transparency and film hardness of a cured product by introducing an ester compound containing an alicyclic group of an unsaturated carboxylic acid and an N-substituted maleimide compound in a binder polymer However, these compounds are excellent in transparency and film hardness of the cured product, but have a large amount of out gas generated in a high-temperature process, have poor coloring of the composite, .
Korean Patent Laid-Open Publication No. 10-2012-0125472 discloses a photosensitive resin composition comprising at least a photosensitive polyurethane resin, a phosphorus-containing flame retardant, a polymerizable compound and a photopolymerization initiator, wherein the photosensitive polyurethane resin has an ethylenically unsaturated bonding group and a carboxyl group , And a polyurethane skeleton containing a polyol group as a repeating unit is known. However, the photosensitive polyurethane resin is a photosensitive polyurethane resin which contains a polymer polyol compound, a diisocyanate compound, and a polymer having two hydroxyl groups in the molecule ) Acrylate compound with a carboxylic acid having two hydroxyl groups in the molecule, there is a problem that the photosensitive effect is relatively lowered.
Korean Patent Laid-Open No. 10-2013-0132411 discloses a resin composition containing (A) a compound having a carboxyl group, (B) a compound having a reactive group reacting with a carboxyl group, (C) an oxime ester-based photopolymerization initiator, and (D) A photosensitive resin composition containing a compound having a photosensitive group has been known to be effective for storage stability and low-temperature curability after storage for a long period of time. However, it does not provide any out gas effect at a high temperature .
Accordingly, the present invention has been accomplished based on the discovery that the phosphorus-containing unsaturated acrylic composition is effective in forming fine patterns and improving the development speed and generating less out gas in a high-temperature process of 200 ° C or more after the development process.
Disclosure of the Invention In order to solve the above problems, the present invention provides a photosensitive resin composition comprising a carboxylic acid compound containing an unsaturated group, a methacrylate compound containing phosphorus, an ethylenically unsaturated compound, and an ethylenically unsaturated compound having an epoxy group, It is an object of the present invention to solve the problem of forming an excellent fine pattern and improving the development speed by using the phosphorus-containing unsaturated acrylic composition, and causing an out gas to be generated in a high temperature process of 200 ° C or more after the development process.
In order to solve the above-described problems, the present invention provides a resin composition comprising: (A) a carboxylic acid compound containing an unsaturated group; (B) a phosphorus-containing methacrylate compound represented by the following formula (1); (C) an ethylenically unsaturated compound; (D) an ethylenically unsaturated compound having an epoxy group, as a solution to the problem.
[Chemical Formula 1]
(Wherein R 1 represents H, CH 3 or C 2 H 5 , R 2 represents an alicyclic or aromatic group, and n represents 0 or 1 to 5.)
The photosensitive phosphorus containing unsaturated acrylic composition comprises (A) 10 to 40% by weight of a carboxylic acid compound containing an unsaturated group; (B) 1 to 50% by weight of a phosphorus-containing methacrylate compound represented by the formula (1); (C) 15 to 80% by weight of an ethylenically unsaturated compound; (D) 5 to 40% by weight of an ethylenically unsaturated compound having an epoxy group as a solution to the problem.
The carboxylic acid compound containing unsaturated group (A) may be at least one selected from the group consisting of acrylic acid, methacrylic acid, methacrylic acid dimer, maleic acid, crotonic acid, itaconic acid, fumaric acid, monomethyl maleic acid, isoprenesulfonic acid, styrenesulfonic acid, 2- (Meth) acryloyloxyethylphthalic acid, (meth) acryloyloxyethylhexahydrophthalic acid, omega -carboxypolycaprolactone mono (meth) acrylate, 5-norbornene-2- (Hydroxymethyl) acrylic acid, and the like.
The phosphorus-containing methacrylate compound represented by the above-mentioned formula (B) is preferably selected from the group consisting of phosphate 2-hydroxyethylmethacrylate, phosphate caprolactone-modified 2-hydroxyethylmethacrylate caprolactone modified 2-hydroxyehtylmethacrylate).
The ethylenically unsaturated compound (C) is a compound selected from the group consisting of styrene,? -Methylstyrene, (o, m, p) -vinyltoluene, (o, m, p) -methoxystyrene, Selected aromatic vinyls; Butyl (meth) acrylate, dimethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acyloctyloxy- (Meth) acrylate, ethoxydiethylene glycol (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (Meth) < / RTI > tri Acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoro (Meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, methyl? -Hydroxymethylacrylate, ethyl? -Hydroxymethylacrylate, (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentanyl Unsaturated carboxylic acid esters selected from dicyclopentenyloxyethyl (meth) acrylate; Unsaturated imides selected from N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide; N-vinyl tertiary amines selected from N-vinyl pyrrolidone, N-vinyl carbazole, N-vinyl morpholine; Unsaturated ethers selected from vinyl methyl ether and vinyl ethyl ether; Maleic anhydride, and maleic anhydride selected from maleic anhydride and methylmaleic anhydride.
The ethylenically unsaturated compound (D) having an epoxy group is preferably at least one selected from the group consisting of glycidyl (meth) acrylate,? -Methyl glycidyl (meth) acrylate,? -Ethyl glycidyl (meth) (Meth) acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 3-ethyl- (Meth) acrylate, 5-methyl-5,6-epoxyhexyl (meth) acrylate, and glycidyl vinyl ether. .
The photosensitive phosphorus containing unsaturated acrylic composition has an acid value of 20 to 200 KOH mg / g and a weight average molecular weight of 1,000 to 100,000.
The present invention also relates to a composition comprising (A) a carboxylic acid compound containing an unsaturated group; (B) a phosphorus-containing methacrylate compound represented by the following formula (1); (C) copolymerizing an ethylenically unsaturated compound; (D) an additional ring-opening reaction of an ethylenically unsaturated compound having an epoxy group during or during the copolymerization reaction of (A), (B) and (C) .
The photosensitive phosphorus-containing unsaturated acrylic composition according to the present invention exhibits excellent fine pattern formation and improvement in development speed, developability, re-solubility, color characteristics (luminance), and out gas at a high temperature process of 200 ° C or more after the development process And it can be used for manufacturing a photosensitive resin composition color filter capable of realizing high quality color of LED TV, notebook, touch screen, desktop monitor and face-to-face application.
BRIEF DESCRIPTION OF THE DRAWINGS FIG.
Fig. 2 is a cross-
3 is a comparative photograph showing developing speed and developability
Figure 4 shows a comparison of measurement of color characteristics (luminance) and out gas
The present invention relates to a resin composition comprising (A) a carboxylic acid compound containing an unsaturated group; (B) a phosphorus-containing methacrylate compound represented by the following formula (1); (C) an ethylenically unsaturated compound; And (D) an ethylenically unsaturated compound having an epoxy group.
[Chemical Formula 1]
(Wherein R 1 represents H, CH 3 or C 2 H 5 , R 2 represents an alicyclic or aromatic group, and n represents 0 or 1 to 5.)
The photosensitive phosphorus containing unsaturated acrylic composition comprises (A) 10 to 40% by weight of a carboxylic acid compound containing an unsaturated group; (B) 1 to 50% by weight of a phosphorus-containing methacrylate compound represented by the formula (1); (C) 15 to 80% by weight of an ethylenically unsaturated compound; (D) 5 to 40% by weight of an ethylenically unsaturated compound having an epoxy group is characterized by the technical constitution.
The carboxylic acid compound containing unsaturated group (A) may be at least one selected from the group consisting of acrylic acid, methacrylic acid, methacrylic acid dimer, maleic acid, crotonic acid, itaconic acid, fumaric acid, monomethyl maleic acid, isoprenesulfonic acid, styrenesulfonic acid, 2- (Meth) acryloyloxyethylphthalic acid, (meth) acryloyloxyethylhexahydrophthalic acid, omega -carboxypolycaprolactone mono (meth) acrylate, 5-norbornene-2- (Hydroxymethyl) acrylic acid, and the like.
The phosphorus-containing methacrylate compound represented by the above-mentioned formula (B) is preferably selected from the group consisting of phosphate 2-hydroxyethylmethacrylate, phosphate caprolactone-modified 2-hydroxyethylmethacrylate caprolactone modified 2-hydroxyehtylmethacrylate).
The ethylenically unsaturated compound (C) is a compound selected from the group consisting of styrene,? -Methylstyrene, (o, m, p) -vinyltoluene, (o, m, p) -methoxystyrene, Selected aromatic vinyls; Butyl (meth) acrylate, dimethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acyloctyloxy- (Meth) acrylate, ethoxydiethylene glycol (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (Meth) < / RTI > tri Acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoro (Meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, methyl? -Hydroxymethylacrylate, ethyl? -Hydroxymethylacrylate, (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentanyl Unsaturated carboxylic acid esters selected from dicyclopentenyloxyethyl (meth) acrylate; Unsaturated imides selected from N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide; N-vinyl tertiary amines selected from N-vinyl pyrrolidone, N-vinyl carbazole, N-vinyl morpholine; Unsaturated ethers selected from vinyl methyl ether and vinyl ethyl ether; And maleic anhydride selected from maleic anhydride and methylmaleic anhydride.
The ethylenically unsaturated compound (D) having an epoxy group is preferably at least one selected from the group consisting of glycidyl (meth) acrylate,? -Methyl glycidyl (meth) acrylate,? -Ethyl glycidyl (meth) (Meth) acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 3-ethyl- (Meth) acrylate, 5-methyl-5,6-epoxyhexyl (meth) acrylate, and glycidyl vinyl ether. .
The photosensitive phosphorus containing unsaturated acrylic composition has an acid value of 20 to 200 KOH mg / g and a weight average molecular weight of 1,000 to 100,000.
The present invention also relates to a composition comprising (A) a carboxylic acid compound containing an unsaturated group; (B) a phosphorus-containing methacrylate compound represented by the following formula (1); (C) copolymerizing an ethylenically unsaturated compound; (D) an additional ring-opening reaction of an ethylenically unsaturated compound having an epoxy group during or during the copolymerization reaction of the above (A), (B) and (C) It is characterized by the constitution.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention can be spherical in various different forms, and is not limited to the embodiments described herein.
First, the photosensitive phosphorus containing unsaturated acrylic composition of the present invention comprises (A) a carboxylic acid compound containing an unsaturated group; (B) a phosphorus-containing methacrylate compound represented by the following formula (1); (C) an ethylenically unsaturated compound; (D) an ethylenically unsaturated compound having an epoxy group.
(A) [ carboxylic acid compound containing an unsaturated group ]
(A) a carboxylic acid compound containing an unsaturated group is capable of radical copolymerization with (B) and (C), (D) reacting with an ethylenically unsaturated compound having an epoxy group to enable curing by UV irradiation, , And it is preferable to use 10 to 40% by weight based on the whole copolymer.
When the amount is less than 10% by weight, (D) the development by an alkaline developing solution may not be performed well after introduction of an ethylenically unsaturated compound having the same epoxy group, and when it is used in an amount exceeding 40% by weight, There may be a problem.
The unsaturated group-containing carboxylic acid compound (A) is specifically acrylic acid and methacrylic acid, and acrylic acid and methacrylic acid may be used alone or in combination. In addition to acrylic acid and methacrylic acid, other carboxylic acid compounds containing unsaturated groups may also be used. (Meth) acrylic acid dimer, maleic acid, crotonic acid, itaconic acid, fumaric acid, monomethyl maleic acid, isoprenesulfonic acid, styrenesulfonic acid, 2- (meth) acryloyloxyethylsuccinic acid, 2 (Meth) acryloyloxyethylphthalic acid, (meth) acryloyloxyethylhexahydrophthalic acid, omega -carboxypolycaprolactone mono (meth) acrylate, 5-norbornene-2-carboxylic acid and the like. It is also possible to use a carboxylic acid having an unsaturated group such as? - (hydroxymethyl) acrylic acid and containing a hydroxyl group and a carboxyl group in the same molecule.
(B) a phosphorus-containing methacrylate compound represented by the formula ( 1 )
[Chemical Formula 1]
(Wherein R 1 represents H, CH 3 or C 2 H 5 , R 2 represents an alicyclic or aromatic group, and n represents 0 or 1 to 5.)
The phosphorus-containing methacrylate compound represented by the above formula (1) is capable of radical copolymerization with (A) and (C) and is used for the purpose of improving development rate, pattern formation and heat resistance, By weight to 1% by weight to 50% by weight.
If it is used in an amount of less than 1% by weight, there may be a problem that development speed, pattern formation and heat resistance can not be exhibited, and when it is used in excess of 50% by weight, the risk of gel- have.
Examples of the phosphorus-containing (meth) acrylate compound represented by the above formula (1) include phosphate 2-hydroxyethyl methacrylate, phosphate caprolactone modified 2-hydroxyethyl methacrylate (phosphate caprolactone modified 2-hydroxyehtylmethacrylate).
(C) [ Ethylenically unsaturated compound]
The ethylenically unsaturated compound (C) is capable of radical copolymerization with (A) and (B) and is used for the purpose of improving the film strength, and it is preferable to use 15 to 80% by weight based on the total copolymer.
Examples of the ethylenically unsaturated compound (C) include aromatic vinyls such as styrene,? -Methylstyrene, (o, m, p) -vinyltoluene, p) -chlorostyrene; Unsaturated carboxylic acid esters such as benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, isobutyl (Meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (Meth) acrylate, hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy- (Meth) acrylate, 2-hydroxypropyl (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl (Meth) acrylate (Meth) acrylate, methoxytriethylene glycol (meth) acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) (Meth) acrylate, p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluorois (Meth) acrylate, propyl (meth) acrylate, octafluoropentyl (meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (Meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclohexyl (meth) acrylate, As fentanyl oxyethyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate; Unsaturated imides such as N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide; N-vinyl tertiary amines, such as N-vinyl pyrrolidone, N-vinyl carbazole, N-vinylmorpholine; Unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether; Maleic anhydride such as maleic anhydride and methylmaleic anhydride, and the like.
(D) [ Ethylenic unsaturated compound having an epoxy group ]
The ethylenically unsaturated compound (D) having an epoxy group reacts with the carboxyl group of (A) and is capable of curing by UV irradiation, and is preferably used in an amount of 5 to 40% by weight based on the total copolymer.
If it is used in an amount of less than 5% by weight, the pattern may be damaged after the alkali development due to the lack of crosslinking density after UV irradiation, and if it is used in excess of 40% by weight, gelation of the composite may occur.
Examples of the ethylenically unsaturated compound having an epoxy group (D) include glycidyl (meth) acrylate,? -Methyl glycidyl (meth) acrylate,? -Ethyl glycidyl (meth) (Meth) acrylates such as glycidyl (meth) acrylate,? -Methyl glycidyl? -Ethyl acrylate, 3-methyl-3,4-epoxybutyl , 4-methyl-4,5-epoxypentyl (meth) acrylate, 5-methyl-5,6-epoxyhexyl (meth) acrylate and glycidyl vinyl ether.
The photosensitive phosphorus containing unsaturated acrylic composition of the present invention may contain, in addition to the above-mentioned components, a solvent, a thermal polymerization initiator and other additives. Among the various polymerization methods known in the art such as radical polymerization, cationic polymerization, It can be produced by applying any one of the methods, and radical polymerization, in particular, radical solution polymerization, is particularly preferable.
Further, various organic solvents may be used as the solvent further included in the production of the photosensitive phosphorus containing unsaturated acrylic composition of the present invention. Specific examples thereof include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether; Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether; Ethylene glycol alkyl ether acetates such as methyl cellosolve acetate, ethyl cellosolve acetate; Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate, methoxypentyl acetate; Aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone; Alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerin; Esters such as ethyl 3-ethoxypropionate, methyl 3-methoxypropionate; Cyclic esters such as? -Butyrolactone, and the like.
Specific examples of the thermal polymerization initiator include azo-based compounds such as 2,2'-azobisisobutyronitrile, 2,2'-azobis (2-methylbutyronitrile), 1,1'- Azobis (cyclohexane-1-carbonitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4- Nitrile), dimethyl-2,2'-azobis (2-methylpropionate), 4,4'-azobis (4-cyanovaleric acid), 2,2'-azobis Propionitrile); Organic peroxides such as tert-butyl hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate , tert-butyl peroxyneodecanoate, tert-butyl peroxy pivalate, (3,5,5-trimethylhexanoyl) peroxide; Inorganic peroxides such as potassium persulfate, ammonium persulfate, and hydrogen peroxide, which can be selected depending on the reaction temperature.
In order to produce the photosensitive phosphorus-containing acrylic resin according to the present invention, the components (A), (B) and (C) are subjected to radical copolymerization to obtain a copolymer.
The components (A), (B) and (C) are subjected to radical copolymerization in order to obtain the copolymer, and the copolymerization is carried out under the usual conditions of radical solution polymerization.
(A), (B), and (C) prepared in a four-necked flask equipped with a thermometer, a stirrer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, And the air in the flask is replaced with nitrogen. Next, the temperature of the solvent is raised to 50 to 150 캜, and one or two or more kinds of thermal polymerization initiators of 0.05 to 10% by weight based on the total weight of the prepared components (A), (B) and (C) This mixture is added dropwise for 1 to 5 hours using a dropping funnel. 0.01 to 3% by weight, based on the total weight of the components (A), (B) and (C), prepared for removing unreacted monomers after 1 to 4 hours from completion of the dropwise addition, Into a four-necked flask. Subsequently, the mixture in a four-necked flask is stirred at 50 to 150 DEG C for 1 to 8 hours to obtain a copolymer.
In the above method, the components (A), (B), (C) and the thermal polymerization initiator may be filled in a four-necked flask all or in part before the initial temperature is raised to 50 to 150 ° C.
In order to control the molecular weight and the molecular weight distribution, chain transfer agents such as alkyl mercaptans,? -Methyl styrene dimers, organohalogen compounds, terpinolene and alpha terpinene having 8 to 18 carbon atoms may be used. Is preferably 0.1 to 5% by weight based on the total weight of (A), (B) and (C). The input method, the reaction temperature and the reaction time of each of the above components can be appropriately adjusted according to the characteristics of the production apparatus and each component.
Next, the photosensitive phosphorus containing unsaturated acrylic resin of the present invention is prepared by subjecting a part of the carboxyl group of the obtained copolymer and the epoxy group of the component (D) to a ring-opening addition reaction to give a UV curing property.
Specifically, the content of the component (D) prepared in the four-necked flask filled with the copolymer obtained in Example 1 and the content of the component (A), the component (B) and the component (C) 0.01 to 3% by weight of an epoxy ring-opening catalyst such as an alkylammonium salt, triphenylphosphine, triphenylantimony, dimethylaminopyridine and the like, and 0.01 to 3% by weight based on the total weight of the components (A), (B) For example, hydroquinones, t-butyl catechol, pyrocatechol p-anisole and the like, and reacted at 60 to 130 ° C for 1 to 8 hours to prepare a final phosphorus-containing unsaturated acrylic resin. The input method, the reaction temperature and the reaction time of each of the above components can be appropriately adjusted according to the characteristics of the production apparatus and each component.
The weight ratio of the monomer component constituting the photosensitive phosphorus-containing unsaturated acrylic resin is preferably in the following range.
(A) 10 to 40% by weight of a carboxylic acid compound containing an unsaturated group;
(B) 1 to 50% by weight of a (meth) acrylate compound containing phosphorus;
(C) 15 to 80 parts by weight of an ethylenically unsaturated compound;
(D) 5 to 40% by weight of an ethylenically unsaturated compound having an epoxy group
The photosensitive phosphorus-containing unsaturated acrylic resin preferably has a weight average molecular weight of 1,000 to 100,000, more preferably 5,000 to 50,000, and an acid value of 20 to 200 KOH mg / g.
When the weight average molecular weight is less than 1,000, the basic hardness, heat resistance and chemical resistance deteriorate and the pattern disappears in the alkaline developer. When the weight average molecular weight exceeds 100,000, the hardness, heat resistance and chemical resistance are good, .
When the acid value is less than 20 KOHmg / g, the linearity of the pattern is good. However, since the solubility of the alkaline developer is low, the development time is long and the development is poor. If the acid value exceeds 200 KOHmg / g, The development time is short, but the pattern may be damaged by the developer, so that the pattern desorption phenomenon and the pattern straightness can not be secured.
The molecular weight distribution (weight average molecular weight divided by number average molecular weight) of the photosensitive phosphorus containing unsaturated acrylic resin is preferably 1.7 to 5.0. When the molecular weight distribution is within the above range, the developing property is excellent.
The photosensitive phosphorus-containing unsaturated acrylic resin produced by the present invention can be mixed with a photopolymerizable compound, a photopolymerization initiator, a pigment, and a solvent to be used as a photosensitive resin composition for producing a color filter.
Examples of the photopolymerizable compound of the photosensitive phosphorus containing unsaturated acrylic resin composition include ethylene glycol diacrylate, triethylene glycol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol di Acrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol pentaacrylate, pentaerythritol hexaacrylate, bisphenol A Diacrylate, trimethylolpropane triacrylate, novolak epoxy acrylate, ethylene glycol dimethacrylate, dimethylene glycol dimethacrylate, triethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,4 -Butanediol dimethacrylate, 1,6-hexanediol dimethacrylate, and the like have.
Examples of the photopolymerization initiator of the photosensitive resin composition include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, (2-hydroxy-2-methylethyl) phenylketone, pt Dichloro-4-phenoxyacetophenone, 2-methyl-1- (4-methylthio) phenyl) -2-tert-butyldichloroacetophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'- 3,3'-dimethyl-2-methoxybenzophenone, 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone; As the thioxanthone compound, thioxanthone, 2-crothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone , 2-chlorothioxanthone; As the benzoin compound, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal; As the triazine compound, there may be mentioned 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6 (Trichloromethyl) -s-triazine, 2- (4-methoxynaphtho-1-yl) -4,6-bis Methyl (piperonyl) -6-triazine, 2,4-trichloromethyl (4'-methoxystyryl) -6-triazine and the like.
Examples of the pigment of the photosensitive resin composition include an anthraquinone pigment and a condensed polycyclic pigment such as a perylene pigment, an organic pigment such as a phthalocyanine pigment and an azo pigment, and an inorganic pigment such as carbon black.
As the solvent of the photosensitive resin composition, a solvent used in the production of the alkali developable photosensitive binder according to the present invention may be used.
278.5 g of propylene glycol monomethyl ether acetate and 278.5 g of ethylene glycol monomethyl ether were charged into a 1 L-4 flask equipped with a thermometer, a stirrer, a reflux condenser, a dropping funnel and a nitrogen inlet tube, and air in the flask was replaced with nitrogen. The flask was heated to 70 DEG C, and 107.1 parts by weight of benzylmethacrylate, 11.9 parts by weight of 2-hydroxy-3-hydroxyethyl methacrylate, 72.0 parts by weight of methacrylic acid, 1.9 parts by weight of 2,2'-azobisisobutyronitrile, and 0.8 part by weight of? -methylstyrene dimer were mixed, and the mixture was dropped into the flask using a dropping funnel for 3 hours. One hour after completion of the dropwise addition, 0.4 part by weight of benzoyl peroxide was added, and the mixture in the flask was subsequently stirred at 70 DEG C for 6 hours. The flask was heated to 110 占 폚, and 0.2 parts by weight of triphenylphosphine, 0.2 parts by weight of hydroquinone monomethyl ether and 47.7 parts by weight of glycidyl methacrylate were charged and reacted for 6 hours while maintaining the flask at 110 占 폚 to obtain a weight average molecular weight of 21,000 , And an acid value of 124 KOH mg / g were prepared.
In Example 2, 95.1 parts by weight of benzylmethacrylate and 23.9 parts by weight of 2-hydroxy-2-hydroxyethyl methacrylate were used, and the remaining raw materials, solvent and process were prepared in the same manner as in Example 1 to give a weight average molecular weight of 23,500, an acid value of 131 KOHmg / g, pale yellowish, photosensitive phosphorus containing unsaturated acrylic resin.
In Example 3, 83.2 parts by weight of benzylmethacrylate and 35.8 parts by weight of phosphate 2-hydroxyethyl methacrylate were used, and the remaining raw materials, solvent and process were prepared in the same manner as in Example 1, and the weight average molecular weight was 24,100, the acid value was 143 KOHmg / g pale yellowish photosensitive phosphorus containing unsaturated acrylic resin.
[Comparative Example 1]
In Comparative Example 1, 80.8 parts by weight of benzylmethacrylate, 19.1 parts by weight of N-phenylmaleimide and 19.1 parts by weight of isobornylmethacrylate were used, and the remaining raw materials and processes were prepared in the same manner as in Example 1 to give a weight average molecular weight of 20,500, An acid value of 122 KOHmg / g thick dark brown unsaturated acrylic resin was prepared.
[Comparative Example 2]
In Comparative Example 2, 19.1 parts by weight of cyclohexyl methacrylate was used, and the remaining raw materials and processes were prepared in the same manner as in Comparative Example 1 to prepare a dark yellowish brown unsaturated acrylic resin having a weight average molecular weight of 20,100 and an acid value of 118 KOHmg / g.
[Experimental Example]
In order to evaluate fine pattern formation, development speed and developability, color characteristics and out gas generation amount of the photosensitive phosphorus containing unsaturated acrylic resin of the present invention, a photosensitive resin composition was first prepared as shown in FIG.
Each of the prepared photosensitive resin compositions was coated on a transparent glass substrate to a uniform thickness using a spin coater, and preliminarily heat-treated at 100 ° C for 3 minutes in a clean oven. After cooling, the coating film was exposed at an energy of 200 mJ / cm 2 under a high-pressure mercury lamp using a photomask, and then the coating film was immersed in an aqueous developer containing a nonionic surfactant at a concentration of 0.12% and potassium hydroxide at a concentration of 0.06% For 80 seconds, the aqueous developing solution was stirred to cause development, and the membrane was washed with deionized water. Thereafter, post-heat treatment was performed at 220 캜 for 20 minutes to obtain a cured pattern (2 탆).
The results of measurement of fine pattern formation, developability and outgassing amount obtained are shown in [FIG. 2] to [FIG. 4].
Compared to [Comparative Examples 1] to [Comparative Example 2], [Embodiment 1] to [Embodiment 3] are different from Embodiment 1 to Embodiment 2 in terms of pattern formation, developing speed, It can be seen that it is excellent in solubility.
In addition, as shown in FIG. 4, a colorimeter is used for measurement of the color characteristic (luminance). Since the color characteristic (luminance) is better as the RY value is larger, [Examples 1 to 3] Which is superior to that of [Example 1] to [Comparative Example 2].
The out gas of [Figure 4] was analyzed by pyrolysis of the pattern obtained in the above experiment through Py-GC / MS at 230 ° C for 30 minutes. The smaller the value, the better , It can be seen that [Examples 1] to [3] are superior to those of [Comparative Examples 1] to [Comparative Example 2].
In conclusion, the photosensitive phosphorus-containing unsaturated acrylic resin of [Examples 1] to [3] prepared according to the present invention had a very light yellow color, while [Comparative Examples 1] to [Comparative Example 2] The color tone was yellow and the color was not good and the pattern formation, development speed, developability and remelability, color characteristics (luminance) and low outgassing (out) of the photosensitive phosphorus containing unsaturated acrylic resin of [Examples 1] to [Example 3] gas generation rate is superior to that of [Comparative Example 1] to [Comparative Example 2].
It will be apparent to those skilled in the art that various modifications, substitutions and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims. will be. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all technical ideas within the scope of equivalents should be construed as falling within the scope of the present invention.
Claims (8)
[Chemical Formula 1]
(Wherein R 1 represents H, CH 3 or C 2 H 5 , R 2 represents an alicyclic or aromatic group, and n represents 1 to 5.)
The carboxylic acid compound containing unsaturated group (A) may be at least one selected from the group consisting of acrylic acid, methacrylic acid, methacrylic acid dimer, maleic acid, crotonic acid, itaconic acid, fumaric acid, monomethyl maleic acid, isoprenesulfonic acid, styrenesulfonic acid, 2- (Meth) acryloyloxyethylphthalic acid, (meth) acryloyloxyethylhexahydrophthalic acid, omega -carboxypolycaprolactone mono (meth) acrylate, 5-norbornene-2- Containing unsaturated acrylic resin composition is at least one selected from the group consisting of acrylic acid, methacrylic acid,
Wherein the phosphorus-containing methacrylate compound represented by the above formula (B) is phosphate caprolactone modified 2-hydroxyehtylmethacrylate. 2. The photosensitive phosphorus-containing unsaturated acrylic resin composition according to claim 1, Composition
The ethylenically unsaturated compound (C) is a compound selected from the group consisting of styrene,? -Methylstyrene, (o, m, p) -vinyltoluene, (o, m, p) -methoxystyrene, Selected aromatic vinyls; Butyl (meth) acrylate, dimethyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (Meth) acrylate, cyclohexyl (meth) acrylate, isobonyl (meth) acrylate, ethylhexyl (meth) acrylate, 2-phenoxyethyl Acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxy-3-chloropropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, acyloctyloxy- (Meth) acrylate, ethoxydiethylene glycol (meth) acrylate, glycerol (meth) acrylate, 2-methoxyethyl (meth) acrylate, 3-methoxybutyl (Meth) < / RTI > tri Acrylate, methoxytripropylene glycol (meth) acrylate, poly (ethylene glycol) methyl ether (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, p-nonylphenoxypolyethylene glycol p-nonylphenoxypolypropylene glycol (meth) acrylate, tetrafluoropropyl (meth) acrylate, 1,1,1,3,3,3-hexafluoroisopropyl (meth) acrylate, octafluoro (Meth) acrylate, heptadecafluorodecyl (meth) acrylate, tribromophenyl (meth) acrylate, methyl? -Hydroxymethylacrylate, ethyl? -Hydroxymethylacrylate, (Meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentanyl Unsaturated carboxylic acid esters selected from dicyclopentenyloxyethyl (meth) acrylate; Unsaturated imides selected from N-phenylmaleimide, N- (4-chlorophenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide; N-vinyl tertiary amines selected from N-vinyl pyrrolidone, N-vinyl carbazole, N-vinyl morpholine; Unsaturated ethers selected from vinyl methyl ether and vinyl ethyl ether; A maleic anhydride, and a maleic anhydride selected from maleic anhydride and methylmaleic anhydride. The photosensitive phosphorus containing unsaturated acrylic composition
The ethylenically unsaturated compound (D) having an epoxy group is preferably at least one selected from the group consisting of glycidyl (meth) acrylate,? -Methyl glycidyl (meth) acrylate,? -Ethyl glycidyl (meth) (Meth) acrylate, 3-methyl-3,4-epoxybutyl (meth) acrylate, 3-ethyl- (Meth) acrylate, 5-methyl-5,6-epoxyhexyl (meth) acrylate, and glycidyl vinyl ether. Unsaturated acrylic composition
Wherein the photosensitive phosphorus containing unsaturated acrylic composition has an acid value of 20 to 200 KOH mg / g and a weight average molecular weight of 1,000 to 100,000.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20060111178A (en) * | 2005-04-22 | 2006-10-26 | 주식회사 엘지화학 | Alkali-developable resin and photosensitive resin composition comprising the same |
| KR20090047620A (en) * | 2007-11-08 | 2009-05-13 | 주식회사 엘지화학 | Colored dispersions, photoresist resin composition and black matrix |
| KR20090098416A (en) * | 2008-03-14 | 2009-09-17 | 애경화학 주식회사 | Alkaline developing photosensitive binder and the method for processing thereof |
| KR20120106408A (en) * | 2011-03-18 | 2012-09-26 | 주식회사 엘지화학 | Photoactive compound and photosensitive resin composition comprising the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20060111178A (en) * | 2005-04-22 | 2006-10-26 | 주식회사 엘지화학 | Alkali-developable resin and photosensitive resin composition comprising the same |
| KR20090047620A (en) * | 2007-11-08 | 2009-05-13 | 주식회사 엘지화학 | Colored dispersions, photoresist resin composition and black matrix |
| KR20090098416A (en) * | 2008-03-14 | 2009-09-17 | 애경화학 주식회사 | Alkaline developing photosensitive binder and the method for processing thereof |
| KR20120106408A (en) * | 2011-03-18 | 2012-09-26 | 주식회사 엘지화학 | Photoactive compound and photosensitive resin composition comprising the same |
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