KR20160118865A - Photosensitive resin composition and color filter using the same - Google Patents
Photosensitive resin composition and color filter using the same Download PDFInfo
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- KR20160118865A KR20160118865A KR1020150047732A KR20150047732A KR20160118865A KR 20160118865 A KR20160118865 A KR 20160118865A KR 1020150047732 A KR1020150047732 A KR 1020150047732A KR 20150047732 A KR20150047732 A KR 20150047732A KR 20160118865 A KR20160118865 A KR 20160118865A
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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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—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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Abstract
Description
The present invention relates to a photosensitive resin composition and a color filter manufactured using the same.
The color filter is used for a liquid crystal display (LCD), an optical filter of a camera, and the like, and is manufactured by coating a fine area colored with three or more colors onto a transparent substrate or a solid-state imaging element. Such a colored thin film is usually formed by a dyeing method, a printing method, an electrodeposition method, a pigment dispersion method or the like. The manufacturing process of the color filter includes many chemical treatment steps.
In order to maintain the pattern formed under these conditions, there is a demand for a photosensitive resin for a color filter which can improve the yield of a color filter with excellent chemical resistance while ensuring a developing margin.
Particularly, a process of forming a transparent electrode on a color filter is required while a color filter-on-array (CoA) method of forming a color filler on a TFT array panel in a liquid crystal display device is employed. The transparent electrode may be formed by sequentially forming a transparent conductive layer and a photosensitive resin film on a color filter, patterning the photosensitive resin film by exposure and development, and etching the transparent conductive layer using the patterned photosensitive resin film. At this time, the chemical filter is important because the color filter can be exposed to various chemical liquids such as a peeling liquid for developing the photosensitive resin film.
However, the organic film composition as described above has a further high sensitivity and has a limitation in improving the characteristics of the Gotzma film. In addition, heat resistance is very important because a color filter requires many heat treatment processes during the process.
Therefore, efforts to develop a photosensitive resin composition having excellent heat resistance and developing property have been continued.
One embodiment is to provide a photosensitive resin composition having excellent heat resistance and developing property.
Another embodiment is to provide a color filter manufactured using the photosensitive resin composition.
One embodiment includes (A) a binder resin comprising a repeating unit represented by the following formula (1); (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant; And (E) a solvent.
[Chemical Formula 1]
In Formula 1,
R 1 to R 3 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
L 1 to L 5 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or a substituted or unsubstituted C6 to C20 arylene group.
The L 1 to L 5 may be a single bond or a substituted or unsubstituted C1 to C20 alkylene group.
The repeating unit represented by Formula 1 may be contained in an amount of more than 0 wt% to 70 wt% or less with respect to the total amount of the binder resin.
The repeating unit represented by the formula (1) may be contained in an amount of 10% by weight to 60% by weight based on the total amount of the binder resin.
The binder resin may include an acrylic binder resin.
The binder resin may further include at least one of repeating units represented by the following formulas (2) to (5).
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
In the above Chemical Formulas 2 to 5,
R 4 , R 5 , R 7 and R 11 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R 6 , R 8 , R 9 , R 10 and R 12 each independently represents a hydrogen atom, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group or a substituted or unsubstituted C 6 to C 20 Lt; / RTI >
L 6 and L 7 are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.
The binder resin may have a weight average molecular weight of 11,500 g / mol to 50,000 g / mol.
The binder resin may have an acid value of 110 mgKOH / g to 140 mgKOH / g.
The colorant may include a pigment, a dye, or a combination thereof.
The pigments and dyes may be included in a weight ratio of 1: 9 to 9: 1.
The pigments may include a green pigment, a yellow pigment, or a combination thereof, and the dye may include a green dye, a yellow dye, or a combination thereof.
Wherein the photosensitive resin composition comprises 1 wt% to 10 wt% of the binder resin relative to the total amount of the photosensitive resin composition; 0.1% to 5% by weight of the photopolymerizable monomer; 0.1% by weight to 5% by weight of the photopolymerization initiator; 30% to 80% by weight of the colorant; And the solvent balance.
The photosensitive resin composition may further include additives such as malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine surfactant, a radical polymerization initiator, or a combination thereof.
Another embodiment provides a color filter comprising the photosensitive resin composition.
Other aspects of the present invention are included in the following detailed description.
The photosensitive resin composition according to an embodiment includes a binder resin containing a repeating unit having a specific structure, and is excellent in heat resistance and developability, and thus can provide a color filter or the like having excellent brightness and processability.
1 is an optical microscope photograph of a pattern in a color filter prepared using the photosensitive resin composition according to Example 1. Fig.
Fig. 2 is an optical microscope photograph of a pattern in a color filter prepared using the photosensitive resin composition according to Example 2. Fig.
3 is an optical microscope photograph of a pattern in a color filter manufactured using the photosensitive resin composition according to Example 3. Fig.
4 is an optical microscope photograph of a pattern in a color filter manufactured using the photosensitive resin composition according to Example 4. Fig.
5 is an optical microscope photograph of a pattern in a color filter prepared using the photosensitive resin composition according to Example 5. Fig.
6 is an optical microscope photograph of a pattern in a color filter manufactured using the photosensitive resin composition according to Comparative Example 1. Fig.
Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.
Unless otherwise specified herein, "alkyl group" means a C1 to C20 alkyl group, "alkenyl group" means a C2 to C20 alkenyl group, "cycloalkenyl group" means a C3 to C20 cycloalkenyl group Quot; means a C3 to C20 heterocycloalkenyl group, "an aryl group" means a C6 to C20 aryl group, an "arylalkyl group" means a C6 to C20 arylalkyl group, Refers to a C 1 to C 20 alkylene group, "arylene group" refers to a C6 to C20 arylene group, "alkylarylene group" refers to a C6 to C20 alkylarylene group, "heteroarylene group" refers to a C3 to C20 hetero Quot; means an arylene group, and the "alkoxysilylene group" means a C1 to C20 alkoxysilylene group.
Unless otherwise specified herein, "substituted" means that at least one hydrogen atom is replaced by a halogen atom (F, Cl, Br, I), a hydroxy group, a C1 to C20 alkoxy group, a nitro group, a cyano group, An ester group, an ether group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1-C10 alkyl group, a C1- A C2 to C20 alkenyl group, a C2 to C20 alkynyl group, a C6 to C20 aryl group, a C3 to C20 cycloalkyl group, a C3 to C20 cycloalkenyl group, a C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkyl group, To C20 heterocycloalkenyl groups, C2 to C20 heterocycloalkynyl groups, C3 to C20 heteroaryl groups, or combinations thereof.
Also, unless otherwise specified herein, "hetero" means that at least one heteroatom of N, O, S, and P is included in the formula.
&Quot; (Meth) acrylic acid "refers to both" acrylic acid "and" methacrylic acid " "It means both are possible.
"Combination" as used herein, unless otherwise specified, means mixing or copolymerization.
Also, unless otherwise specified herein, "*" means the same or different atom or moiety connected to the formula.
The photosensitive resin composition according to one embodiment comprises (A) a binder resin comprising a repeating unit represented by the following formula (1); (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant; And (E) a solvent.
[Chemical Formula 1]
In Formula 1,
R 1 to R 3 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
L 1 to L 5 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or a substituted or unsubstituted C6 to C20 arylene group.
For the binder resin constituting the photosensitive resin composition for a color filter, a monomer containing a bulky group was generally applied for securing heat resistance, but the developability thereof was relatively lowered, and there was a problem that the fairness such as residue was inferior .
However, since the photosensitive resin composition according to one embodiment includes the repeating unit represented by the above formula (1), not only superior heat resistance but also excellent developing property can be obtained, and a color filter having excellent brightness and fairness Filter can be provided.
Hereinafter, each component constituting the photosensitive resin composition will be described in detail.
(A) Binder resin
The photosensitive resin composition according to one embodiment includes a binder resin, and the binder resin includes the repeating unit represented by the formula (1).
For example, in Formula 1, L 1 to L 5 may be a single bond or a substituted or unsubstituted C1 to C20 alkylene group.
The repeating unit represented by Formula 1 may be contained in an amount of more than 0 wt% to 70 wt% or less, for example, 10 wt% to 60 wt% with respect to the total amount of the photosensitive resin composition. When the repeating unit represented by the above formula (1) is contained in the above range, the heat resistance of the photosensitive resin composition is excellent.
The binder resin may include an acrylic binder resin. For example, the binder resin may be an acrylic binder resin.
The acrylic binder resin is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer, and may be a resin containing at least one acrylic repeating unit.
The first ethylenically unsaturated monomer is an ethylenically unsaturated monomer containing at least one carboxyl group, and may be represented by, for example, the following formula (1-1). The first ethylenically unsaturated monomer may further include acrylic acid, methacrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.
[Formula 1-1]
In Formula 1-1,
R 3 is a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
L 1 to L 5 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or a substituted or unsubstituted C6 to C20 arylene group.
For example, L 1 to L 5 may be a single bond or a substituted or unsubstituted C1 to C20 alkylene group.
As described above, the first ethylenically unsaturated monomer may be contained in an amount of more than 0 wt% to 70 wt% or less, for example, 10 wt% to 60 wt% with respect to the total amount of the acrylic binder resin.
The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-hydroxyethyl Unsaturated carboxylic acid ester compounds such as methyl (meth) acrylate, cyclohexyl (meth) acrylate, tricyclodecane (meth) acrylate and phenyl (meth) acrylate; Unsaturated carboxylic acid aminoalkyl ester compounds such as 2-aminoethyl (meth) acrylate and 2-dimethylaminoethyl (meth) acrylate; Carboxylic acid vinyl ester compounds such as vinyl acetate and vinyl benzoate; Unsaturated carboxylic acid glycidyl ester compounds such as glycidyl (meth) acrylate; A vinyl cyanide compound such as (meth) acrylonitrile; Unsaturated amide compounds such as (meth) acrylamide; These may be used singly or in combination of two or more.
The binder resin may further include at least one of repeating units represented by the following Chemical Formulas 2 to 5, and the repeating units represented by Chemical Formulas 2 to 5 may be derived from the second ethylenically unsaturated monomer .
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
In the above Chemical Formulas 2 to 5,
R 4 , R 5 , R 7 and R 11 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R 6 , R 8 , R 9 , R 10 and R 12 each independently represents a hydrogen atom, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group or a substituted or unsubstituted C 6 to C 20 Lt; / RTI >
L 6 and L 7 are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.
For example, when R < 6 > is a substituted alkyl group, the substituent may not be an aryl group.
The binder resin may have a weight average molecular weight of 11,500 g / mol to 50,000 g / mol, such as 11,500 g / mol to 30,000 g / mol, such as 11,500 g / mol to 20,000 g / mol. When the weight average molecular weight of the binder resin is within the above range, the photosensitive resin composition is excellent in physical and chemical properties, has an appropriate viscosity, and is excellent in adhesion with a substrate in the production of a color filter.
The acid value of the binder resin may be from 110 mgKOH / g to 140 mgKOH / g. When the acid value of the binder resin is within the above range, the resolution of the pixel pattern is excellent.
The binder resin may be included in an amount of 1 wt% to 20 wt%, for example 1 wt% to 15 wt%, such as 1 wt% to 10 wt%, such as 1 wt% to 5 wt%, based on the total amount of the photosensitive resin composition . When the binder resin is contained within the above range, the color filter is excellent in developing property and the crosslinking property is improved, whereby excellent surface smoothness can be obtained.
(B) Photopolymerization Monomer
The photopolymerizable monomer may be a monofunctional or polyfunctional ester of (meth) acrylic acid having at least one ethylenically unsaturated double bond.
By having the ethylenically unsaturated double bond, the photopolymerizable monomer can form a pattern having excellent heat resistance, light resistance and chemical resistance by causing sufficient polymerization during exposure in the pattern formation step.
Specific examples of the photopolymerizable monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (meth) acrylate, (Meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol monomethacrylate (Meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolac epoxy (meth) acrylate and the like.
Examples of commercially available products of photopolymerizable monomers are as follows. The (meth) acrylic acid is one example of a polyfunctional ester, such as doah Gosei Kagaku Kogyo's (primary)社Aronix M-101 ®, the same M-111 ®, the same M-114 ®; KAYARAD TC-110S ® and TC-120S ® from Nihon Kayaku Co., Ltd.; Osaka yukki the like Kagaku Kogyo (main)社of V-158 ®, V-2311 ®. The (meth) transfer function of an example esters of acrylic acid are, doah Gosei Kagaku Kogyo (Note)社of Aronix M-210 ®, copper or the like M-240 ®, the same M-6200 ®; KAYARAD HDDA ® , HX-220 ® and R-604 ® from Nihon Kayaku Corporation; Osaka yukki the like Kagaku Kogyo Co., Ltd. of 社V-260 ®, V- 312 ®, V-335 HP ®. Examples of the tri-functional ester of (meth) acrylic acid, doah Gosei Kagaku Kogyo (Note)社of Aronix M-309 ®, the same M-400 ®, the same M-405 ®, the same M-450 ®, Dong M -710 ® , copper M-8030 ® , copper M-8060 ® and the like; Nippon Kayaku (Note)社of KAYARAD TMPTA ®, copper DPCA-20 ®, ® copper -30, -60 ® copper, copper ® -120 and the like; Osaka yukki Kayaku high (primary)社of V-295 ®, copper ® -300, -360 ® copper, copper -GPT ®, copper -3PA ®, and the like copper -400 ®. These products may be used alone or in combination of two or more.
The photopolymerizable monomer may be treated with an acid anhydride to give better developing properties.
The photopolymerizable monomer may be contained in an amount of 0.1 wt% to 5 wt%, for example, 0.1 wt% to 4 wt% with respect to the total amount of the photosensitive resin composition. When the photopolymerizable monomer is contained within the above range, the photopolymerizable monomer sufficiently cures upon exposure in the pattern forming step, and therefore, the photopolymerizable monomer is excellent in reliability and developability in an alkaline developer.
(C) Light curing Initiator
The photopolymerization initiator may be, for example, an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, an oxime-based compound or a combination thereof as an initiator generally used in a photosensitive resin composition.
Examples of the acetophenone-based compound include 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt-butyltrichloroacetophenone, dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropanone, p-butyldichloroacetophenone, 1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one.
Examples of the benzophenone compound include benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone, '-Bis (diethylamino) benzophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, and 3,3'-dimethyl-2-methoxybenzophenone.
Examples of the thioxanthone compound include thioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2- Chlorothioxanthone and the like.
Examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, and benzyl dimethyl ketal.
Examples of the triazine-based compound include 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -Dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) (Trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) - 4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphthol-1-yl) -Bis (trichloromethyl) -6- (4-methoxystyryl) -s-triazine, and the like. .
Examples of the oxime compounds include O-acyloxime compounds, 2- (o-benzoyloxime) -1- [4- (phenylthio) phenyl] -1,2-octanedione, 1- ) -1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] ethanone, O-ethoxycarbonyl- Etc. may be used. Specific examples of the O-acyloxime-based compound include 1,2-octanedione, 2-dimethylamino-2- (4-methylbenzyl) -1- (4-morpholin- (4-phenylsulfanylphenyl) -butane-1,2-dione 2-oxime-O-benzoate, 1- -Oxime-O-benzoate, 1- (4-phenylsulfanylphenyl) -octane-1-one oxime-O-acetate and 1- (4-phenylsulfanylphenyl) Acetate and the like.
The photopolymerization initiator may be a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound, an imidazole compound, or a nonimidazole compound in addition to the above compounds.
The photopolymerization initiator may be used in combination with a photosensitizer that generates a chemical reaction by absorbing light to be in an excited state and transferring its energy.
Examples of the photosensitizer include tetraethylene glycol bis-3-mercaptopropionate, pentaerythritol tetrakis-3-mercaptopropionate, dipentaerythritol tetrakis-3-mercaptopropionate and the like .
The photopolymerization initiator may be contained in an amount of 0.01 to 10% by weight, for example, 0.1 to 10% by weight, for example, 0.1 to 5% by weight, for example, 0.1 to 3% by weight based on the total amount of the photosensitive resin composition. When the photopolymerization initiator is contained within the above range, the photopolymerization initiator is sufficiently cured upon exposure in the pattern formation step to obtain excellent reliability, and the pattern is excellent in heat resistance, light resistance, chemical resistance, resolution and adhesion, It is possible to prevent the transmittance from being lowered.
(D) Colorant
The photosensitive resin composition according to one embodiment includes a colorant, and the colorant may include, for example, a pigment, a dye, or a combination thereof.
The pigment is used in the form of a pigment dispersion, and the pigment dispersion may include a solid pigment, a dispersant, a solvent, and the like. In this case, the pigment of solid content relative to the total amount of the pigment dispersion may be 8 wt% to 30 wt%, for example 8 wt% to 15 wt%, for example 8 wt% to 12 wt%. In this case, the pigment can be effectively dispersed, dispersion stability can be ensured, and color characteristics such as luminance can be improved.
The pigment may comprise a green pigment, a yellow pigment or a combination thereof.
The green pigment may be a halogenated phthalocyanine-based green pigment, for example, a compound classified as a pigment in the color index. Green pigment (Color Index Pigment Green) 7, 36, 58 and the like.
The yellow pigments have a C.I. Pigment yellow 139, C.I. Pigment yellow 138, C.I. Pigment yellow 150, etc. These may be used alone or in combination of two or more.
The primary particle diameter of the pigment may be from 10 nm to 80 nm, for example from 10 nm to 70 nm. When the primary particle diameter is within the above-mentioned particle diameter range, the stability in the pigment dispersion is excellent and there is no fear of deterioration of the resolution of the pixel, which is preferable.
As the solvent in the pigment dispersion, ethylene glycol acetate, ethyl cellosolve, propylene glycol monomethyl ether acetate, ethyl lactate, polyethylene glycol, cyclohexanone, propylene glycol methyl ether or 3-methoxy-1-butanol may be used Among them, propylene glycol monomethyl ether acetate can be preferably used. At this time, the content of the solvent is preferably adjusted so that the solid content of the pigment dispersion is 5 wt% to 30 wt%, but is not limited thereto.
The solvent may be present in an amount of from 30% by weight to 90% by weight, such as from 40% by weight to 90% by weight, such as from 50% by weight to 90% by weight, such as from 60% by weight to 90% 70% to 90% by weight, such as 80% to 90% by weight.
In addition, the pigment dispersion may further include a dispersant. As the dispersing agent, nonionic, anionic or cationic dispersing agents can be used. Examples thereof include polyalkylene glycols and esters thereof, polyoxyalkylene, polyhydric alcohol ester alkylene oxide adducts, alcohol alkylene oxide adducts , A sulfonic acid ester, a sulfonic acid salt, a carboxylic acid ester, a carboxylate, an alkylamide alkylene oxide adduct, and an alkylamine. These dispersants may be used singly or in combination of two or more.
The dispersing agent may be contained in an amount of 0.01 to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersing agent is contained within the above range, the dispersibility of the photosensitive resin composition is excellent, so that excellent stability, developability and patternability can be obtained.
The dye may include a green dye, a yellow dye, or a combination thereof. The dye can exhibit excellent color characteristics while constituting the colorant.
The colorant may comprise the pigments and dyes, wherein the pigments and dyes may be included in a weight ratio of from 1: 9 to 9: 1, such as from 5: 5 to 9: 1. For example, the content of the pigment in the colorant may be greater than the content of the dye. In this case, the heat resistance of the photosensitive resin composition containing the colorant is improved.
The amount of the colorant to be used is 20% by weight to 80% by weight, such as 20% by weight to 75% by weight, such as 25% by weight to 80% by weight, such as 25% by weight to 75% To 80% by weight, for example, from 30% by weight to 75% by weight. When the content of the colorant is within the above range, reliability and developability such as color characteristics such as luminance and chemical resistance can be improved.
(E) Solvent
The solvent may be a binder resin, a photopolymerizable monomer, a photopolymerization initiator, and a material that is compatible with the colorant but does not react with the binder resin.
Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether; Cellosolve acetates such as methyl cellosolve acetate, ethyl cellosolve acetate and diethyl cellosolve acetate; Carbitols such as methylethylcarbitol, diethylcarbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether and diethylene glycol diethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol methyl ether acetate and propylene glycol propyl ether acetate; Aromatic hydrocarbons such as toluene and xylene; Ketones such as methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl-n-propyl ketone, methyl- ; Saturated aliphatic monocarboxylic acid alkyl esters such as ethyl acetate, n-butyl acetate and isobutyl acetate; Lactic acid esters such as methyl lactate and ethyl lactate; Oxyacetic acid alkyl esters such as methyl oxyacetate, ethyl oxyacetate and butyl oxyacetate; Alkoxyacetic acid alkyl esters such as methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, and ethyl ethoxyacetate; 3-oxypropionic acid alkyl esters such as methyl 3-oxypropionate and ethyl 3-oxypropionate; 3-alkoxypropionic acid alkyl esters such as methyl 3-methoxypropionate, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate and methyl 3-ethoxypropionate; 2-oxypropionic acid alkyl esters such as methyl 2-oxypropionate, ethyl 2-oxypropionate and propyl 2-oxypropionate; 2-alkoxypropionic acid alkyl esters such as methyl 2-methoxypropionate, ethyl 2-methoxypropionate, ethyl 2-ethoxypropionate and methyl 2-ethoxypropionate; 2-methylpropionic acid esters such as methyl 2-oxy-2-methylpropionate and ethyl 2-oxy-2-methylpropionate, methyl 2-methoxy- Monooximonocarboxylic acid alkyl esters of 2-alkoxy-2-methylpropionic acid alkyls such as ethyl methyl propionate; Esters such as ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl hydroxyacetate and methyl 2-hydroxy-3-methylbutanoate; Ketone acid esters such as ethyl pyruvate, and the like, and also include N-methylformamide, N, N-dimethylformamide, N-methylformanilide, N-methylacetamide, N, N-dimethylacetamide , N-methylpyrrolidone, dimethylsulfoxide, benzyl ethyl ether, dihexyl ether, acetylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, And high boiling solvents such as ethyl acetate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate.
Among them, glycol ethers such as ethylene glycol monoethyl ether and the like are preferably used in consideration of compatibility and reactivity; Ethylene glycol alkyl ether acetates such as ethyl cellosolve acetate; Esters such as ethyl 2-hydroxypropionate; Carbitols such as diethylene glycol monomethyl ether; Propylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate and propylene glycol propyl ether acetate can be used.
The solvent may be contained in a residual amount, for example, from 15% by weight to 65% by weight, for example, from 15% by weight to 60% by weight based on the total amount of the photosensitive resin composition. When the solvent is contained within the above range, the photosensitive resin composition has an appropriate viscosity, and thus the processability in the production of the color filter is excellent.
(F) Other additives
In order to prevent spots or spots during coating and to improve the leveling performance and to prevent the formation of residues due to unexposed phenomenon, the photosensitive resin composition is preferably prepared by adding malonic acid, 3-amino-1,2-propanediol, Or other additives such as a silane-based coupling agent containing a (meth) acryloxy group, a leveling agent, a surfactant, a radical polymerization initiator, or a combination thereof.
Examples of the silane coupling agent include trimethoxysilylbenzoic acid,? -Methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane,? -Isocyanatopropyltriethoxysilane,? -Glycidoxypropyltrimethoxysilane, and? - (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These may be used singly or in combination of two or more.
As the surfactant, a fluorochemical surfactant may be used. Examples of the fluorine-based surfactant, BM Chemie Corporation BM-1000 ®, BM-1100 ® , and the like; Mecha Pack F 142D ® , Copper F 172 ® , Copper F 173 ® , Copper F 183 ® and the like manufactured by Dainippon Ink & Chemicals Incorporated; M. Sumitomo Co., Inc. Pro rod FC-135 ®, the same FC-170C ®, copper FC-430 ®, the same FC-431 ®, and the like; Asahi Grass Co., Inc. Saffron S-112 ®, the same S-113 ®, the same S-131 ®, the same S-141 ®, the same S-145 ®, and the like; Toray Silicone Co., Ltd.'s SH-28PA ®, ® -190 copper, may be a commercially available product such as copper -193 ®, SZ-6032 ®, SF-8428 ®.
The content of the additive can be easily adjusted according to desired properties.
The photosensitive resin composition may further include an epoxy compound to improve adhesion with the substrate.
Examples of the epoxy compound include a phenol novolak epoxy compound, a tetramethylbiphenyl epoxy compound, a bisphenol A type epoxy compound, an alicyclic epoxy compound, or a combination thereof.
The epoxy compound may be contained in an amount of 0.01 to 5 parts by weight, for example, 0.1 to 5 parts by weight based on 100 parts by weight of the photosensitive resin composition. When the epoxy compound is contained in the above range, it has excellent adhesion, heat resistance and chemical resistance.
Another embodiment provides a color filter manufactured using the above-described photosensitive resin composition.
A method of manufacturing the color filter is as follows.
The above-mentioned photosensitive resin composition is coated on the glass substrate by a suitable method such as spin coating, roller coating, spray coating or the like to a thickness of 0.5 占 퐉 to 10 占 퐉, for example, to form a resin composition layer.
Then, light is irradiated to form a pattern necessary for the color filter on the substrate on which the resin composition layer is formed. As the light source used for the irradiation, UV, electron beam or X-ray can be used. For example, UV in the range of 190 nm to 450 nm, specifically 200 nm to 400 nm can be irradiated. A photoresist mask may be further used in the above irradiation step. After the step of irradiating in this manner, the resin composition layer irradiated with the light source is treated with a developing solution. At this time, the non-exposed portions in the resin composition layer are dissolved to form a pattern necessary for the color filter. By repeating such a process according to the number of necessary colors, a color filter having a desired pattern can be obtained. In addition, when the image pattern obtained by development in the above step is heated again or cured by actinic ray irradiation or the like, crack resistance and solvent resistance can be improved.
Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are only a preferred embodiment of the present invention, and the present invention is not limited by the following examples.
( Example )
(Synthesis of binder resin)
Synthetic example 1 to Synthetic example 5 and Comparative Synthetic Example One
Azobis (2,4-dimethylvaleronitrile) (initiator) was added to a flask equipped with a condenser and a stirrer at a weight ratio of 10% by weight of the monomer mixture and the monomers shown in Table 1 below, 200 parts by weight of glycol monomethyl ether acetate (PGMEA, solvent) was added to 100 parts by weight of the total amount of the initiator and the monomer, and then stirring was started slowly under a nitrogen atmosphere. The reaction solution was heated to 75 캜 and stirred for 8 hours to synthesize an acrylic binder resin. The solid content concentration of the acrylic binder resin solution obtained by the above method was 30% by weight, and the weight average molecular weight was shown in Table 1. Here, the weight average molecular weight is an average molecular weight in terms of polystyrene measured by GPC (Gel Permeation Chromatography).
(Formula 1-2)
(Preparation of photosensitive resin composition)
Example 1 to Example 5 and Comparative Example One
After the content of the photopolymerization initiator was precisely measured, the solvent was added and sufficiently stirred (more than 30 minutes) until the photopolymerization initiator was completely dissolved. The binder resin and the photopolymerizable monomer were sequentially added thereto, followed by stirring for about 1 hour. Thereafter, a coloring agent and other additives were added, and the entire composition was finally stirred for 2 hours or more to prepare a photosensitive resin composition.
The composition of each component used in the production of the photosensitive resin composition is shown in Table 2 below.
The types of the respective components shown in Table 2 are as follows.
Photopolymerization Monomer
A: Photopolymerizable monomer (Sartomer, diphenyl pentaerythritol hexaacrylate)
B: Photopolymerizable monomer (SHIN-NAKAMURA CHEMICAL, A-BPE-20)
Light curing Initiator
Oxime initiator (CIBA, CGI-124)
coloring agent
A: G58 pigment dispersion (ENF)
B: Y138 pigment dispersion (ENF)
C: yellow dye (Gyeongin)
menstruum
Propylene glycol monomethyl ether acetate (PGMEA)
Other additives
F-559 (DIC)
Evaluation: Heat resistance and Developability evaluation
(K-Spin 8, KDNS) on a 1 mm-thick glass substrate subjected to degreasing and development for evaluation of residues and developability, a 2 μm-thick glass substrate with a thickness of 2 μm according to Examples 1 to 5 and Comparative Example 1 , A part of the solvent was removed through a depressurization facility, pre-baking was performed on a hot plate at 90 DEG C, pattern exposure was performed on the exposure machine under exposure conditions of 50 mJ / 300 mu m, Respectively.
The developer was diluted with the KOH solution of the whisker, and the developed image was observed through an optical microscope for a predetermined time (60 seconds). The results are shown in FIGS. 1 to 6.
The post-baked substrate was baked by convection oven at 230 ° C for 20 minutes. The post-baking color was measured using MCPD (Otsuka), and ΔEab * (del Eab *) Were calculated, and the results are shown in Table 3 below.
(230 DEG C, 30 minutes)
Additional heat resistance characteristics
Through Table 3 and FIG. 1 to FIG. 6, it was confirmed that the photosensitive resin compositions of Examples 1 to 5 including the binder resin containing the repeating unit represented by the formula (1) Developing property and brightness as compared with the photosensitive resin composition of the present invention.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.
Claims (14)
(B) a photopolymerizable monomer;
(C) a photopolymerization initiator;
(D) a colorant; And
(E) Solvent
: ≪ EMI ID =
[Chemical Formula 1]
In Formula 1,
R 1 to R 3 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
L 1 to L 5 are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group or a substituted or unsubstituted C6 to C20 arylene group.
Wherein L 1 to L 5 are a single bond or a substituted or unsubstituted C1 to C20 alkylene group.
Wherein the repeating unit represented by Formula 1 is contained in an amount of more than 0 wt% to 70 wt% with respect to the total amount of the binder resin.
Wherein the repeating unit represented by the formula (1) is contained in an amount of 10% by weight to 60% by weight based on the total amount of the binder resin.
Wherein the binder resin comprises an acrylic binder resin.
Wherein the binder resin further comprises at least one of repeating units represented by the following formulas (2) to (5).
(2)
(3)
[Chemical Formula 4]
[Chemical Formula 5]
In the above Chemical Formulas 2 to 5,
R 4 , R 5 , R 7 and R 11 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C20 alkyl group,
R 6 , R 8 , R 9 , R 10 and R 12 each independently represents a hydrogen atom, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group or a substituted or unsubstituted C 6 to C 20 Lt; / RTI >
L 6 and L 7 are each independently a single bond or a substituted or unsubstituted C1 to C20 alkylene group.
The binder resin has a weight average molecular weight of 11,500 g / mol to 50,000 g / mol.
The binder resin has an acid value of 110 mgKOH / g to 140 mgKOH / g.
Wherein the coloring agent comprises a pigment, a dye, or a combination thereof.
Wherein the pigment and the dye are contained in a weight ratio of 1: 9 to 9: 1.
Wherein the pigment comprises a green pigment, a yellow pigment or a combination thereof,
Wherein the dye comprises a green dye, a yellow dye or a combination thereof.
The above-mentioned photosensitive resin composition is preferably used in an amount of
1% by weight to 10% by weight of the binder resin;
0.1% to 5% by weight of the photopolymerizable monomer;
0.1% by weight to 5% by weight of the photopolymerization initiator;
30% to 80% by weight of the colorant; And
The solvent balance
.
Wherein the photosensitive resin composition further comprises an additive of malonic acid, 3-amino-1,2-propanediol, a silane coupling agent, a leveling agent, a fluorine surfactant, a radical polymerization initiator or a combination thereof.
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| KR1020150047732A KR20160118865A (en) | 2015-04-03 | 2015-04-03 | Photosensitive resin composition and color filter using the same |
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| KR1020150047732A KR20160118865A (en) | 2015-04-03 | 2015-04-03 | Photosensitive resin composition and color filter using the same |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190094713A (en) * | 2018-02-05 | 2019-08-14 | 삼성에스디아이 주식회사 | Photosensitive resin composition, black pixel defining layer using the same and display device |
| JP2021518584A (en) * | 2018-03-23 | 2021-08-02 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Negative actuated ultra-thick photoresist |
-
2015
- 2015-04-03 KR KR1020150047732A patent/KR20160118865A/en not_active Application Discontinuation
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190094713A (en) * | 2018-02-05 | 2019-08-14 | 삼성에스디아이 주식회사 | Photosensitive resin composition, black pixel defining layer using the same and display device |
| JP2021518584A (en) * | 2018-03-23 | 2021-08-02 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Negative actuated ultra-thick photoresist |
| US11698586B2 (en) | 2018-03-23 | 2023-07-11 | Merck Patent Gmbh | Negative-working ultra thick film photoresist |
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