KR20160035272A - Color photosensitive resin composition, color filter manufactured thereby, and liquid crystal display comprising the same - Google Patents
Color photosensitive resin composition, color filter manufactured thereby, and liquid crystal display comprising the same Download PDFInfo
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- KR20160035272A KR20160035272A KR1020140126641A KR20140126641A KR20160035272A KR 20160035272 A KR20160035272 A KR 20160035272A KR 1020140126641 A KR1020140126641 A KR 1020140126641A KR 20140126641 A KR20140126641 A KR 20140126641A KR 20160035272 A KR20160035272 A KR 20160035272A
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- photosensitive resin
- colored photosensitive
- acrylate
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
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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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/23—Photochromic filters
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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
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
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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
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Chemical & Material Sciences (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials For Photolithography (AREA)
Abstract
BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a colored photosensitive resin composition, a color filter manufactured thereby, and a liquid crystal display having the same. More particularly, the present invention relates to a color filter, , A photopolymerizable monomer, a photopolymerization initiator and a solvent, a color filter manufactured thereby, and a liquid crystal display device having the same.
The colored photosensitive resin composition is a high-quality color filter which eliminates the problem of luminance and yellowing, has excellent color characteristics, is excellent in adhesion with a substrate and has excellent reliability, has a high developing speed and has no residue, and a liquid crystal display As shown in FIG.
Description
The present invention relates to a colored photosensitive resin composition excellent in chemical resistance and heat resistance, free of residue, and excellent in developing margin, a color filter manufactured thereby, and a liquid crystal display device having the same.
The liquid crystal display implements a screen by mixing the three primary colors of white light emitted from the backlight through a color filter having red, green, and blue patterns.
The color filter is an important part for supporting a liquid crystal display device, and has been adopted for a wide variety of applications such as a notebook PC, a monitor, and a portable terminal, along with the spread of a flat panel display.
In order to realize a high-quality screen, the physical properties of the color filter should be excellent, and color characteristics and contrast should be improved first. In addition, the transmittance and contrast ratio must be high, the adhesion, uniformity and flatness must be kept high, and reliability is required to operate stably even in an environment exposed to light and heat.
The manufacturing method of the color filter is the most popular method of manufacturing a photosensitive resin composition containing a dye or a pigment and manufacturing the photosensitive resin composition through a photolithography process.
The photosensitive resin composition contains a colorant, a binder resin, a photopolymerizable compound, an initiator and a solvent as main components. In order to satisfy the required properties mentioned above, the composition of the photosensitive resin composition is changed or the photolithography process conditions are changed Various attempts have been made.
For example, International Publication No. WO 2013/047454 discloses a photosensitive resin composition using a pigment compound such as a dipyrammethene metal complex compound or an azopyromethene metal complex compound and a porphyrin compound in order to obtain high brightness and contrast.
International Publication WO 2013/050431 can also include a salt comprising at least one cationic cyanine compound as the cation and at least one anionic xanthene compound as the anion to improve the thermal stability and brightness of the color filter .
These patents, however, are advantageous in that the brightness can be improved to some extent by changing the composition of the pigments, but they are still insufficient in terms of other properties such as color characteristics.
In addition, Korean Patent Publication No. 2010-0078845 discloses a photosensitive composition comprising an alkali-soluble resin, a photopolymerizable monomer, a photopolymerization initiator, a pigment, and a solvent in order to improve color characteristics and developability, to a bisphenol type ethoxylate epoxy acrylate compound Is used. Although such a composition has improved color characteristics to some extent, a new problem has arisen in that the yellowing occurs and the luminance is lowered.
In other words, the compounds disclosed in the above-mentioned patents cause yellowing due to the action of a chromophore which is a functional group exhibiting color as the benzene ring of bisphenol forms a quinone ring by an internal redox reaction, and when yellowing proceeds, There are two problems, such as yellow color changing to red color.
As a result of various studies to produce a photosensitive composition having a novel composition, the Applicant has found that the use of an ethoxylate epoxy acrylate compound having no aromatic ring causing yellowing enhances the brightness of a color filter, It is possible to improve the adhesion, the chemical resistance, the heat resistance, the residue characteristic and the developing margin as well as having excellent color characteristics, and completed the present invention.
Accordingly, an object of the present invention is to provide a colored photosensitive resin composition comprising an ethoxylate epoxy acrylate compound so as to be applicable to a color filter.
Another object of the present invention is to provide a use of the colored photosensitive resin composition which can be used for the production of a color filter.
It is still another object of the present invention to provide a liquid crystal display device provided with a color filter made of the colored photosensitive resin composition.
The present invention is characterized by a colored photosensitive resin composition comprising an ethoxylate epoxy acrylate compound represented by the following Formula 1:
[Chemical Formula 1]
(In the formula 1,
R is a quaternary carbon having an alkyl group of C1 to C4,
Y is an acryloyl group or a methacryloyl group,
a is an integer of 1 to 15,
and n is an integer of 4 to 6)
At this time,
Preferably, R < 1 > is a methyl group.
More preferably, the compound of Formula 1 is a compound represented by Formula 2 or 3:
(2)
(3)
(In the above formulas 2 and 3,
R 1 is an alkyl group having from 1 to 4 carbon atoms,
and a is an integer of 1 to 15)
The present invention also features a colored photosensitive resin composition comprising a colorant, a binder resin, a photopolymerizable monomer, a photopolymerization initiator and a solvent together with the ethoxylate epoxy acrylate compound.
Wherein the colored photosensitive resin composition comprises 1.5 to 30% by weight of an ethoxylate epoxy acrylate compound, 3 to 60% by weight of a colorant, 2 to 80% by weight of a binder resin, 5 to 50% by weight, a photopolymerization initiator in an amount of 0.1 to 40% by weight, and a solvent.
Further, the present invention is characterized by a color filter manufactured using the colored photosensitive resin composition.
Further, the present invention features a liquid crystal display device provided with a color filter made of the colored photosensitive resin composition of the present invention.
The colored photosensitive resin composition according to the present invention solves the problems of luminance and yellowing, has excellent color characteristics, is excellent in adhesion with a substrate and has excellent reliability, has a high developing speed and does not leave residues, and includes high quality color filters and the like The present invention can be applied to a liquid crystal display device.
The present invention provides a colored photosensitive resin composition which can be used as a color filter of a liquid crystal display device so as to realize a high-quality screen.
The colored photosensitive resin composition comprises an ethoxylate epoxy acrylate represented by the following Formula 1:
(In the formula 1,
R is quaternary carbon having C1 to C4 alkyl groups,
Y is an acryloyl group or a methacryloyl group,
a is an integer of 1 to 15,
and n is an integer of 4 to 6)
R in the above formula (1)
In this way, R is composed only of carbon and does not contain an aromatic ring such as a benzene ring. When a compound containing the aromatic ring is applied to a color filter, the problem of yellowing and luminance lowering due to the benzene ring can be solved.
In addition, the number of functional groups (n) of R, for example, tetrafunctional, hexafunctional and the like, can be controlled, so that the compound of formula (1) has a plurality of Ys each having a double bond. Y is an acryloyl group or a methacryloyl group, and is capable of polymerization in the presence of a double bond in a molecular structure, thereby improving the reactivity.
At the same time, the speed and reactivity during the development process are improved by the ethoxylate group (-O- (CH 2 CH 2 -O) a -) present in the molecular structure and surface defects such as development unevenness or water stain do not occur A high quality color filter can be manufactured while increasing the developing margin. Such physical properties can be obtained by controlling the number (a) of ethoxylate groups, and a is an integer of 1 to 15, preferably an integer of 1 to 10.
In addition, the hydroxyl group (OH) present in the molecular structure has a high possibility of hydrogen bonding and can further improve the adhesion to the substrate.
Specifically, the ethoxylate epoxy acrylate compound of Formula 1 is represented by the following Formula 2 or 3:
(In the above formulas (2) and (3), a is an integer of 1 to 15)
More specifically, the ethoxylate epoxy acrylate compound of Formula 1 is a compound represented by the following Formula 4 or 5:
The ethoxylate epoxy acrylate compound of the formula (1) is used in an amount of 1.5 to 30% by weight, preferably 2 to 15% by weight, in the entire colored photosensitive resin composition in consideration of the fact that the above-mentioned physical properties can be sufficiently secured. If the content is less than the above range, it is difficult to expect a reduction in developing speed and an improvement in adhesion. On the other hand, when the content exceeds the above range, the viscosity of the colored photosensitive resin composition is increased to cause poor coating performance, Use properly within the range.
According to Experimental Example 1 of the present invention, it was confirmed that by using the ethoxylate epoxy acrylate compound, there was no residue, the development speed was fast, the adhesion was excellent, the heat resistance and the solvent resistance were also excellent, It was confirmed that the problem of yellowing (heat resistance test) occurred was solved.
In addition to the above-mentioned ethoxylate epoxy acrylate compounds, the colored photosensitive resin composition according to the present invention includes a colorant, a binder resin, a photopolymerizable compound, a photopolymerization initiator, and a solvent.
coloring agent
The coloring agent is not limited in color tone, and the color tone can be selected according to the use of the color filter to be produced. The colorant may be any one of pigments, dyes, and natural pigments, or a combination of two or more pigments. Among them, pigments may be preferably used because they are excellent in heat resistance and color development.
The pigment may be an inorganic pigment or an organic pigment generally used in the art, and these pigments may be used alone or in combination of two or more.
Examples of the inorganic pigments include metallic compounds such as metal oxides and metal complex salts. Specific examples thereof include oxides of metals such as iron, cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, And the like. Preferably, the pigment is a compound classified as a pigment in the color index (published by The Society of Dyers and Colourists). More specifically, pigments having a color index (C.I.) number as described below are exemplified, but are not limited thereto.
C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 137, 138, 139, 147 , 148, 150, 153, 154, 166, 173, 180, 185, 194 and 214
C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71 and 73
C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 180, 192, 209, 215, 216, 224, 242, 254, 264 and 265
C.I. Pigment Blue 15 (15: 3, 15: 4, 15: 6, etc.) and 60
C.I. Pigment Violet 1, 19, 23, 29, 32, 36 and 38
C.I. Pigment Violet 1, 19, 23, 29, 32, 36 and 38
C.I. Pigment Green 7, 36 and 58
C.I Pigment Brown 23 and 25
C.I Pigment Black 1 and 7, etc.
The organic pigment may be subjected to surface treatment using a pigment derivative or the like into which an acidic group or a basic group is introduced, graft treatment of the surface of the pigment with a polymer compound or the like, atomization treatment using a sulfuric acid atomization method (refinement) A cleaning treatment with a solvent or water, a removal treatment with an ion exchange method of ionic impurities, or the like.
The colorant according to the present invention has a sufficient color density when the color filter is produced and may contain the polymer in a necessary amount in the colored photosensitive resin composition so that the content thereof is adjusted so as to form a pattern having sufficient mechanical strength . Preferably, the colorant is used in an amount of 3 to 60% by weight, more preferably 5 to 55% by weight, in 100% by weight of the total colored photosensitive composition. If the content is less than the above range, the above-mentioned effect can not be ensured. On the other hand, if the content exceeds the above range, the pattern quality obtained after patterning may deteriorate.
In the case of using a pigment as a coloring agent, it is preferable to use a pigment having an average particle diameter uniform in order to improve the quality of the color filter. The method of making the particle diameter of the pigment uniform is not particularly limited in the present invention, and a known method may be used.
For example, a pigment dispersion may be obtained in which the pigment is uniformly dispersed in a solution by dispersing the pigment using a surfactant as a pigment dispersant. Examples of the pigment dispersant include cationic surfactants, anionic surfactants, nonionic surfactants, and amphoteric surfactants, which may be used alone or in combination of two or more.
The pigment dispersant is used in an amount of 1 part by weight or less, preferably 0.05 to 0.5 part by weight based on 1 part by weight of the colorant in the colored photosensitive resin composition. When used in such a content range, a pigment having a uniform average particle diameter can be obtained, and as a result, a high-quality color filter can be produced.
Binder resin
The binder resin may be any binder resin that acts as a dispersion medium for solids such as a colorant, functions as a binder resin, and is soluble in the alkaline developer used in the development of the film.
The binder resin is an alkali-soluble resin and is selected from those having an acid value of 20 to 200 (KOH mg / g). The acid value is a value measured as the amount (mg) of potassium hydroxide necessary to neutralize 1 g of the acrylic polymer, and it is related to the solubility. When the acid value of the resin falls within the above range, the solubility in the developer is improved, and the non-exposed portion easily dissolves and the sensitivity increases. As a result, the pattern of the exposed portion remains at the time of development and the film remaining ratio is improved.
In order to improve the surface hardness of the alkali-soluble resin for use as a color conversion layer, it is possible to consider the molecular weight and the molecular weight distribution (MW / MN). Preferably a weight average molecular weight of 3,000 to 200,000, preferably 5,000 to 100,000, and a molecular weight distribution of 1.5 to 6.0, preferably 1.8 to 4.0. The alkali-soluble resin having the above molecular weight and molecular weight distribution in the above range can improve the hardness and the high residual film ratio as mentioned above, as well as the solubility of the non-exposed portion in the developer and improve the resolution.
The alkali-soluble resin includes one selected from the group consisting of a polymer of a carboxyl group-containing unsaturated monomer, a copolymer of a monomer having a copolymerizable unsaturated bond and a combination thereof.
The carboxyl group-containing unsaturated monomer may be an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, or an unsaturated tricarboxylic acid.
Specific examples of the unsaturated monocarboxylic acid include acrylic acid, methacrylic acid, crotonic acid,? -Chloroacrylic acid, cinnamic acid, and the like. Examples of the unsaturated dicarboxylic acid include maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid. The unsaturated polycarboxylic acid may be an acid anhydride, and specific examples thereof include maleic anhydride, itaconic anhydride, citraconic anhydride and the like. The unsaturated polycarboxylic acid may also be a mono (2-methacryloyloxyalkyl) ester thereof, for example, succinic acid mono (2-acryloyloxyethyl), succinic acid mono (2-methacryloyloxyethyl ), Phthalic acid mono (2-acryloyloxyethyl), phthalic acid mono (2-methacryloyloxyethyl), and the like. The unsaturated polycarboxylic acid may be a mono (meth) acrylate of the dicarboxylic polymer of both ends thereof, and examples thereof include ω-carboxypolycaprolactone monoacrylate and ω-carboxypolycaprolactone monomethacrylate. have. These carboxyl group-containing monomers may be used alone or in combination of two or more.
The monomer copolymerizable with the carboxyl group-containing unsaturated monomer may be an aromatic vinyl compound, an unsaturated carboxylic acid ester compound, an unsaturated carboxylic acid aminoalkyl ester compound, an unsaturated carboxylic acid glycidyl ester compound, a carboxylic acid vinyl ester compound, An aliphatic conjugated diene compound, a macromonomer having a monoacryloyl group or monomethacryloyl group at the end of the molecular chain, a vulcanizable monomer, and a combination thereof in the group consisting of an ether compound, a vinyl cyanide compound, an unsaturated imide compound, an aliphatic conjugated diene compound, One selected paper is available.
More specifically, the copolymerizable monomer is selected from the group consisting of styrene,? -Methylstyrene, o-vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m- Vinylbenzyl methyl ether, p-vinyl benzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl Aromatic vinyl compounds such as ether and indene; Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl acrylate, n-propyl methacrylate, i-propyl acrylate, i-propyl methacrylate, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene Acrylate, dicyclopentadienyl methacrylate, adamantyl (meth) acrylate, (Meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate and the like Unsaturated carboxylic acid esters; Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl ester compounds; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ether compounds such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide; Acrylamide, vinyltoluene, m-vinyltoluene, p-vinyltoluene, p-chlorostyrene, o-methoxystyrene, m-methoxystyrene, p-methoxystyrene, o-vinylbenzyl methyl ether, Aromatic vinyl compounds such as methyl ether, p-vinylbenzyl methyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-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, butyl methacrylate, i-butyl acrylate, i-butyl methacrylate, sec-butyl acrylate, sec-butyl methacrylate, t-butyl acrylate, t-butyl methacrylate, Ethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, 3-hydroxypropyl acrylate, 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 3-hydroxybutyl acrylate, 3-hydroxybutyl methacrylate, 4-hydroxybutyl acrylate, 4-hydroxybutyl methacrylate, Acrylate, benzyl acrylate, benzyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl Methacrylate, 2-phenoxyethyl acrylate, 2-phenoxyethyl methacrylate, methoxy diethylene glycol acrylate, methoxy diethylene glycol methacrylate, methoxy triethylene glycol acrylate, methoxy triethylene glycol methacrylate Acrylate, methoxypropylene glycol methacrylate, methoxypropylene glycol acrylate, methoxydipropylene glycol methacrylate, isobornyl acrylate, isobornyl methacrylate, dicyclopentadiene Acrylate, dicyclopentadienyl methacrylate, adamantyl (meth) acrylate, (Meth) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-hydroxy-3-phenoxypropyl methacrylate, glycerol monoacrylate, glycerol monomethacrylate and the like Unsaturated carboxylic acid esters; Aminoethyl methacrylate, 2-aminoethyl methacrylate, 2-dimethylaminoethyl acrylate, 2-dimethylaminoethyl methacrylate, 2-aminopropyl acrylate, 2-aminopropyl methacrylate, 2- Unsaturated carboxylates such as methyl acrylate, ethyl acrylate, propyl methacrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, isopropyl acrylate, Acid amino alkyl ester compounds; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl acrylate and glycidyl methacrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate; Unsaturated ether compounds such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether; Vinyl cyanide compounds such as acrylonitrile, methacrylonitrile,? -Chloroacrylonitrile, and vinylidene cyanide; Unsaturated amides such as acrylamide, methacrylamide,? -Chloroacrylamide, N-2-hydroxyethyl acrylamide and N-2-hydroxyethyl methacrylamide; Maleimide, benzyl maleimide, N-phenyl maleimide. Unsaturated imide compounds such as N-cyclohexylmaleimide; Aliphatic conjugated dienes such as 1,3-butadiene, isoprene and chloroprene; And a monoacryloyl group or monomethacryloyl group at the end of the polymer molecular chain of polystyrene, polymethyl acrylate, polymethyl methacrylate, poly-n-butyl acrylate, poly-n-butyl methacrylate, Macromonomers; A bulky monomer such as a monomer having a norbornyl skeleton, a monomer having an adamantane skeleton, or a monomer having a rosin skeleton which can lower the relative dielectric constant can be used.
If the binder resin is a copolymer of a carboxyl group-containing monomer and another monomer capable of copolymerizing with the monomer, the content ratio of the constituent unit derived from the carboxyl group-containing monomer is preferably within a range of from Is 10 to 50% by weight, preferably 15 to 40% by weight, more preferably 25 to 40% by weight. When the content ratio of the constituent unit derived from the carboxyl group-containing monomer is 10 to 50% by weight based on the above-mentioned criteria, the solubility in a developer is good and a pattern is accurately formed at the time of development.
More preferably, the binder resin is an acrylate resin, and the binder resin is a (meth) acrylic acid / methyl (meth) acrylate copolymer, a (meth) acrylic acid / benzyl (meth) acrylate copolymer, (Meth) acrylic acid / methyl (meth) acrylate / polystyrene macromonomer copolymer, (meth) acrylic acid / methyl (meth) acrylate / polymethyl (Meth) acrylate macromonomer copolymer, a (meth) acrylic acid / benzyl (meth) acrylate / polystyrene macromonomer copolymer, a (meth) acrylic acid / benzyl (Meth) acrylic acid / 2-hydroxyethyl (meth) acrylate / benzyl (meth) acrylate / polystyrene macromonomer copolymer, (Meth) acrylic acid / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / succinic acid mono (meth) acrylate / polymethyl (2-acryloyloxy) / styrene / benzyl (meth) acrylate / N-phenylmaleimide copolymer, (meth) acrylic acid / (Meth) acrylic acid / benzyl (meth) acrylate / N-phenylmaleimide / styrene / glycerol mono (meth) acrylate copolymer. Of these, (meth) acrylic acid / benzyl (meth) acrylate copolymer, (meth) acrylic acid / benzyl (meth) acrylate / styrene copolymer, , (Meth) acrylic acid / methyl (meth) acrylate / styrene copolymer, and combinations thereof.
Such a binder resin may be used in an amount of 2 to 80% by weight, preferably 3 to 40% by weight, based on 100% by weight of the whole composition. Such a content is a range selected considering various factors such as solubility in a developing solution, pattern formation, etc. When used within the above range, solubility in a developing solution is sufficient and pattern formation is easy, So that the dropout of the non-pixel portion is improved.
Photopolymerization Monomer
The photopolymerizable monomer is an acrylate monomer capable of polymerizing under the action of light and a photopolymerization initiator. These monomers may be monofunctional monomers, double-walled monomers, and other multifunctional monomers depending on the structure thereof.
Specific examples of monofunctional monomers include nonylphenylcarbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexylcarbitol acrylate, 2-hydroxyethyl acrylate, N- Money and so on. Specific examples of the bifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (Acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, butylene glycol dimethacrylate, hexanediol di (meth) acrylate, diethylene glycol di ) Acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate, ethoxylate Neopentyl glycol diacrylate, propyloxylate neopentyl glycol diacrylate, and the like.
Specific examples of the trifunctional monomer include 1,6-hexanediol di (meth) acrylate, ethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, triethylene glycol di (meth) , Bis (acryloyloxyethyl) ether of bisphenol A, 3-methylpentanediol di (meth) acrylate, and the like.
Specific examples of the tetrafunctional monomer include pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, ditrimethylol propane tetraacrylate, ditrimethylol propane tetramethacrylate, dipentaerythritol tetraacrylate, Tetramethylolmethane tetraacrylate, ethoxylated pentaerythritol tetraacrylate, glycerin tetraacrylate, glycerin tetramethacrylate, and the like.
Specific examples of the pentafunctional monomer include dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate, dipentaerythritol monohydroxypentaacrylate, dipentaerythritol monohydroxypentamethacrylate, and the like. .
Specific examples of the hexafunctional monomer include dipentaerythritol hexaacrylate, dipentaerythritol hexa methacrylate, and the like.
Of these, the photopolymerizable monomer may preferably be a multifunctional monomer having a bifunctionality or higher, and in particular, a multifunctional monomer having a functionality of 5 or more may be preferably used.
Such photopolymerizable monomers may be used in an amount of 5 to 50% by weight, preferably 7 to 45% by weight, based on 100% by weight of the total colored photosensitive composition. Such a content range is a range determined in consideration of various factors such as strength and smoothness of a finally obtained color filter (i.e., R, G, B pattern). If the content is less than the above range, If it is insufficient, on the other hand, if it exceeds the above range, patterning is not easy due to high strength. Therefore, it is suitably used within the above range.
Light curing Initiator
The photopolymerization initiator may be any known initiator capable of photopolymerization as a compound for initiating polymerization of the photopolymerizable compound.
These photopolymerization initiators are classified into an active radical generator, a sensitizer, and an acid generator according to the mechanism thereof. In the present invention, an acetophenone-based compound, which is an active radical generator, is used.
Specific examples of the acetophenone-based compound include diethoxyacetophenone, 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan- 1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, benzyldimethylketal, (1-methylvinyl) phenyl] propane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy- And oligomers of 2-methyl-2-morpholino-1- (4-methylthiophenyl) propane-1-one.
These acetophenone-based compounds may be used alone or in combination of two or more. Further, other types of photopolymerization initiators may be used in combination.
Examples of other types of photopolymerization initiators include an active radical generator, a sensitizer, and an acid generator that generate an active radical upon irradiation with light. Examples of the active radical generator include benzoin-based compounds, benzophenone-based compounds, thioxanthone-based compounds, and triazine-based compounds.
Specific examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether.
Specific examples of the benzophenone compound include methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3 ', 4,4'-tetra (t- Carbonyl) benzophenone, 2,4,6-trimethylbenzophenone, and the like.
Specific examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1- Propanedioxanthone, and the like.
Specific examples of triazine compounds include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6 - (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- (4- methoxystyryl) Bis (trichloromethyl) -6- [2- (5-methylfuran-2-yl) ethenyl] -1,3,5-triazine, 2,4- (Trichloromethyl) -6- [2- (4-diethylamino-2- (trifluoromethyl) Methylphenyl) ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (3,4 dimethoxyphenyl) ethenyl] -1,3,5-tri Azine, and the like.
The photopolymerization initiator such as the acetophenone-based photopolymerization initiator is an active radical generator, and a photopolymerization initiator of a sensitizer and an acid generator can also be used.
The sensitizer may be 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2-bis (o-chlorophenyl) -4,4 ', 5,5'-tetraphenyl-1,2'- , 10-butyl-2-chloroacridone, 2-ethyl anthraquinone, benzyl, 9,10-phenanthrenequinone, camphorquinone, methyl phenylglyoxylate, and titanocene compounds.
Examples of the acid generator include 4-hydroxyphenyldimethylsulfonium p-toluenesulfonate, 4-hydroxyphenyldimethylsulfonium hexafluoroantimonate, 4-acetoxyphenyldimethylsulfonium p-toluenesulfonate, 4 -Acetoxyphenylmethylbenzylsulfonium hexafluoroantimonate, triphenylsulfonium p-toluene sulfonate, triphenylsulfonium hexafluoroantimonate, diphenyl iodonium p-toluene sulfonate, diphenyl iodo Heptafluoroantimonate, and heptafluoroantimonate; and nitrobenzyltosylates, benzoin tosylates, and the like.
Among these compounds, there are compounds which simultaneously generate an active radical and an acid. For example, a triazine-based compound is also used as an acid generator.
The photopolymerization initiator according to the present invention can sensitize the colored photosensitive resin composition to shorten the exposure time, thereby improving the productivity and controlling the content so as to maintain high resolution. Preferably, the photopolymerization initiator is used in an amount of 0.1 to 40% by weight, preferably 1 to 30% by weight in the total composition. If the content is less than the above range, the polymerization rate is too slow. On the other hand, if the content exceeds the above range, the physical properties of the coating film may be lowered due to excessive reaction due to the crosslinking reaction.
In addition, the photopolymerization initiator according to the present invention can be used in combination with a photopolymerization initiator auxiliary adjuvant. The photopolymerization initiator may be used to promote the polymerization of the photopolymerizable monomer initiated by the photopolymerization initiator.
Examples of the photopolymerization initiator include amine compounds, alkoxy anthracene compounds, and the like.
Specific examples of the amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, , 4-dimethylaminobenzoic acid-2-ethylhexyl, N, N-dimethylparatoluidine, 4,4'-bis (dimethylamino) benzophenone (collectively, Michler's ketone), 4,4'- Amino) benzophenone, and 4,4'-bis (ethylmethylamino) benzophenone. Of these, 4,4'-bis (diethylamino) benzophenone is preferable.
Specific examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, .
These photopolymerization initiators may be used alone or in combination of two or more. The photopolymerization initiator may be a commercially available product, such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.).
Specific examples of preferred combinations of the photopolymerization initiator and the photopolymerization initiator include diethoxyacetophenone and 4,4'-bis (diethylamino) benzophenone; 2-methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and 4,4'-bis (diethylamino) benzophenone; 2-hydroxy-2-methyl-1-phenylpropan-1-one and 4,4'-bis (diethylamino) benzophenone; 2-hydroxy-2-methyl-1- [4- (2-hydroxyethoxy) phenyl] propan-1-one and 4,4'-bis (diethylamino) benzophenone; 1-hydroxycyclohexyl phenyl ketone and 4,4'-bis (diethylamino) benzophenone; Oligomers of 2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propan-1-one and 4,4'-bis (diethylamino) benzophenone; A combination of 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butan-1-one and 4,4'-bis (diethylamino) benzophenone, -Methyl-2-morpholino-1- (4-methylthiophenyl) propan-1-one and 4,4'-bis (diethylamino) benzophenone.
When the photopolymerization initiator and the photopolymerization initiator are used together, the content of the photopolymerization initiator is preferably 0.01 to 5 moles relative to 1 mole of the photopolymerization initiator. If the photopolymerization initiator is contained within the above range, the sensitivity of the colored photosensitive resin composition becomes higher and the productivity of the color filter formed using the composition is improved.
solvent
Any solvent may be used as long as it can dissolve or disperse the above-mentioned composition, and the solvent is not particularly limited in the present invention. Preferably, an organic solvent having a boiling point of 100 to 200 DEG C in terms of coatability and dryness can be used.
Representative examples of usable solvents include ethers, aromatic hydrocarbons, ketones, alcohols, esters, amides and the like.
More specifically, the solvent is selected from the group consisting of ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl Diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether and the like, ethylene glycol alkyl ether acetates such as methyl cellosolve acetate and ethyl cellosolve acetate, propylene glycol monomethyl ether Alkylene glycol alkyl ether acetates such as acetone, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, methoxybutyl acetate and methoxypentyl acetate, aromatic hydrocarbons such as benzene, toluene, xylene and mesitylene, Ethyl ketone , Ketones such as acetone, methyl amyl ketone, methyl isobutyl ketone and cyclohexanone, alcohols such as ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol and glycerin, ethyl 3-ethoxypropionate, 3- Esters such as methyl methoxypropionate, and cyclic esters such as? -Butyrolactone.
Most preferably, the solvent is propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, cyclohexanone, ethyl lactate, butyl lactate, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, Can be used.
Such a solvent may be used as the remainder to satisfy 100 wt% of the entire colored photosensitive resin composition. Such a content is selected in consideration of dispersion stability of the composition and easiness of process in the production process (for example, applicability). In other words, the colored photosensitive resin composition according to the present invention can produce a color filter by wet coating, wherein the wet coating method can be used as a roll coater, a spin coater, a slit and spin coater, a slit coater ), An inkjet or the like can be used.
Other additives
In addition, the colored photosensitive resin composition according to the present invention may further contain known additives for various purposes. As such additives, additives such as other polymer compounds, curing agents, surfactants, adhesion promoters, antioxidants, ultraviolet absorbers, and anti-aggregation agents may be used in combination. These additives may be used alone or in combination of two or more, and it is preferable to use 1 wt% or less in the whole composition in consideration of light efficiency and the like.
Specific examples of the other polymer compound include curable resins such as epoxy resin and maleimide resin, thermoplastic resins such as polyvinyl alcohol, polyacrylic acid, polyethylene glycol monoalkyl ether, polyfluoroalkyl acrylate, polyester, and polyurethane .
The curing agent is used for enhancing deep curing and mechanical strength. Specific examples of the curing agent include an epoxy compound, a polyfunctional isocyanate compound, a melamine compound, and an oxetane compound.
Specific examples of the epoxy compound in the curing agent include bisphenol A epoxy resin, hydrogenated bisphenol A epoxy resin, bisphenol F epoxy resin, hydrogenated bisphenol F epoxy resin, novolak epoxy resin, other aromatic epoxy resin, alicyclic epoxy resin Alicyclic or aromatic epoxy compounds, butadiene (co) polymeric epoxides and isoprene (co) polymers other than the brominated derivatives, epoxy resins and brominated derivatives of these epoxy resins, glycidyl ester resins, glycidyl amine resins, (Co) polymer epoxides, glycidyl (meth) acrylate (co) polymers, and triglycidyl isocyanurate.
Specific examples of the oxetane compound in the curing agent include carbonate bisoxetane, xylene bisoxetane, adipate bisoxetane, terephthalate bisoxetane, cyclohexanedicarboxylic acid bisoxetane, and the like .
Such a curing agent may be used together with a curing agent in combination with a curing auxiliary compound capable of ring-opening polymerization of the epoxy group of the epoxy compound and the oxetane skeleton of the oxetane compound.
The curing assistant compounds include, for example, polyvalent carboxylic acids, polyvalent carboxylic anhydrides, and acid generators. The polyvalent carboxylic acid anhydrides may be those commercially available as an epoxy resin curing agent. Specific examples of the above-mentioned epoxy resin curing agent include epoxy resin curing agents such as epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, epoxy resins, Manufactured by Japan Ehwa Co., Ltd.). The curing agents exemplified above may be used alone or in combination of two or more.
Further, the surfactant can be used for further improving the film-forming property of the photosensitive resin composition, and a fluorine-based surfactant or a silicon-based surfactant can be preferably used.
Examples of silicone surfactants include DC3PA, DC7PA, SH11PA, SH21PA, and SH8400 from Dow Corning Toray Silicone Co., Ltd. and TSF-4440, TSF-4300, TSF-4445, TSF- TSF-4452 and so on. Examples of the fluorine-based surfactant include Megapis F-470, F-471, F-475, F-482 and F-489 commercially available from Dainippon Ink and Chemicals, Incorporated. The above-exemplified surfactants may be used alone or in combination of two or more.
Specific examples of the adhesion promoter include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N Aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (2-aminoethyl) (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3- Methoxysilane, 3-isocyanatepropyltrimethoxysilane, 3-isocyanatepropyltriethoxysilane, and the like. The adhesion promoters exemplified above may be used alone or in combination of two or more. These adhesion promoters may be contained in the colored photosensitive resin composition in an amount of 0.01 to 10% by weight, preferably 0.05 to 2% by weight.
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-chlorobenzotriazole and alkoxybenzophenone.
Specific examples of the anti-aggregation agent include sodium polyacrylate and the like.
The production of the above-described colored photosensitive composition is not particularly limited in the present invention, and follows a known production method of the photosensitive composition.
For example, a colorant may be added to a solvent, followed by addition of an ethoxylate epoxy acrylate compound of Formula 1, the remainder of the composition, and other additives, followed by stirring. The colorant may be dissolved or dispersed in a solvent or a binder resin, and may be added in advance to a solvent together with a colorant when the additive is in a solution form.
The thus-prepared colored photosensitive resin composition is preferably used in a display device, preferably a color filter of a liquid crystal display device.
At this time, the color filter is made of a colored photosensitive resin composition containing an ethoxylate epoxy acrylate of the formula (1), and has an excellent adhesion with a base material and an excellent reliability, so that a developing speed is fast and there is no residue.
The production of the color filter using the colored photosensitive resin composition is not particularly limited in the present invention and can be produced by a known method. For example, the patterning process of the color filter according to the photolithography method may include,
a) applying a colored photosensitive resin composition;
b) prebaking step of drying the solvent;
c) applying a photomask onto the obtained film to irradiate an actinic ray to cure the exposed portion;
d) performing a developing step of dissolving the unexposed portion using an aqueous alkali solution; And
e) Perform drying and post-baking.
A glass substrate or a polymer plate is used as the substrate. As the glass substrate, in particular, soda lime glass, barium-strontium-containing glass, lead glass, aluminosilicate glass, borosilicate glass, barium borosilicate glass or quartz can be preferably used. Examples of the polymer plate include polycarbonate, acrylic, polyethylene terephthalate, polyether sulfide, and polysulfone.
At this time, a wet coating method using a coating apparatus such as a roll coater, a spin coater, a slit and spin coater, a slit coater (which may be referred to as a die coater), an ink jet or the like is possible so as to obtain a desired thickness.
Prebaking is performed by heating with an oven, a hot plate or the like. At this time, the heating temperature and the heating time in the pre-baking are appropriately selected depending on the solvent to be used, for example, at a temperature of 80 to 150 ° C for 1 to 30 minutes.
The exposure performed after the pre-baking is performed by an exposure machine, and exposed through a photomask to expose only the portion corresponding to the pattern. The light to be irradiated may be, for example, visible light, ultraviolet light, X-ray, electron beam, or the like.
Alkali development after exposure is carried out for the purpose of removing the photosensitive resin composition in the portion where the non-exposed portion is not removed, and a desired pattern is formed by this development. As a developer suitable for the alkali development, for example, an aqueous solution of a carbonate of an alkali metal or an alkaline earth metal may be used. Particularly, a weakly alkaline aqueous solution containing 1 to 3% by weight of a carbonate such as sodium carbonate, potassium carbonate or lithium carbonate is used at a temperature of 10 to 50 캜, preferably 20 to 40 캜, using a developing machine or an ultrasonic cleaner .
The post-baking is performed in order to enhance the adhesion between the patterned film and the substrate, and is performed by heat treatment at 80 to 220 DEG C for 10 to 120 minutes. Post-baking is performed by using an oven, a hot plate, or the like as in pre-baking.
Such a color filter can satisfy the color characteristics, chemical resistance, heat resistance, and residue characteristics required for all of them, and there is no problem of occurrence of luminance and yellowing occurring conventionally, and thus the reliability of the liquid crystal display device can be improved.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims. In the following, "%" and "part" representing the content are on a mass basis unless otherwise specified.
Manufacturing example One: Four-sensory Ethoxylate Epoxy Acrylate Preparation of compound (a = 1)
The compound of formula (2) was prepared according to the reaction shown in Scheme 1 below.
[Reaction Scheme 1]
First, 250 g of pentaerythritol (PET) (Taian Dadao Chemicals) and 120 g (10 mol) of chloroethanol (Aldrich) were added to a heating device connected to a mechanical stirrer, a temperature sensor and a temperature sensor, 0.25 g of p-toluenesulfonic acid (Aldrich) and toluene as a solvent were added thereto, and the mixture was allowed to react at 75 ° C for 3 hours (see Scheme 1- (1)).
150 g of NaOH and 290 g of epichlorohydrin (ECH) (Aldrich) were mixed and the reaction temperature was raised to 85 ° C to reflux toluene and epichlorohydrin. After completion of the reaction, unreacted epichlorohydrin (ECH) was removed by a rotary evaporator and 1.4 L of a 10 wt% NaOH aqueous solution was slowly added dropwise at 40 ° C to carry out a terminal epoxidation reaction. After completion of the dropwise addition, the mixture was reacted at 80 ° C. for 3 hours, cooled to room temperature, dissolved in toluene (1 L), and washed three times with distilled water. Subsequently, distillation under reduced pressure at 120 ° C was carried out to remove toluene completely to obtain a product (85%) in the form of a clear oil (see Scheme 1- (2)).
The reaction was carried out at 90 占 폚 by mixing 191 g of the obtained product, 72 g of acrylic acid (AA) (Aldrich), 1.3 g of triethylamine (TEA) (Aldrich) and 0.1 g of 4-methoxyphenol (MEHQ, Aldrich). At this time, the wet correct titration acid value was measured, and the reaction was confirmed by confirming the area of 915 cm -1 which is an epoxy characteristic absorption peak in the spectrum of FT-IR. The reaction was terminated when the acid value became 3 mg KOH / g or less - (3)).
The reaction was carried out to obtain the title compound. The molecular weight was measured and the structure was confirmed by NMR measurement (yield: 95%).
Manufacturing example 2: 6 sensation Ethoxylate Epoxy Acrylate Preparation of compound (a = 1)
The compound of Formula 3 was prepared based on the reaction shown in Reaction Scheme 2 below.
[Reaction Scheme 2]
First, 250 g of dipentaerythritol (DPET) (Taian Dadao Chemicals), 120 g of chloroethanol (Chloroethanol, Aldrich), 10 g, and p-toluene were placed in a three-necked reactor equipped with a mechanical stirrer, 0.25 g of sulfonic acid (Aldrich) and toluene as a solvent were added thereto, followed by reaction at 75 ° C for 3 hours (see Scheme 2 (1)).
Then, 150 g of NaOH and 290 g of epichlorohydrin (ECH) (Aldrich) were mixed and the reaction temperature was raised to 85 ° C to reflux toluene and epichlorohydrin. After completion of the reaction, unreacted epichlorohydrin was removed by a rotary evaporator and 1.4 L of a 10 wt% NaOH aqueous solution was slowly added dropwise at 40 ° C to carry out a terminal epoxidation reaction. After completion of the dropwise addition, the mixture was reacted at 80 DEG C for 3 hours, cooled to room temperature, dissolved in toluene (1 L) and washed three times with distilled water. Subsequently, distillation under reduced pressure was performed at 120 ° C to remove toluene completely to obtain a product (85%) in the form of a clear oil (see Scheme 2- (2)).
The reaction was carried out at 90 占 폚 by mixing 191 g of the obtained product, 72 g of acrylic acid (AA) (Aldrich), 1.3 g of triethylamine (TEA) (Aldrich) and 0.1 g of 4-methoxyphenol (MEHQ, Aldrich). At this time, the wet correct titration acid value was measured, and the reaction was confirmed by confirming the area of 915 cm -1 which is an epoxy characteristic absorption peak in the spectrum of FT-IR. The reaction was terminated when the acid value became 3 mg KOH / g or less - (3)).
The reaction was carried out to obtain the title compound. The molecular weight was measured and the structure was confirmed by NMR measurement (yield: 92%).
Example 1-4 and Comparative Example 1-4
After adding a solvent to the mixer, a pigment, an epoxylated polybutadiene, an alkali-soluble resin, a photopolymerizable compound, a photopolymerization initiator, and other additives were added thereto and uniformly mixed by stirring to prepare a colored photosensitive resin composition. Wherein the compositions are according to the composition of Table 1 below.
The colored photosensitive resin composition thus prepared was coated on a glass substrate (# 1737, Corning) by spin coating, and then placed on a heating plate and maintained at a temperature of 100 ° C for 3 minutes to form a thin film.
Subsequently, a test photomask having a pattern for changing the transmittance in the range of 1 to 100% in a stepwise manner was placed on the thin film, and the gap between the test photomask and the test photomask was set to 1000 탆, and an ultrahigh pressure mercury lamp (USH-250D, (365 nm) at 40 mJ / cm 2 under the atmosphere.
Next, the thin film irradiated with the ultraviolet rays was developed in a KOH aqueous solution of pH 12.5 for 80 seconds using a spray developing machine.
Then, the glass substrate coated with the thin film was rinsed with distilled water, and then nitrogen gas was blown dry and heated in a heating oven at 220 ° C for 20 minutes to prepare a color filter. The fabricated color filter had a pattern shape (thin film) thickness of 1.9 to 2.1 탆
Epoxy acrylate compound
coloring agent
additive
2) hexafunctional epoxy acrylate: Compound of formula 5
3) BPA-102, Han Cong Hwaseong, KR2010-78845 presented
4) Binder resin: copolymer of methacrylic acid and benzyl methacrylate (ratio of methacrylic acid unit to benzyl methacrylate unit is 31:69 in terms of mol, acid value is 100 mgKOH / g, weight average molecular weight in terms of polystyrene is 20,000 )
5) Photopolymerizable monomer: dipentaerythritol hexaacrylate (KAYARAD DPHA; manufactured by Nippon Kayaku Co., Ltd.)
6) Photopolymerization initiator: 2-Benzyl-2-dimethylamino-1 (4-morpholinophenyl) butan-1-one (Irgacure 369, manufactured by Ciba Specialty Chemical)
7) Solvent: Propylene glycol monomethyl ether acetate
8) Surfactant: SH-8400 Toray Silicon Manufacturing
9) Epoxy resin: SUMI-EPOXY ESCN-195XL; Manufactured by Sumitomo Chemical Co., Ltd.
10) Adhesion promoter: 3-methacryloxypropyltrimethoxysilane
Experimental Example 1: Measurement and comparison of physical properties
The physical properties of the color filters prepared in the Examples and Comparative Examples were measured, and the results are shown in Table 2 below.
(1) Evaluation of residue and developing rate
After development, the presence or absence and remaining amount of remnants remained without being washed away were observed. It was evaluated as good when there was no residue and when it was remained, it was evaluated as defective. During the manufacturing process of the color filter, the developing time was measured by measuring the time at which peeling of the non-exposed thin film portion occurred.
(2) Adhesion
The prepared substrate is cut into 100 matrix structures in a region of 10 × 10 mm, the tape is adhered thereon, and the number of dislodged matrices is shown while vertically and strongly releasing: (number of dropped / 100)
(3) Heat resistance
After the pattern was finally formed, the color change (heat resistance) around 230 ° C / 2 hr was compared and evaluated. The equation to be used at this time is calculated by Equation (1) representing the color change in the three-dimensional colorimetry defined by L *, a *, b *, and as the color change value is smaller, a highly reliable color filter can be manufactured.
[Equation 1]
△ Eab * = [(△ L *) 2 + (△ a *) 2 + (△ b *) 2] (1/2)
(4) NMP content
The prepared substrate was cut into 3 × 3 cm, and then immersed in 14.6 ml of NMP solution at 80 ° C. for 40 minutes. The solution is then measured for UV-Vis spectrophotometry.
As shown in Table 2, the coating films of Examples 1 to 4 containing the ethoxylate epoxy acrylate compound according to the present invention had no residue, had a rapid developing speed, and had adhesion properties comparable to those of Comparative Examples 1 to 4 Excellent in heat resistance and solvent resistance.
In particular, it was confirmed that the residue and developability were improved as compared with Comparative Example 4 using a bisphenol type ethoxylate epoxy acrylate compound in the past, and the use of an ethoxylate epoxy acrylate compound showed yellowing Test basis) problem could be solved.
From these results, it can be seen that when the ethoxylate epoxy acrylate compound according to the present invention is used, a color filter of excellent quality can be produced.
The liquid crystal display device of the colored photosensitive resin composition according to the present invention can be used as a color filter.
Claims (15)
[Chemical Formula 1]
(In the formula 1,
R is quaternary carbon having C1 to C4 alkyl groups,
Y is an acryloyl group or a methacryloyl group,
a is an integer of 1 to 15,
and n is an integer of 4 to 6)
(2)
(3)
(In the above formulas 2 and 3,
R 1 is an alkyl group having from 1 to 4 carbon atoms,
and a is an integer of 1 to 15)
[Chemical Formula 4]
[Chemical Formula 5]
3 to 60% by weight of a colorant,
2 to 80% by weight of a binder resin,
5 to 50% by weight of a photopolymerizable monomer,
0.1 to 40% by weight of a photopolymerization initiator, and
And the remaining part contains a solvent.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190052273A (en) * | 2017-11-08 | 2019-05-16 | 주식회사 이엔에프테크놀로지 | Photosensitive resin composition |
| US11202796B2 (en) * | 2017-06-28 | 2021-12-21 | Jenkem Technology Co., Ltd. (Tianjin) | Branched polyethylene glycol epoxy derivative crosslinked sodium hyaluronate gel, preparation and application thereof |
-
2014
- 2014-09-23 KR KR1020140126641A patent/KR20160035272A/en not_active Application Discontinuation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11202796B2 (en) * | 2017-06-28 | 2021-12-21 | Jenkem Technology Co., Ltd. (Tianjin) | Branched polyethylene glycol epoxy derivative crosslinked sodium hyaluronate gel, preparation and application thereof |
| KR20190052273A (en) * | 2017-11-08 | 2019-05-16 | 주식회사 이엔에프테크놀로지 | Photosensitive resin composition |
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