KR20150082935A - Photosensitive resin composition and light blocking layer using the same - Google Patents
Photosensitive resin composition and light blocking layer using the same Download PDFInfo
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- KR20150082935A KR20150082935A KR1020140002477A KR20140002477A KR20150082935A KR 20150082935 A KR20150082935 A KR 20150082935A KR 1020140002477 A KR1020140002477 A KR 1020140002477A KR 20140002477 A KR20140002477 A KR 20140002477A KR 20150082935 A KR20150082935 A KR 20150082935A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D498/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D498/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having nitrogen and oxygen atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
- C07D498/04—Ortho-condensed systems
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
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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
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
- G02F1/1333—Constructional arrangements; Manufacturing methods
- G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
- G02F1/133509—Filters, e.g. light shielding masks
- G02F1/133512—Light shielding layers, e.g. black matrix
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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
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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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
- G03F7/022—Quinonediazides
- G03F7/023—Macromolecular quinonediazides; Macromolecular additives, e.g. binders
- G03F7/0233—Macromolecular quinonediazides; Macromolecular additives, e.g. binders characterised by the polymeric binders or the macromolecular additives other than the macromolecular quinonediazides
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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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- Chemical & Material Sciences (AREA)
- Optics & Photonics (AREA)
- Organic Chemistry (AREA)
- Nonlinear Science (AREA)
- Mathematical Physics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials For Photolithography (AREA)
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Abstract
(A) a binder resin comprising an acrylic resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant; And (E) a solvent, wherein the acrylic resin comprises a first copolymer comprising a repeating unit represented by the following formula (1):
[Chemical Formula 1]
(Wherein each substituent is as defined in the specification).
Description
The present invention relates to a photosensitive resin composition comprising a binder resin containing an acrylic resin and a light-shielding layer using the same.
A liquid crystal display device includes a lower substrate on which a light-shielding layer, a color filter, and ITO pixel electrodes are formed; An active circuit composed of a liquid crystal layer, a thin film transistor, and a capacitor capacitor layer; And an upper substrate on which ITO pixel electrodes are formed.
The light-shielding layer functions to cut off light which is transmitted through the substrate other than the transparent pixel electrode in order to prevent lowering of contrast due to light transmitted through the thin film transistor, and the colored layers of red, green, The main role is to transmit light of a specific wavelength and to be able to express color.
In the pigment dispersion method, a photopolymerizable composition containing a colorant is coated on a transparent substrate, a pattern of a pattern to be formed is exposed, and a non-exposed region is removed with a solvent And repeating a series of steps of thermosetting.
However, when a photosensitive polyimide or a phenolic resin is used as a binder resin according to the pigment dispersion method, it has a high heat resistance, but has a low sensitivity and has a drawback that it is developed with an organic solvent. Conventional systems using azide compounds as photosensitizers have low sensitivity and poor heat resistance or are subject to the influence of oxygen upon exposure.
The acrylic-containing resin is excellent in heat resistance, shrinkage resistance and chemical resistance, but tends to be poor in sensitivity, developability and adhesiveness. Furthermore, in the case of the light-shielding layer, since the content of the black pigment is increased to meet the required optical density, the sensitivity, developability and adhesiveness may be significantly deteriorated.
One embodiment is to provide a photosensitive resin composition excellent in developability, adhesion, patternability, heat resistance, chemical resistance, and the like.
Another embodiment is to provide a light-shielding layer made using the photosensitive resin composition.
Another embodiment is to provide a color filter including the light shielding layer.
One embodiment includes (A) a binder resin comprising an acrylic resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant; And (E) a solvent, wherein the acrylic resin comprises a first copolymer comprising a repeating unit represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R 1 and R 3 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R 2 represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkenyl group, a substituted or unsubstituted C1 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, A substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted A C2 to C30 heteroaryl group,
R 4 represents a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, an amino group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclo An alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,
R 5 is a substituted or unsubstituted C2 to C30 heterocyclic group,
L 1 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.
For example, R 5 may be a substituted or unsubstituted pyridine group, a substituted or unsubstituted pyrrole group, a substituted or unsubstituted indole group, a substituted or unsubstituted quinoline group, or a substituted or unsubstituted pyrimidine group.
The repeating unit represented by the formula (1) may be contained in an amount of 5 mol% to 30 mol% based on the total amount of the first copolymer.
Wherein the first copolymer further comprises a repeating unit derived from an unsaturated carboxylic acid compound, wherein the unsaturated carboxylic acid compound is an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid anhydride, or a combination thereof . ≪ / RTI >
The first copolymer may have a weight average molecular weight of 300 g / mol to 3,000 g / mol.
The acrylic resin may further comprise a second copolymer which is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer.
The acrylic resin may include the first copolymer and the second copolymer in a weight ratio of 10:90 to 90:10.
The binder resin may further comprise a cardade resin.
The colorant may comprise a dye, a pigment or a combination thereof.
Wherein the pigment comprises an organic pigment, an inorganic pigment or a combination thereof, wherein the organic pigment comprises a black organic pigment and the inorganic pigment is selected from the group consisting of carbon black, chromium oxide, iron oxide, titanium black, titanium carbon, aniline black, Combinations thereof.
The photosensitive resin composition comprises (A) 1 to 20% by weight of the binder resin; (B) 0.5% to 3.5% by weight of the photopolymerizable monomer; (C) 0.1% to 2% by weight of the photopolymerization initiator; (D) 10% to 50% by weight of the colorant; And (E) the solvent balance.
The photosensitive resin composition may include malonic acid; Oxazolidin-2-one; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; A radical polymerization initiator; Or a combination thereof.
Another embodiment provides a light-shielding layer made using the photosensitive resin composition.
Another embodiment provides a color filter comprising the light shielding layer.
Other aspects of the present invention are included in the following detailed description.
A photosensitive resin composition excellent in developability, adhesion, patternability, heat resistance, chemical resistance, and the like is provided, so that the composition can be effectively applied to a light shielding layer or the like.
FIGS. 1 and 2 are scanning electron microscopic photographs evaluating the adhesion of color filters according to Examples 2 and 4, respectively, and FIG. 3 is a scanning electron microscopic photograph evaluating the adhesion of color filters according to Comparative Example 1.
FIGS. 4 to 6 are optical microscopic photographs evaluating the pattern formability of color filters according to Examples 2, 4 and 6, respectively. FIG. 7 is an optical microscope photograph to be.
Figs. 8 to 13 are optical microscopic photographs evaluating the formability of the fine line pattern of the color filter according to each of Examples 1 to 6, Fig. 14 is a graph showing the evaluation of the formability of the fine line pattern of the color filter according to Comparative Example 1 It is an optical microscope photograph.
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, A thiol group, an ester group, an ether group, a silyl group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a sulfonyl group, a sulfonyl group or a salt thereof, , A phosphoric acid or salt thereof such as phosphonic acid, a C1 to C20 alkyl group, 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 cyclo A C3 to C20 cycloalkynyl group, a C2 to C20 heterocycloalkyl group, a C2 to C20 heterocycloalkenyl group, a C2 to C20 heterocycloalkynyl group, a C3 to C20 heteroaryl group,Substituted "
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.
Unless otherwise defined in the chemical formulas in this specification, when no chemical bond is drawn at the position where the chemical bond should be drawn, it means that the hydrogen atom is bonded at the above position.
As used herein, the cadmium resin means a resin in which at least one functional group selected from the group consisting of the following formulas (11) to (21) is contained as a main backbone of the resin.
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 an acrylic resin; (B) a photopolymerizable monomer; (C) a photopolymerization initiator; (D) a colorant; And (E) a solvent. The acrylic resin includes a first copolymer containing a repeating unit represented by the following formula (1), thereby improving developability and adhesion.
Each component will be described in detail below.
(A) Binder resin
The binder resin may include an acrylic resin. The acrylic resin may include a first copolymer containing a repeating unit represented by the following formula (1).
[Chemical Formula 1]
In Formula 1,
R 1 and R 3 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R 2 represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkenyl group, a substituted or unsubstituted C1 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, Or a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, RTI ID = 0.0 > C2-C30 < / RTI > heteroaryl group,
R 4 represents a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, an amino group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclo An alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,
R 5 is a substituted or unsubstituted C2 to C30 heterocyclic group,
L 1 is a single bond, or a substituted or unsubstituted C1 to C20 alkylene group.
For example, R 5 may be a substituted or unsubstituted pyridine group, a substituted or unsubstituted pyrrole group, a substituted or unsubstituted indole group, a substituted or unsubstituted quinoline group, or a substituted or unsubstituted pyrimidine group.
The repeating unit represented by the formula (1) may be derived from an unsaturated compound containing an aziridine group.
When the binder resin comprising the first copolymer containing the repeating unit represented by the formula (1) is used, the developing property, adhesion property, pattern forming property, heat resistance and chemical resistance of the light shielding layer in the color filter can be improved .
The repeating unit represented by the formula (1) may be at least one selected from 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 1 is a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R 2 represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkenyl group, a substituted or unsubstituted C1 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, Or a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, RTI ID = 0.0 > C2-C30 < / RTI >
The repeating unit represented by the formula (1) may be contained in an amount of 5 mol% to 30 mol%, for example, 5 mol% to 25 mol% based on the total amount of the first copolymer. When the repeating unit represented by the above-mentioned formula (1) is included in the above range, the pattern formability and resolution of the color filter can be improved.
The first copolymer may further include a repeating unit derived from an unsaturated carboxylic acid compound in addition to the repeating unit represented by the formula (1).
Examples of the unsaturated carboxylic acid compound include unsaturated monocarboxylic acids such as acrylic acid and methacrylic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid and itaconic acid; Unsaturated dicarboxylic acid anhydrides; Or a combination thereof. Of these, acrylic acid, methacrylic acid or a mixture thereof, which is excellent in copolymerization reactivity and solubility in an aqueous alkali solution, may be used.
The first copolymer may have a weight average molecular weight of from 250 g / mol to 3,000 g / mol, such as from 300 g / mol to 2,500 g / mol. When the weight average molecular weight is within the above range, the photosensitive resin composition is excellent in physical and chemical properties, viscosity is appropriate, developing property and sensitivity can be maintained at an appropriate level, and adhesion Can be excellent.
In the acrylic resin, in addition to the first copolymer, a second copolymer, which is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer, may be used together. That is, the first copolymer may be used in combination with the second copolymer.
The first ethylenically unsaturated monomer contains one or more carboxyl groups, and examples thereof include (meth) acrylic acid, maleic acid, itaconic acid, fumaric acid, or a combination thereof.
The first ethylenically unsaturated monomer may be included in an amount of 5 wt% to 50 wt%, for example, 10 wt% to 40 wt% based on the total amount of the second copolymer.
The second ethylenically unsaturated monomer may be an aromatic vinyl compound such as styrene,? -Methylstyrene, vinyltoluene, or vinylbenzyl methyl ether; (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, benzyl (meth) acrylate, Unsaturated carboxylic acid ester compounds such as cyclohexyl (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.
Specific examples of the second copolymer include acrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate copolymer, methacrylic acid / benzyl methacrylate / styrene copolymer, methacrylic acid / benzyl methacrylate Methacrylic acid / benzyl methacrylate / styrene / 2-hydroxyethyl methacrylate copolymer, but are not limited thereto, and they may be used singly or in combination of two or more. More than two species may be used in combination.
The weight average molecular weight of the second copolymer may be from 2,000 g / mol to 20,000 g / mol, for example from 3,000 g / mol to 15,000 g / mol, such as from 5,000 to 12,000 g / mol. When the weight average molecular weight of the second copolymer is within the above range, the photosensitive resin composition is excellent in physical and chemical properties, viscosity is appropriate, developing property and sensitivity can be maintained at an appropriate level, The adhesion with the substrate can be enhanced.
The acid value of the second copolymer may be from 40 mgKOH / g to 400 mgKOH / g, such as from 60 mgKOH / g to 200 mgKOH / g. When the acid value of the second copolymer is within the above range, developability can be maintained and the resolution of the pixel pattern is excellent.
The first copolymer and the second copolymer may be mixed at a weight ratio of 10:90 to 90:10, for example, 20:80 to 35:65. When used within the above-mentioned weight ratio range, it is possible to realize a wide range of process margin including an increase in adhesion to a substrate and an appropriate level of developability in manufacturing a light shielding layer in a color filter.
In addition to the above-mentioned acrylic resin, a cadmium resin may be used together with the binder resin. That is, the above-mentioned acrylic resin can be used by mixing with the cadene resin.
The cardade resin may be a compound containing a repeating unit represented by the following formula (10).
[Chemical formula 10]
(In the formula (10)
R 34 To R < 37 > are each independently a hydrogen atom, a halogen atom, or a substituted or unsubstituted C1 to C20 alkyl group,
R 38 and R 39 each independently represent a hydrogen atom or -CH 2 OR a (R a is a vinyl group, an acrylate group or a methacrylate group)
R 40 is a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C2 to C20 alkenyl group, an acrylate group or a methacrylate group,
Z 1 is a single bond, -O-, -CO-, -SO 2 -, -CR b R c -, -SiR d R e -, wherein R b to R e are each independently a hydrogen atom or a substituted Or an unsubstituted C1 to C20 alkyl group), or a linking group represented by the following formulas (11) to (21)
Z 2 is an acid anhydride residue.)
(11)
[Chemical Formula 12]
[Chemical Formula 13]
[Chemical Formula 14]
[Chemical Formula 15]
(In the above formula (15)
R f is a hydrogen atom, an ethyl group, -C 2 H 4 Cl, -C 2 H 4 OH, -CH 2 CH = CH 2 , or a phenyl group.
[Chemical Formula 16]
[Chemical Formula 17]
[Chemical Formula 18]
[Chemical Formula 19]
[Chemical Formula 20]
[Chemical Formula 21]
The cation resin can be specifically obtained by reacting a compound represented by the following formula (22) with a tetracarboxylic dianhydride.
[Chemical Formula 22]
The tetracarboxylic dianhydride may be an aromatic tetracarboxylic dianhydride. Examples of the aromatic tetracarboxylic acid dianhydride include pyromellic acid dianhydride, 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4-biphenyltetracarboxylate Acid dianhydride, 2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 3,3', 4,4'-benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4,4 '-Biphenyl ether tetracarboxylic dianhydride, 3,3', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride, 1,2,3,4-cyclopentanetetracarboxylic acid dianhydride, 1 , 2,5,6-naphthalenetetracarboxylic acid dianhydride, 2,3,6,7-naphthalenetetracarboxylic acid dianhydride, 1,4,5,8-naphthalenetetracarboxylic acid dianhydride, 2,3 , 5,6-pyridine tetracarboxylic dianhydride, 3,4,9,10-perylene tetracarboxylic dianhydride, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianhydride And the like, but the present invention is not limited thereto.
The weight average molecular weight of the cardedo resin may be from 1,000 g / mol to 20,000 g / mol, such as from 3,000 g / mol to 10,000 g / mol. When the weight average molecular weight of the carded resin is within the above range, excellent patterning and developability can be obtained in the production of the light shielding layer in the color filter.
The acrylic resin and the cation resin may be mixed in a weight ratio of 99: 1 to 1:99, such as 80:20 to 30:70. When used in the above weight ratio range, developability and substrate adhesion can be improved, and occurrence of an undercut can be prevented while forming a light-shielding layer pattern excellent in taper characteristics.
The binder resin is preferably added to the total amount of the photosensitive resin composition 1% to 20% by weight, 3% to 16% by weight. When the binder resin is contained within the above range, the viscosity can be appropriately maintained and the patterning property, the processability, and the developing property can be improved in the production of the color filter.
(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.
Since the photopolymerizable monomer has the ethylenically unsaturated double bond, sufficient polymerization is caused during exposure in the pattern formation step, whereby a pattern having excellent heat resistance, light resistance and chemical resistance can be formed.
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 Acrylate such as di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, bisphenol A di (meth) acrylate, pentaerythritol di (Meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol hexa (meth) acrylate, dipentaerythritol di Acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, bisphenol A epoxy (meth) acrylate, ethylene glycol There may be mentioned furnace methyl ether (meth) acrylate, trimethylolpropane tri (meth) acrylate, tris (meth) acryloyloxyethyl phosphate, novolak epoxy (meth) acrylate, and the like.
A commercially available product of the photopolymerizable monomer is exemplified 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 -7100 ® , 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 0.5 to 3.5% by weight, for example, 0.8 to 2.5% by weight based on the total amount of the photosensitive resin composition for a color filter. When the photopolymerizable monomer is contained within the above range, the photopolymerizable monomer sufficiently cures upon exposure in the pattern formation process, and the sensitivity in the presence of oxygen is excellent, and the compatibility with the binder resin is excellent.
(C) Light curing Initiator
The photopolymerization initiator may be an acetophenone-based compound, a benzophenone-based compound, a thioxanthone-based compound, a benzoin-based compound, a triazine-based compound, or an oxime-based compound.
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) (Trichloromethyl) -s-triazine, 2- (4'-methoxynaphthyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) Bis (trichloromethyl) -s-triazine, bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho 1-yl) -4,6 Bis (trichloromethyl) -s-triazine, 2,4- bis (trichloromethyl) -s-triazine, 2- (4-methoxynaphtho- (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 included in an amount of 0.1 wt% to 2 wt%, for example, 0.3 wt% to 1.5 wt% with respect to the total amount of the photosensitive resin composition for a color filter. When the photopolymerization initiator is contained within the above range, photopolymerization sufficiently occurs upon exposure in the pattern formation step, and the decrease of the transmittance due to the unreacted initiator can be prevented.
(D) Colorant
The colorant may comprise a dye, a pigment or a combination thereof.
The pigments may include organic pigments, inorganic pigments or combinations thereof. Among them, the organic pigments and the inorganic pigments may be mixed and used for better optical density.
The organic pigments may be black organic pigments. The black organic pigment is insulating.
Examples of the black organic pigments include perylene black and cyanine black, which may be used alone or in combination of two or more.
The black organic pigment may also be a mixture of two or more kinds of organic pigments and having a black color. Any pigment can be used as long as it is a combination of pigments which can be black when mixed on a color coordinate system. Specific examples of the pigments include red pigments, blue pigments, green pigments, violet pigments, yellow pigments, cyanine pigments and magenta ) Based pigments may be combined and blackened. For example, a red pigment, a blue pigment and a green pigment may be mixed and blackened, or a green pigment and a violet pigment may be mixed and blackened.
Examples of the red pigments include perylene pigments, anthraquinone pigments, dianthraquinone pigments, azo pigments, diazo pigments, quinacridone pigments, and anthracene pigments. have. Specific examples of the red pigments include perylene pigments, quinacridone pigments, naphthol AS, sikomine pigments, anthraquinone (sudan I, II, III, R), dianthraquinonyl, Vis azo, benzopyran and the like.
Examples of the blue pigments include metal phthalocyanine pigments, indanthrone pigments, indophenol pigments, and the like. Specific examples of the blue pigments include phthalocyanine metal complexes such as copper phthalocyanine, chloro copper phthalocyanine, chloroal phthalocyanine, titanyl phthalocyanine, vanadinic acid phthalocyanine, magnesium phthalocyanine, zinc phthalocyanine, iron phthalocyanine and cobalt phthalocyanine.
As the green pigments, halogenated phthalocyanine pigments And the like. Specific examples thereof include polychloro-copper phthalocyanine and polychlorobromophthalocyanine.
Examples of the violet pigment include dioxazine violet, first violet B, methyl violet, indanthrene brilliant violet, and the like.
Examples of the yellow pigments include tetrachloroisoindolinone pigments, hansa pigments, benzidine yellow pigments, and azo pigments. Examples of the yellow pigments include tetrachloroisoindolinone pigments, hansa pigments, benzidine yellow pigments, and azo pigments. Specific examples thereof include hansa yellow (10G, 5G, 3G, G, GR, A, RN, R), benzidine (G, GR), chrome yellow, permanent yellow (FGL, H10G, HR), and anthracene.
Examples of the cyanine pigment include metal-free phthalocyanine, merocyanine, and the like.
Examples of the magenta pigment include dimethyl quinacridone, thioindigo, and the like.
Examples of the inorganic pigments include carbon black, chromium oxide, iron oxide, titanium black, titanium carbon, and aniline black. These inorganic pigments exhibit high resistance characteristics, and they can be used singly or in combination of two or more kinds.
The organic pigment and the inorganic pigment may be mixed in a weight ratio of 1 to 10: 1, for example, 2 to 7: 1. When mixed in the weight ratio range, the processability is stable and the dielectric constant can be low.
A dispersant may be used together to disperse the pigment well in the photosensitive resin composition.
The dispersant may be added to the inside of the pigment in the form of surface-treating the pigment in advance, or may be added to the pigment together with the pigment to prepare a photosensitive resin composition for a color filter.
DISPERBYK-161, DISPERBYK-160, DISPERBYK-161, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-160 and DISPERBYK-160 of BYK Co., -166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001 and the like; EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400 and EFKA-450 of EFKA Chemical Co., Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse 13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse 27000, Solsperse 28000 from Zeneka; Or Ajinomoto's PB711 and PB821.
The dispersant may be contained in an amount of 0.1 to 15% by weight based on the total amount of the photosensitive resin composition. When the dispersing agent is contained in the above range, the dispersibility of the photosensitive resin composition is excellent, and thus the stability, developability and patterning property of the light-shielding layer are excellent.
The pigment may be used by pretreatment using a water-soluble inorganic salt and a wetting agent. When the pigment is used in the pretreatment, the primary particle size of the pigment can be reduced.
The pretreatment may be performed by kneading the pigment with a water-soluble inorganic salt and a wetting agent, and filtering and washing the pigment obtained in the kneading step.
The kneading may be carried out at a temperature of 40 to 100 DEG C, and the filtration and washing may be performed by washing the inorganic salt with water, etc., followed by filtration.
Examples of the water-soluble inorganic salt include, but are not limited to, sodium chloride and potassium chloride. The wetting agent acts as a medium through which the pigment and the water-soluble inorganic salt are uniformly mixed to easily pulverize the pigment. Examples of the wetting agent include ethylene glycol monoethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether and the like Alkylene glycol monoalkyl ethers; And alcohols such as ethanol, isopropanol, butanol, hexanol, cyclohexanol, ethylene glycol, diethylene glycol, polyethylene glycol, glycerin polyethylene glycol and the like. These may be used singly or in combination of two or more thereof.
The pigment after the kneading step may have an average particle diameter of 30 nm to 100 nm. When the average particle diameter of the pigment is within the above range, it is possible to effectively form a fine pattern with excellent heat resistance and light resistance.
The colorant may be contained in an amount of 10% by weight to 50% by weight, for example, 15% by weight to 40% by weight based on the total amount of the photosensitive resin composition. When the colorant is included in the above range, the pattern hardenability and adhesion can be enhanced.
(E) Solvent
The solvent may be a material that has compatibility with the binder resin, the photopolymerizable monomer, the photopolymerization initiator, and the colorant but does not react.
Examples of the solvent include alcohols such as methanol and ethanol; Ethers such as dichloroethyl ether, n-butyl ether, diisobutyl ether, methylphenyl ether and tetrahydrofuran; Glycol ethers such as ethylene glycol 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 ethyl methyl 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 Benzyl alcohol, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, benzoic acid, And high boiling solvents such as ethyl benzoate, diethyl oxalate, diethyl maleate,? -Butyrolactone, ethylene carbonate, propylene carbonate, and phenyl cellosolve acetate. These solvents may be used alone or in combination of two or more .
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 methyl ether acetate and propylene glycol propyl ether acetate can be used.
The solvent may be contained in a residual amount, for example, from 40% by weight to 80% by weight, for example, from 50% by weight to 80% 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 therefore, the processability of the light-shielding layer can be improved.
(F) Other additives
The above-mentioned photosensitive resin composition may contain at least one selected from the group consisting of malonic acid, malonic acid, and malonic acid, in order to prevent stains and spots upon application, to prevent leveling, Oxazolidin-2-one; 3-amino-1,2-propanediol; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; 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.
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 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 for a color filter. When the epoxy compound is contained in the above range, it has excellent adhesion, heat resistance and chemical resistance.
Another embodiment provides a light-shielding layer made using the above-described photosensitive resin composition for a color filter.
Another embodiment provides a color filter including the light-shielding layer described above.
A method of manufacturing the color filter is as follows.
(1) Coating and film formation clues
The photosensitive resin composition for a color filter described above is coated on a predetermined pretreated substrate by a method such as spin or slit coat method, roll coating method, screen printing method or applicator method to a desired thickness, for example, 0.5 to 1.5 탆 And then the solvent is removed by heating at a temperature of 70 to 110 캜 for 1 to 10 minutes to form a coating film.
(2) Exposure step
After forming a mask of a predetermined type in order to form a pattern necessary for the obtained coating film, an active line of 190 nm to 500 nm is irradiated. As the light source used for the irradiation, a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, a metal halide lamp, an argon gas laser, and the like can be used.
The exposure dose varies depending on the kind of each component of the photosensitive resin composition, the blending amount, and the dried film thickness. For example, when a high pressure mercury lamp is used, the exposure dose is 500 mJ / cm 2 (By a 365 nm sensor).
(3) Development step
Following the exposure step, an unnecessary portion is dissolved and removed by using an alkaline aqueous solution (for example, KOH or the like) as a developer to leave only the exposed portion to form an image pattern.
(4) Post-treatment step
The image pattern obtained by the above-described development can be cured by heating again or by active ray irradiation or the like in order to obtain a pattern excellent in terms of heat resistance, light resistance, adhesion, crack resistance, chemical resistance, high strength and storage stability.
By using the above-described photosensitive resin composition, it is possible to obtain excellent developability and adhesion required for the light-shielding layer in the color filter.
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.
(Acrylic resin production)
Manufacturing example 1-1
35 wt% of methacrylic acid, 25 wt% of a compound represented by the following formula (30), and 40 wt% of benzyl methacrylate were placed in a reactor, and 4 g of azobisisobutyronitrile (AIBN) Thereafter, the reaction was carried out at 80 DEG C for 8 hours to prepare an acrylic resin.
(30)
The weight average molecular weight of the acrylic resin thus prepared was 2000 g / mol.
Manufacturing example 1-2
An acrylic resin was prepared in the same manner as in Preparation Example 1-1, except that the compound represented by the following formula (31) was used instead of the compound represented by the formula (30).
(31)
The weight average molecular weight of the acrylic resin thus prepared was 2500 g / mol.
Manufacturing example 1-3
An acrylic resin was prepared in the same manner as in Preparation Example 1-1, except that the compound represented by the following formula (32) was used instead of the compound represented by the formula (30).
(32)
The weight average molecular weight of the prepared acrylic resin was 3000 g / mol.
Manufacturing example 1-4
An acrylic resin was prepared in the same manner as in Preparation Example 1-1, except that the compound represented by Formula 33 was used instead of the compound represented by Formula 30 in Production Example 1-1.
(33)
The weight average molecular weight of the prepared acrylic resin was 2800 g / mol.
(Preparation of black pigment dispersion)
Manufacturing example 2
15 g of carbon black (Cabot), 4 g of DISPERBYK-163 (BYK), 3 g of acrylic acid / benzyl methacrylate copolymer (Mizuho Company, NPR8000) and 78 g of propylene glycol methyl ethyl acetate were mixed and mixed in a paint shaker -shaker (Asada) for 12 hours to prepare a black pigment dispersion.
(Preparation of photosensitive resin composition)
The specifications of the components used in the production of the photosensitive resin composition are as follows
(A) Binder resin
(A-1) Acrylic resin
(A-1-1) The acrylic resin prepared in Production Example 1-1 was used.
(A-1-2) The acrylic resin prepared in Production Example 1-2 was used.
(A-1-3) The acrylic resin prepared in Preparation Example 1-3 was used.
(A-1-4) The acrylic resin prepared in Production Example 1-4 was used.
(A-2) Carometer Suzy
V259ME from Shinil Chemical Co., Ltd. was used.
(B) Photopolymerization Monomer
Dipentaerythritol hexaacrylate was used.
(C) Light curing Initiator
IRGACURE OXE02 from Shiba Co. was used.
(D) Colorant
The black pigment dispersion prepared in Production Example 2 was used. At this time, the pigment solid content is 18% by weight based on the total amount of the black pigment dispersion liquid.
(E) Solvent
(E-1) propylene glycol methyl ether acetate was used.
(E-2) diethylene glycol ethyl methyl ether was used.
(F) Additive
Glycidoxypropyltrimethoxysilane (S-510 by Chisso) as a silane coupling agent and F-475 of DIC as a surfactant were mixed and used.
Example 1 to 6 and Comparative Example One
The photosensitive resin compositions according to Examples 1 to 6 and Comparative Example 1 were prepared with the compositions shown in Table 1 below. Specifically, a photopolymerization initiator was dissolved in a solvent, and the mixture was stirred at room temperature for 2 hours. Then, a binder resin and a photopolymerizable monomer were added thereto, followed by stirring at room temperature for 2 hours. Then, the colorant and additives were added to the obtained reaction product, and the mixture was stirred at room temperature for 1 hour. Subsequently, the product was filtered three times to remove impurities, thereby preparing a photosensitive resin composition.
(Pattern formation of color filter)
The photosensitive resin compositions prepared in Examples 1 to 6 and Comparative Example 1 were coated on a glass substrate and then dried at 90 DEG C for 150 seconds to form a coating film. The thus obtained coating film was irradiated with light having a wavelength of 365 nm at a dose of 40 mJ / cm 2 using a pattern mask. Subsequently, the resultant was developed with an aqueous solution containing 1 wt% of potassium hydroxide diluted with a developing solution at 22 DEG C, and then washed with pure water for 1 minute. By this operation, unnecessary portions can be removed and only the pattern can be left. The pattern substrate thus formed was heated in an oven at 230 DEG C for 25 minutes to be cured to obtain a final pattern.
Evaluation 1: Development time
The development time was evaluated based on the time when the desired pattern pattern was first visually recognized as the developer was applied and developed during the formation of the final pattern. The results are shown in Table 2 below.
<Evaluation Criteria of Development Time>
S: 60 seconds or more and 65 seconds or less
M: 57 seconds to less than 60 seconds
F: Less than 57 seconds
Evaluation 2: adhesion
The adhesion pattern was evaluated by an optical microscope for the final pattern obtained above. The results are shown in Table 2 and FIGS. 1 to 3.
≪ Adhesion evaluation standard &
○: When the pattern is not broken
△: When less than 5 patterns were torn off
×: When more than 5 patterns are torn off
Rating 3: Pattern Formability
The final pattern having the height of 1.3 탆 obtained above was visually evaluated for its pattern shape by an optical microscope, and the results are shown in Table 2 and FIGS. 4 to 10.
FIGS. 4 to 6 are optical microscopic photographs evaluating the pattern formability of color filters according to Examples 2, 4 and 6, respectively. FIG. 7 is an optical microscope photograph to be.
<Evaluation Criteria of Pattern Formability>
&Amp; cir &: Excellent pattern formation property
Good: Good pattern formation property
?: Poor pattern formation property
Evaluation 4: Fine line pattern Formability
The size of the pattern shape was measured by an optical microscope with respect to the final pattern obtained above. The results are shown in Table 2 and Figs. 11 to 17.
Figs. 8 to 13 are optical microscopic photographs evaluating the formability of the fine line pattern of the color filter according to each of Examples 1 to 6, Fig. 14 is a graph showing the evaluation of the formability of the fine line pattern of the color filter according to Comparative Example 1 It is an optical microscope photograph.
(탆)
Referring to Table 2 and FIGS. 1 to 14, it can be seen that Examples 1 to 6 using the binder resin according to one embodiment are excellent in developability, adhesion, and patterning property as compared with Comparative Example 1.
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
Lt; / RTI >
Wherein the acrylic resin comprises a first copolymer comprising a repeating unit represented by the following formula (1): < EMI ID =
[Chemical Formula 1]
(In the formula 1,
R 1 and R 3 are each independently a hydrogen atom or a substituted or unsubstituted C1 to C10 alkyl group,
R 2 represents a hydrogen atom, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkenyl group, a substituted or unsubstituted C1 to C20 alkynyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, Or a substituted or unsubstituted C3 to C20 cycloalkenyl group, a substituted or unsubstituted C3 to C20 cycloalkynyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, RTI ID = 0.0 > C2-C30 < / RTI > heteroaryl group,
R 4 represents a hydrogen atom, a halogen atom, a hydroxy group, a cyano group, a nitro group, an amino group, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C2 to C20 heterocyclo An alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,
R 5 is a substituted or unsubstituted C2 to C30 heterocyclic group,
L 1 is a single bond or a substituted or unsubstituted C1 to C20 alkylene group.)
Wherein R 5 is a substituted or unsubstituted pyridine group, a substituted or unsubstituted pyrrole group, a substituted or unsubstituted indole group, a substituted or unsubstituted quinoline group, or a substituted or unsubstituted pyrimidine group.
Wherein the repeating unit represented by the formula (1) is contained in an amount of 5 mol% to 30 mol% based on the total amount of the first copolymer.
Wherein the first copolymer further comprises a repeating unit derived from an unsaturated carboxylic acid compound,
The unsaturated carboxylic acid compound includes an unsaturated monocarboxylic acid, an unsaturated dicarboxylic acid, an unsaturated dicarboxylic acid anhydride, or a combination thereof.
Wherein the first copolymer has a weight average molecular weight of 250 g / mol to 3,000 g / mol.
Wherein the acrylic resin further comprises a second copolymer,
Wherein the second copolymer is a copolymer of a first ethylenically unsaturated monomer and a second ethylenically unsaturated monomer copolymerizable with the first ethylenically unsaturated monomer.
Wherein the acrylic resin comprises the first copolymer and the second copolymer in a weight ratio of 10:90 to 90:10.
Wherein the binder resin further comprises a cadmium resin.
Wherein the colorant comprises a dye, a pigment, or a combination thereof.
The pigment comprises an organic pigment, an inorganic pigment or a combination thereof,
Wherein the organic pigment comprises a black organic pigment,
Wherein the inorganic pigment comprises carbon black, chromium oxide, iron oxide, titanium black, titanium carbon, aniline black or a combination thereof
Sensitive resin composition.
The photosensitive resin composition
(A) 1 to 20% by weight of the binder resin;
(B) 0.5% to 3.5% by weight of the photopolymerizable monomer;
(C) 0.1% to 2% by weight of the photopolymerization initiator;
(D) 10% to 50% by weight of the colorant; And
(E) the solvent remaining amount
.
The photosensitive resin composition may include malonic acid; Oxazolidin-2-one; A silane-based coupling agent comprising a vinyl group or (meth) acryloxy group; Leveling agents; Fluorine surfactants; A radical polymerization initiator; Or a combination thereof. ≪ / RTI >
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140002477A KR20150082935A (en) | 2014-01-08 | 2014-01-08 | Photosensitive resin composition and light blocking layer using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020140002477A KR20150082935A (en) | 2014-01-08 | 2014-01-08 | Photosensitive resin composition and light blocking layer using the same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR20150082935A true KR20150082935A (en) | 2015-07-16 |
Family
ID=53884826
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020140002477A KR20150082935A (en) | 2014-01-08 | 2014-01-08 | Photosensitive resin composition and light blocking layer using the same |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR20150082935A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180063650A (en) * | 2016-12-02 | 2018-06-12 | 삼성에스디아이 주식회사 | Photosensitive resin composition, black pixel defining layer using the same and display device |
-
2014
- 2014-01-08 KR KR1020140002477A patent/KR20150082935A/en not_active Application Discontinuation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20180063650A (en) * | 2016-12-02 | 2018-06-12 | 삼성에스디아이 주식회사 | Photosensitive resin composition, black pixel defining layer using the same and display device |
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