CN102445842A - Photosensitive resin composition and black matrix using the same - Google Patents
Photosensitive resin composition and black matrix using the same Download PDFInfo
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- CN102445842A CN102445842A CN2011101157923A CN201110115792A CN102445842A CN 102445842 A CN102445842 A CN 102445842A CN 2011101157923 A CN2011101157923 A CN 2011101157923A CN 201110115792 A CN201110115792 A CN 201110115792A CN 102445842 A CN102445842 A CN 102445842A
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- methyl
- resin composition
- photosensitive resin
- acid
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- 0 CC1(N)O*c2c1cccc2 Chemical compound CC1(N)O*c2c1cccc2 0.000 description 3
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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
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
- C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
- C07D471/08—Bridged systems
-
- 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
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- 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
-
- 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
-
- 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
-
- 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
-
- 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
Abstract
The present invention discloses a photosensitive resin composition which comprises the following components: (A) cardo group resin which comprises repetitive units that are respectively represented by a chemical formula 1; (B) active unsaturated compound; (C) pigment; (D) initiating agent and (E) dissolvent. The invention also discloses a color blocking layer which is prepared by the photosensitive resin, wherein, in a chemical formula 1, each substitutional group is same with the structure which is limited in the description.
Description
Technical field
Disclosure content of the present invention relates to photosensitive resin composition that comprises cardo base resin (joint base resin, cyclic group resin, cardo-based resin) and the light blocking layer that uses it.
Background technology
LCD comprises infrabasal plate, active circuit part and upper substrate, and infrabasal plate comprises light blocking layer, color filter and ITO pixel electrode; Active circuit partly comprises liquid crystal layer, thin film transistor (TFT) and capacitor layer; Upper substrate comprises the ITO pixel electrode.
Light blocking layer blocks the uncontrolled light that transmits from the transparent pixels electrode of substrate, and therefore prevents owing to see through the contrast that light the caused decline of thin film transistor (TFT).The light that has predetermined wavelength in red, the green and blue light blocking layer transmission white light, and display color.
Light blocking layer is usually through the preparation of pigment dispersing method.The pigment dispersing method comprises: with the photopolymerizable composition coated transparent substrate that contains colorant, through heat curing exposure pattern to be provided and to remove unexposed part with solvent.
Yet when light-sensitive polyimide or phenol resin were used for the pigment dispersing method as adhesive resin, though can obtain high thermotolerance, light sensitivity (sensitivity) reduced, and needs organic solvent as developer solution.(photoresist photoresist) has low speed and thermotolerance to the photoresist of use triazo-compound, and between exposure period, can receive the influence of oxygen.
In addition, acrylic based resin (acryl-based resin) has good thermotolerance, anti-shrinkability, chemical resistance etc., but light sensitivity, developing property and closely contact performance reduction.Comprise black pigment in a large number for the optical density of regulating light blocking layer, can make light sensitivity, developing property and the tight obvious variation of contact performance.
Summary of the invention
One aspect of the present invention provide have excellent light sensitivity, developing property, the tight photosensitive resin composition of contact performance, thermotolerance, anti-shrinkability, chemical resistance and tapering characteristic (taper properties).
Another aspect of the present invention provides the light blocking layer that uses above-mentioned photosensitive resin composition and prepare.
According to an aspect of the present invention, the photosensitive resin composition that comprises following component is provided: the cardo base resin (cardo-based resin) that (A) comprises the repetitive that following Chemical formula 1 is represented; (B) active (reactivity, reactive) unsaturated compound; (C) pigment; (D) initiating agent; And (E) solvent.
[Chemical formula 1]
In Chemical formula 1,
R
3And R
4Identical or different, and be hydrogen, halogen or replacement or unsubstituted C1 to C20 alkyl,
R
1And R
2Identical or different, and be hydrogen or CH
2OCH
2CR
6R
7R
8(wherein, R
6To R
8Identical or different, be hydrogen or replacement or unsubstituted (methyl) acrylic ester), condition is R
1And R
2In at least one be CH
2OCH
2CR
6R
7R
8(wherein, R
6To R
8Identical or different, be hydrogen or replacement or unsubstituted (methyl) acrylic ester, and R
6To R
8In at least one be to replace or unsubstituted (methyl) acrylic ester),
Z
1Be singly-bound, O, CO, SO
2, CR
9R
10, SiR
11R
12(wherein, R
9To R
12Identical or different, and be hydrogen or replacement or unsubstituted C1 to C20 alkyl) or at least one linking group of representing to 2-11 by following Chemical formula 2-1,
Z
2Be acid anhydrides residue or acid dianhydride residue,
m
1And m
2Be the integer of 0 to 4 scope independently, and n is 1 to 1000 integer.
[Chemical formula 2-1]
[Chemical formula 2-2]
[Chemical formula 2-3]
[Chemical formula 2-4]
[Chemical formula 2-5]
In Chemical formula 2-5,
R
aBe hydrogen, ethyl, C
2H
4Cl, C
2H
4OH, CH
2CH=CH
2Or phenyl.
[Chemical formula 2-6]
[Chemical formula 2-7]
[Chemical formula 2-8]
[Chemical formula 2-9]
[Chemical formula 2-10]
[Chemical formula 2-11]
This cardo base resin can have 1,000 to 50, the weight-average molecular weight of 000g/mol.
Cardo base resin can comprise the end group of following chemical formula 4 expressions at least one place in two ends.
[chemical formula 4]
In chemical formula 4,
Z
3It is at least one linking group of representing by following chemical formula 5-1 to 5-7.
[chemical formula 5-1]
In chemical formula 5-1, R
bAnd R
cIdentical or different, and be hydrogen, replacement or unsubstituted C1 to C20 alkyl, ester group or ether.
[chemical formula 5-2]
[chemical formula 5-3]
[chemical formula 5-4]
[chemical formula 5-5]
In chemical formula 5-5, R
dBe O, S, NH, replacement or unsubstituted C1 to C20 alkyl, C1 to C20 alkylamino radical or C2 to C20 allyl amido.
[chemical formula 5-6]
[chemical formula 5-7]
This photosensitive resin composition can comprise 1 to 30wt% cardo base resin (A); 1 to 30wt% active unsaturated compound (B); 1 to 30wt% pigment (C); 0.01 initiating agent (D) to 10wt%; And the solvent of surplus (E).
This photosensitive resin composition may further include acrylic based resin (acrylic resin; Acryl-based resin); And this acrylic based resin comprises the multipolymer of first ethylenically unsaturated monomers (first ethylenic unsaturated monomer) and second ethylenically unsaturated monomers (second ethylenic unsaturated monomer), and wherein first ethylenically unsaturated monomers is (methyl) acrylic acid, maleic acid, itaconic acid, fumaric acid or their combination; Second ethylenically unsaturated monomers is a styrene; AMS; Vinyltoluene; The vinyl benzyl methyl ether; (methyl) methyl acrylate; (methyl) ethyl acrylate; (methyl) butyl acrylate; (methyl) acrylic acid 2-hydroxy methacrylate; (methyl) acrylic acid 2-hydroxyl butyl ester; (methyl) benzyl acrylate; (methyl) cyclohexyl acrylate; (methyl) phenyl acrylate; (methyl) acrylic acid 2-amino ethyl ester; (methyl) acrylic acid 2-dimethylamino ethyl ester; Vinyl acetate; Vinyl benzoate; (methyl) glycidyl acrylate; (methyl) vinyl cyanide; (methyl) acrylic amide; Or their combination.
It is about 3,000 to 40 that acrylic based resin can have, the weight-average molecular weight of 000g/mol.
The cardo base resin that can comprise and the weight ratio of acrylic based resin are 99: 1 to 30: 70.
Initiating agent can comprise Photoepolymerizationinitiater initiater, free radical polymerization (radical polymerization) initiating agent or their combination.
Based on the photosensitive resin composition of 100 weight portions, photosensitive resin composition can comprise the epoxy compound of 0.01 to 20 weight portion.
According to a further aspect in the invention, the light blocking layer that uses above-mentioned photosensitive resin composition and prepare is provided.
Hereinafter, will describe other embodiment in detail.
This photosensitive resin composition has excellent light sensitivity, developing property, tight contact performance, thermotolerance, anti-shrinkability, chemical resistance and tapering characteristic (taper properties), and can be applicable to light blocking layer etc. valuably.
Description of drawings
Fig. 1 is the electron scanning micrograph that illustrates according to the residue (residue) of the photosensitive resin composition of embodiment 1.
Fig. 2 is the electron scanning micrograph that illustrates according to the residue of the photosensitive resin composition of comparative example 3.
Fig. 3 is the electron scanning micrograph that illustrates according to the residue of the photosensitive resin composition of comparative example 1.
Fig. 4 illustrates the electron scanning micrograph that forms characteristic according to the pattern of the photosensitive resin composition of embodiment 2.
Fig. 5 illustrates the electron scanning micrograph that forms characteristic according to the pattern of the photosensitive resin composition of embodiment 1.
Fig. 6 illustrates the electron scanning micrograph that forms characteristic according to the pattern of the photosensitive resin composition of comparative example 3.
Fig. 7 illustrates the electron scanning micrograph that forms characteristic according to the pattern of the photosensitive resin composition of comparative example 2.
Fig. 8 is the optical microscope photograph that illustrates according to the pattern dimension of the photosensitive resin composition of embodiment 2.
Fig. 9 is the optical microscope photograph that illustrates according to the pattern dimension of the photosensitive resin composition of comparative example 2.
Figure 10 is the optical microscope photograph that illustrates according to the pattern dimension of the photosensitive resin composition of comparative example 4.
Embodiment
Hereinafter will be described the illustrative embodiments of the disclosure of invention in detail.Yet these embodiments only are exemplary, are not the restriction to the disclosure of invention.
As used herein; When concrete definition not being provided in addition; Term " substituted " is meant by halogen (F, Cl, Br or I), hydroxyl, C1 to C20 alkoxy, nitro, cyanic acid, amido, imino group, azido, amidino groups, diazanyl, hydrazono-, carbonyl, carbamyl, sulfydryl, ester group, ether, carboxyl or its salt, sulfonic group or its salt, phosphate or its salt, C1-C20 alkyl, C2-C20 thiazolinyl, C2-C20 alkynyl, C6-C30 aryl, C3-C20 naphthenic base, C3-C20 cycloalkenyl group, C3-C20 cycloalkynyl radical, C2-C20 Heterocyclylalkyl, C2-C20 heterocycloalkenyl, C2-C20 heterocycle alkynyl, C3-C30 heteroaryl or their combination, replaces at least one hydrogen.
As used herein, when concrete definition not being provided in addition, term " is mixed " and can be referred in cyclic group, comprise that at least one is selected from the heteroatoms of N, O, S and P.
As used herein, when concrete definition not being provided in addition, " (methyl) acrylic ester " be meant " acrylic ester " and " methacrylate " the two, and " (methyl) acrylic acid " is meant " acrylic acid " and " methacrylic acid ".
Photosensitive resin composition according to an embodiment comprises (A) cardo base resin, (B) active unsaturated compound, (C) pigment, (D) initiating agent and (E) solvent.
Hereinafter, will describe every kind of component in detail.
(A) cardo base resin
Cardo base resin comprises the repetitive that following Chemical formula 1 is represented.
[Chemical formula 1]
In Chemical formula 1,
R
3And R
4Identical or different, and be hydrogen, halogen or replacement or unsubstituted C1 to C20 alkyl,
R
1And R
2Identical or different, and be hydrogen or CH
2OCH
2CR
6R
7R
8(wherein, R
6To R
8Identical or different, be hydrogen or replacement or unsubstituted (methyl) acrylic ester), condition is R
1And R
2In at least one be CH
2OCH
2CR
6R
7R
8(wherein, R
6To R
8Identical or different, be hydrogen or replacement or unsubstituted (methyl) acrylic ester, condition is R
6To R
8In at least one be to replace or unsubstituted (methyl) acrylic ester),
Z
1Be singly-bound, O, CO, SO
2, CR
9R
10, SiR
11R
12(wherein, R
9To R
12Identical or different, and be hydrogen or replacement or unsubstituted C1 to C20 alkyl) or at least one linking group of representing to 2-11 by following Chemical formula 2-1,
Z
2Be acid anhydrides residue or acid dianhydride residue,
[Chemical formula 2-1]
[Chemical formula 2-2]
[Chemical formula 2-3]
[Chemical formula 2-4]
[Chemical formula 2-5]
In Chemical formula 2-5,
R
aBe hydrogen, ethyl, C
2H
4Cl, C
2H
4OH, CH
2CH=CH
2Or phenyl.
[Chemical formula 2-6]
[Chemical formula 2-7]
[Chemical formula 2-8]
[Chemical formula 2-9]
[Chemical formula 2-10]
[Chemical formula 2-11]
Cardo base resin can comprise the R in the Chemical formula 1 wherein
1And R
2The basic resin of substituent cardo that each following naturally chemical formula 3 is represented.
[chemical formula 3]
The repetitive that above Chemical formula 1 is represented is at R
1And R
2The position on comprise at least one (methyl) acrylic ester, especially six (methyl) acrylic ester.Because cardo base resin comprises six (methyl) acrylic ester in each repetitive; Thereby can realize excellent compatibility, developing property, photonasty, tight contact performance and physical strength; And when it is applied to photosensitive resin composition; Because excellent thermotolerance and photostability, making at high temperature works becomes possibility.
Cardo base resin can be in two ends at least one on comprise the end group of following chemical formula 4 expressions.
[chemical formula 4]
In chemical formula 4,
Z
3It is at least one linking group of representing by following chemical formula 5-1 to 5-7.
[chemical formula 5-1]
In chemical formula 5-1, R
bAnd R
cIdentical or different, and be hydrogen, replacement or unsubstituted C1 to C20 alkyl, ester group or ether.
[chemical formula 5-2]
[chemical formula 5-3]
[chemical formula 5-4]
[chemical formula 5-5]
In chemical formula 5-5, R
dBe O, S, NH, replacement or unsubstituted C1-C20 alkyl, C1-C20 alkylamino radical or C2-C20 allyl amido.
[chemical formula 5-6]
[chemical formula 5-7]
The instance of cardo base resin can comprise in the following compound two kinds or more kinds of: contain fluorene compound, and as 9,9-is two-(4-epoxy ethyl methoxyphenyl) fluorenes etc.; Anhydride compound; Like benzene tertacarbonic acid's dianhydride, naphthalene tetracarboxylic acid dianhydride, biphenyl tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride, pyromellitic acid anhydride, cyclo-butane tetracarboxylic dianhydride 、 perylenetetracarboxylic dianhydride (perylene tetracarboxylic dianhydride, perylenetetracarboxylic acid dianhydride), tetrahydrofuran tetracarboxylic dianhydride, tetrabydrophthalic anhydride (tetrahydrophthacid anhydride) etc.; Diol compound is like monoethylene glycol, propylene glycol, polyglycol etc.; Alcoholic compound is like methyl alcohol, ethanol, propyl alcohol, normal butyl alcohol, cyclohexanol, phenmethylol etc.; Solvated compounds is like propylene glycol methyl ether acetate (propylene glycol methyl ether acetate), N-Methyl pyrrolidone etc.; Phosphorus compound is like triphenylphosphine etc.; Amine or ammonium salt compound are like tetramethyl ammonium chloride, tetraethylammonium bromide, benzyl diethylamine, triethylamine, tri-n-butylamine, benzyltriethylammoinium chloride etc.
Cardo base resin can have 1,000 to 50,000g/mol, and particularly 2,000 to 50,000g/mol is more especially 2,000 to 20, the weight-average molecular weight of 000g/mol.When cardo base resin has the weight-average molecular weight in this scope, during the preparation light blocking layer, form the pattern that does not have residue, and not loss of film thickness during developing, thereby obtain good pattern.
Based on the general assembly (TW) of photosensitive resin composition, the amount of the cardo base resin that can comprise is 1-30wt%, particularly 2-20wt%.When included cardo base resin is in this scope, can realize excellent light sensitivity, developing property, thermotolerance, photostability and tight contact performance.
Except that cardo base resin, photosensitive resin composition can also comprise acrylic based resin.
Acrylic based resin be first ethylenically unsaturated monomers with can with the multipolymer of second ethylenically unsaturated monomers of the first ethylenically unsaturated monomers copolymerization, and be the resin that comprises at least one acrylic (acryl-based) repetitive.
First ethylenically unsaturated monomers is alkene class (ethylenic) unsaturated monomer that comprises at least one carboxyl.The instance of this monomer comprises acrylic acid, (methyl) acrylic acid, maleic acid, itaconic acid, fumaric acid or their combination.
Based on the total amount of acrylic based resin, the amount of first ethylenically unsaturated monomers that can comprise is 5-50wt%, particularly 10-40wt%.
The instance of second ethylenically unsaturated monomers can comprise: aromatic ethenyl compound, like styrene, AMS, vinyltoluene, vinyl benzyl methyl ether etc.; Unsaturated carboxylic ester compound is like (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid cinnamic ester, (methyl) butyl acrylate, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxyl butyl ester, (methyl) benzyl acrylate, (methyl) cyclohexyl acrylate, (methyl) phenyl acrylate etc.; The amino alkane ester compounds of unsaturated carboxylic acid is like (methyl) acrylic acid 2-amino ethyl ester, (methyl) acrylic acid 2-dimethylamino ethyl ester etc.; The vinyl esters of carboxylic acids compound is like vinyl acetate, vinyl benzoate etc.; The unsaturated carboxylic acid epihydric alcohol ester compound is like (methyl) glycidyl acrylate etc.; Propylene cyanogen (vinyl cyanide, vinyl cyanide) compound is like (methyl) vinyl cyanide etc.; The unsaturated acyl amines is like (methyl) acrylic amide etc.; Or the like.They can use separately or use with two kinds or more kinds of potpourri.
The instance of acrylic based resin can comprise methacrylic acid/benzyl methacrylate multipolymer, methacrylic acid/benzyl methacrylate/styrol copolymer, methacrylic acid/benzyl methacrylate/2-hydroxyethyl methacrylate multipolymer, methacrylic acid/benzyl methacrylate/styrene/methacrylic acid 2-hydroxy methacrylate multipolymer etc., but is not limited to these.They can use separately or use with two kinds or more kinds of potpourri.
Acrylic based resin can have 3,000 to 150,000g/mol, and particularly 3,000 to 40,000g/mol is more especially 5,000 to 30, the weight-average molecular weight of 000g/mol.Under the situation of the weight-average molecular weight in acrylic based resin has this scope; When photosensitive resin composition is applied to light blocking layer; Photosensitive resin composition has good physics and chemical characteristic, suitable viscosity, and with the tight contact performance (close contacting properties) of substrate.
The acid number scope that acrylic based resin can have is 30 to 200mgKOH/g, and particularly 50 to 180mgKOH/g.During acid number in acrylic based resin has this scope, can realize excellent pixel resolution.
When comprising acrylic based resin in the photosensitive resin composition, the cardo base resin that can exist and the weight ratio of acrylic based resin are 99: 1 to 1: 99, particularly 95: 5 to 50: 50.When comprising cardo base resin and acrylic based resin with this weight ratio, realize excellent developing property and light sensitivity, and can obtain to have the light blocking layer pattern that excellent pattern forms ability, suppress undercutting (undercut) simultaneously and produce.
(B) active unsaturated compound
Active unsaturated compound can be monomer or the oligomer that generally uses in the photosensitive resin composition.It can be (methyl) acrylic acid simple function or the multifunctional ester that comprises at least one alkene class (ethylenic) unsaturated double-bond.
In the pattern forming process, active unsaturated compound owing to alkene class unsaturated double-bond causes abundant polymerization, has excellent heat resistance, photostability and chemical-resistant pattern thereby form when exposure.
The instance of active unsaturated compound can comprise glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, triethylene glycol dimethylacrylate, 1; 6-hexanediyl ester, 1,6-hexanediol dimethacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylic ester, dipentaerythritol acrylate, bisphenol A epoxy acrylate, glycol monoethyl ether acrylic ester, trimethylolpropane triacrylate, three acryloyl ethoxy phosphates etc.
The commercially available instance of active unsaturated compound is following.Simple function (methyl) acrylic ester can comprise Aronix M-
M-
M-
(TOAGOSEI CHEMICAL INDUSTRYCO., LTD.); KAYARAD TC-
TC-
(NIPPON KAYAKU CO., LTD.); V-
V-
(OSAKA ORGANIC CHEMICAL IND., LTD.) etc.The instance of difunctionality (methyl) acrylic ester can comprise Aronix M-
M-
M-
(TOAGOSEI CHEMICAL INDUSTRY CO.; LTD.), KAYARAD
HX-
R-
(NIPPON KAYAKU CO.; LTD.), V-
V-
V-335
(OSAKA ORGANIC CHEMICAL IND., LTD.) etc.The instance of trifunctional (methyl) acrylic ester can comprise Aronix M-
M-
M-
M-
M-
M-
M-
(TOAGOSEI CHEMICALINDUSTRY CO.; LTD.), KAYARAD
DPCA-
DPCA-
DPCA-
DPCA-
(NIPPON KAYAKU CO.; LTD.), V-
V-
V-
V-
V-
V-
(OSAKA YUKI KAYAKU KOGYO CO., LTD.) etc.Active unsaturated compound can use separately or use with two kinds or more kinds of potpourris.
Can handle active unsaturated compound to improve developing property with acid anhydrides.
Based on the total amount of photosensitive resin composition, the amount of the active unsaturated compound that can comprise is 1-30wt%, particularly 1-15wt%.When included active unsaturated compound is in this scope, in the pattern forming process, solidifies during exposure and fully carry out, and can realize reliability, thermotolerance, photostability and chemical resistance, resolution and the tight contact performance of pattern.
(C) pigment
Pigment can be organic pigment or inorganic pigment.
Pigment can comprise red, green pigment, blue pigment, yellow pigment, mineral black etc.
The instance of red comprises C.I. red 254, C.I. red 255, C.I. red 264, C.I. red 270, C.I. red 272, C.I. red 177, C.I. red 89 etc.The instance of green pigment comprises the substituted copper phthalocyanine of halogen, like C.I. green pigment 36, C.I. green pigment 7 etc.The instance of blue pigment comprises copper phthalocyanine, like the blue pigment 15:6 of C.I., the blue pigment 15 of C.I., the blue pigment 15:1 of C.I., the blue pigment 15:2 of C.I., the blue pigment 15:3 of C.I., the blue pigment 15:4 of C.I., the blue pigment 15:5 of C.I., the blue pigment 16 of C.I. etc.The instance of yellow pigment comprises isoindoline pigment such as C.I. yellow pigment 139 etc., quinophthalone pigment such as C.I. yellow pigment 138 etc., nickel complex pigment such as C.I. yellow pigment 150 etc.The instance of mineral black comprises that nigrosine (aniline black), perylene black (perylene black), titanium are black, carbon black etc.Above-mentioned pigment can use separately or use with two kinds or more kinds of potpourri, and is not limited to the pigment of above description.
Wherein, for the light of realizing light blocking layer effectively blocks (being in the light property, light blocking), can comprise mineral black.When using mineral black, can also use color calibration agent (color calibrating agent), like anthraquinonyl pigment, perylene base pigment, phthalocyanine base pigment, azo group pigment etc.
In order to improve pigment dispersing, photosensitive resin composition can also comprise spreading agent.
Particularly, can carry out surface preparation to pigment, perhaps can during the preparation photosensitive resin composition, add pigment and spreading agent together with spreading agent.
Spreading agent can comprise non-ionic dispersing agent, anionic dispersing agents, cation dispersing agent etc.The instance of spreading agent comprises PAG and ester thereof, polyoxyalkylene (polyglycol), polyol ester oxyalkylene addition compound product (polyhydric alcohol ester alkylene oxide addition product), pure oxyalkylene addition compound product (alcohol alkylene oxide addition product), sulphonic acid ester, sulphonate, carboxylate, carboxylate, alkylamide oxyalkylene addition compound product, alkyl amine etc., but is not limited to these.Above-mentioned spreading agent can use separately or use with two kinds or more kinds of potpourri.
The commercially available instance of spreading agent is following: (BYK) such as DISPERBYK-101, DISPERBYK-130, DISPERBYK-140, DISPERBYK-160, DISPERBYK-161, DISPERBYK-162, DISPERBYK-163, DISPERBYK-164, DISPERBYK-165, DISPERBYK-166, DISPERBYK-170, DISPERBYK-171, DISPERBYK-182, DISPERBYK-2000, DISPERBYK-2001; (EFKAchemicals) such as EFKA-47, EFKA-47EA, EFKA-48, EFKA-49, EFKA-100, EFKA-400, EFKA-450; (Zeneka) such as Solsperse 5000, Solsperse 12000, Solsperse 13240, Solsperse13940, Solsperse 17000, Solsperse 20000, Solsperse 24000GR, Solsperse27000, Solsperse 28000; Or PB711, PB821 etc. (Ajinomoto).
Based on the total amount of photosensitive resin composition, the amount of the spreading agent that can comprise is 0.01 to 10wt%.When included spreading agent is in above-mentioned scope, improved the dispersion of photosensitive resin composition, cause excellent stability, developing property and patterning characteristic during the preparation light blocking layer.
Based on the total amount of photosensitive resin composition, the amount of the pigment that can comprise is 1 to 30wt%, and particularly 2 to 20wt%.When included pigment was in above-mentioned scope, the colorrendering quality of pattern (color reproducibility), ability to cure and tight contact performance all were excellent.
(D) initiating agent
Initiating agent can be Photoepolymerizationinitiater initiater, radical polymerization initiator or their combination.
Photoepolymerizationinitiater initiater can be the initiating agent that generally uses in the photosensitive resin composition, like acetophenone (acetophenone) based compound, benzophenone based compound, thioxanthones based compound, styrax (diphenylhydroxyethanone) based compound, triazine-based compound etc.
Acetophenone based compound (acetophenone-based compound) comprises 2; 2 '-diethoxy acetophenone, 2; 2 '-dibutoxy acetophenone, 2-hydroxy-2-methyl propiophenone, to tert-butyl group trichloroacetophenone, to tert-butyl group dichloroacetophenone, 4-chloro-acetophenone, 2,2 '-two chloro-4-metaphenoxy acetophenones, 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone etc.
Benzophenone based compound (benzophenone-based compound) comprises benzophenone, benzoylbenzoic acid ester, benzoylbenzoic acid methyl esters (benzoyl methyl benzoate), 4-phenyl benzophenone, dihydroxy benaophenonel, acroleic acid esterification benzophenone (acrylated benzophenone), 4; 4 '-two (dimethylamino) benzophenone, 4; 4 '-two (diethylamino) benzophenone, 4; 4 '-dimethylamino benzophenone, 4; 4 '-dichloro benzophenone, 3,3 '-dimethyl-2-methoxy benzophenone etc.
Thioxanthones based compound (thioxanthone-based compound) comprises thioxanthones, 2-methyl thioxanthones, isopropyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropyl thioxanthones, 2-clopenthixal ketone etc.
Styrax based compound (benzoin-based compound) comprises styrax, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal etc.
Triazine-based compound (triazine-based compound) comprises 2; 4,6-three chloro-s-triazines, 2-phenyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-(3 '; 4 '-dimethoxy-styryl)-4; Two (the trichloromethyl)-s-triazines of 6-, 2-(4 '-methoxyl naphthyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-methoxyphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-methylphenyl)-4; Two (the trichloromethyl)-s-triazines of 6-, 2-xenyl 4; Two (the trichloromethyl)-s-triazines of 6-, two (trichloromethyl)-6-styryl-s-triazine, 2-(naphthols-1-yl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-methoxynaphthol-1-yl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-4-trichloromethyl (piperonyl)-6-triazine, 2-4-trichloromethyl (4 '-methoxyl-styrene)-6-triazine etc.
Photoepolymerizationinitiater initiater can also comprise carbazyl compound, diketo compound, boric acid sulfonium (sulfonium borate) based compound, diazo compound, bisglyoxaline based compound etc.
Radical polymerization initiator can comprise superoxide based compound, azo double-basis compound (azobis-based compound) etc.
The instance of superoxide based compound (peroxide-based compound) comprises the peroxidating ketone, like methyl ethyl ketone peroxide, peroxidating methyl isobutyl ketone, cyclohexanone peroxide, peroxidating methyl cyclohexanone, diacetone peroxide etc.; Peroxidating two acyl classes, like peroxidating isobutyryl, peroxidating 2,4-dichloro-benzoyl, peroxidating o-methyl-benzene formyl, peroxidating are two-3,5,5-trimethyl acetyl etc.; Hydroperoxide kind, as 2,4,4-tri-methyl-amyl-2-hydrogen peroxide, diisopropylbenzyl hydrogen peroxide, cumene hydroperoxide hydrogen, TBHP etc.; The dialkyl peroxide class, like cumyl peroxide, 2,5-dimethyl-2,5-two (t-butyl peroxy) hexane, 1,3-is two-(tert-butoxy isopropyl) benzene, t-butyl peroxy n-butyl pentanoate etc.; Alkyl super-acid ester, as 2,4,4-tri-methyl-amyl peroxide phenoxyacetic acid ester, α-cumenyl peroxide neodecanoic acid ester, t-butyl peroxy benzoic ether, di-t-butyl peroxide trimethyladipic acid ester etc.; Peroxocarbonate is like two-3-methoxyl butyl peroxy, two carbonic esters, two-2-ethylhexyl peroxide, two carbonic esters, two-4-tert-butylcyclohexyl peroxide two carbonic esters, diisopropyl peroxydicarbonate, acetyl cyclohexyl sulfonyl-peroxide, t-butyl peroxy aryl carbonates etc.
The instance of azo double-basis compound (azobis-based compound) comprises 1,1 '-azo bis cyclohexane-1-nitrile, 2,2 '-azo two (2; The 4-methyl pentane nitrile), 2; 2-azo two (methyl isobutyrate), 2,2 '-azo two (4-methoxyl-2,4-methyl pentane nitrile), α; α '-azo two (isobutyronotrile) and 4,4 '-azo two (4-cyanopentanoic acid) etc.
Owing to the initiating agent absorbing light is excited, transmit energy subsequently, it can use and initiating chamical reaction with photosensitizer (photo sensitizer).
The instance of photosensitizer comprise TEG two-3-mercapto propionate (ester), pentaerythrite four-3-mercapto propionate (ester), dipentaerythritol four-3-mercapto propionate (ester) etc.
Based on the total amount of photosensitive resin composition, the amount of the initiating agent that can comprise is 0.01wt% to 10wt%, and particularly 0.1 to 5wt%.When included initiating agent is in this scope;, realizing by pattern fully curing under the exposure during forming; Thereby obtain excellent reliability, thermotolerance, photostability and chemical resistance, resolution and tight contact performance, simultaneously because non-reaction initiator causes transmissivity can not descend.
(E) solvent
Solvent and cardo base resin, active unsaturated compound, pigment are compatible with initiating agent, but with they reactions.
The instance of solvent can comprise alcohols, like methyl alcohol, ethanol etc.; Ethers is like dichloroethyl ether, n-butyl ether, isoamyl ether, methyl phenyl ether, tetrahydrofuran etc.; Glycol ethers (glycol ethers) is like glycol monoethyl ether, ethylene glycol monoethyl ether etc.; Cellosolve acetate (cellosolve acetic acid esters, cellosolve acetates) class is like methylcellosolve acetate, ethyl cellosolve acetate, ethylene glycol diethyl ether acetic acid esters etc.; The carbitol class is like Methylethyl carbitol, diethyl carbitol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether etc.; Propylene glycol alkyl ether acetic acid ester class is like propylene glycol methyl ether acetate, propylene glycol propyl ether acetic acid esters etc.; Aromatic hydrocarbon is like toluene, xylene etc.; Ketone is like methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2 pentanone, methyl-n-pro-pyl ketone, methyl-normal-butyl ketone, methyl-n-amyl ketone, 2-heptanone etc.; Radical of saturated aliphatic monocarboxylic acid Arrcostab is like ethyl acetate, n-butyl acetate, isobutyl acetate etc.; The lactic acid alkyl ester class is like methyl lactate, ethyl lactate etc.; Glycolic alkyl esters (hydroxyacetic acid alkyl esters) is like glycolic methyl esters, glycolic ethyl ester, glycolic butyl ester etc.; Acetate alkoxy alkyl class (acetic acid alkoxyalkyl esters) is like acetate methoxyl methyl esters, acetate methoxyl ethyl ester, methoxy butyl acetate, acetate ethoxy methyl esters, ethoxyethyl acetate(EA) etc.; 3-hydracrylic acid alkyl esters (3-hydroxypropionic acid alkyl esters) is like 3-hydroxy methyl propionate, 3-hydracrylic acid ethyl ester etc.; 3-alkoxypropan acid alkyl ester class (3-alkoxypropionic acid alkyl esters) is like 3-methoxypropionic acid methyl esters, 3-methoxy propyl acetoacetic ester, 3-ethoxyl ethyl propionate, 3-ethoxy-propionic acid methyl esters etc.; 2 hydroxy propanoic acid alkyl esters (2-hydroxypropionic acid alkyl esters) is like 2 hydroxy propanoic acid methyl esters, 2 hydroxy propanoic acid ethyl ester, 2 hydroxy propanoic acid propyl ester etc.; 2-alkoxypropan acid alkyl ester class (2-alkoxypropionic acid alkyl esters) is like 2-methoxypropionic acid methyl esters, 2-methoxy propyl acetoacetic ester, 2-ethoxyl ethyl propionate, 2-ethoxy-propionic acid methyl esters etc.; 2-oxygen-2 Methylpropionic acid alkyl esters is like 2-hydroxy-2-methyl methyl propionate, 2-hydroxy-2-methyl ethyl propionate etc.; 2-alkoxy-2 Methylpropionic acid alkyl esters is like 2-methoxyl-2 Methylpropionic acid methyl esters, 2-ethoxy-2 Methylpropionic acid ethyl ester etc.; The ester class is like 2 hydroxy propanoic acid ethyl ester, 2-hydroxy-2-methyl ethyl propionate, hydroxyl ethyl acetate, 2-hydroxy-3-methyl methyl butyrate etc.; Keto ester class (ketonic acid esters) is like ethyl pyruvate; Or the like, and their combination.In addition; Solvent can be N-NMF, N; Dinethylformamide, N-methyl formyl aniline, N-methylacetamide, DMAC N,N, N-Methyl pyrrolidone, dimethyl sulfoxide, benzylisoeugenol, two hexyl ethers, diacetone, isophorone, caproic acid, sad, 1-octanol, 1 nonyl alcohol, benzylalcohol, benzyl acetate, ethyl benzoate, diethy-aceto oxalate, diethyl maleate, gamma-butyrolacton, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetic acid esters etc.These solvents can be used alone or in combination.
Consider compatibility and reactivity, glycol ethers preferably is like ethylene glycol monoethyl ether etc.; Monoethylene glycol alkyl ether acetate esters is like ethyl cellosolve acetate etc.; The ester class is like 2 hydroxy propanoic acid ethyl ester etc.; The carbitol class is like diethylene glycol monomethyl ether etc.; Propylene glycol alkyl ether acetic acid ester class is like propylene glycol methyl ether acetate, propylene glycol propyl ether acetic acid esters etc.
The use amount of solvent is a surplus, and particularly based on the photosensitive resin composition total amount 20 to 95wt%.When included solvent was in this scope, photosensitive resin composition can have suitable viscosity, thereby caused the light blocking layer processability to improve.
(F) other adjuvant
Photosensitive resin composition can also comprise that epoxy compound is with the tight contact performance of raising with substrate.
The instance of epoxy compound comprises phenolic aldehyde epoxy compound (phenol novolac epoxy compound), tetramethyl biphenyl epoxy compound, bisphenol-A epoxy compound, alicyclic epoxide compound or their combination.
Based on the photosensitive resin composition of 100 weight portions, the amount of the epoxy compound that can comprise is 0.01 to 5 weight portion, particularly 0.1 to 5 weight portion.When included epoxy compound is in above-mentioned scope, can improve tight contact performance, thermotolerance and chemical resistance.
Photosensitive resin composition can also comprise have active substituent such as carboxyl, the silane coupling agent of methacryl, isocyanate group (isocyanate group), epoxy radicals etc., to improve adhering to substrate.
The instance of silane coupling agent comprises trimethoxysilyl benzoic acid, γ-methacryloxypropyl trimethoxy silane, vinyltriacetoxy silane, vinyltrimethoxy silane, γ-isocyanic acid propyl-triethoxysilicane, γ-glycidoxypropyltrimewasxysilane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane etc.These coupling agents can use separately or use with two kinds or more kinds of potpourri.
Based on the photosensitive resin composition of 100 weight portions, the amount of the silane coupling agent that can comprise is 0.01 to 10 weight portion.When included silane coupling agent is in above-mentioned scope, improve tight contact performance, storage characteristics etc.
Photosensitive resin composition can also comprise surfactant, applies characteristic and suppresses dirty (spots) to improve.
The instance of surfactant can comprise fluorine based surfactant; As, BM-
and BM-
(BM Chemie Inc.); MEGAFACE F
F
F
and F
DAINIPPON INK KAGAKU KOGYO CO., LTD.); FULORADFC-
FULORAD FC-
FULORAD FC-
and FULORADFC-
(SUMITOMO 3M CO., LTD.); SURFLON S-
SURFLONS-
SURFLON S-
SURFLON S-
and SURFLON S-
(ASAHIGLASS CO., LTD.); And SH-
SH-
SH-
SZ-
and SF-
etc. (TORAY SILICONE CO., LTD.).
Based on the photosensitive resin composition of 100 weight portions, the amount of the surfactant that can comprise is 0.001 to 5 weight portion.When included surfactant is in above-mentioned scope, can guarantee to apply homogeneity, can not produce stain, and improve wetting property glass substrate.
When their characteristics reduced, photosensitive resin composition can also comprise adjuvant such as anti-oxidant, the stabilizing agent etc. of other scheduled volume.
According to another embodiment, the light blocking layer that uses the photosensitive resin composition preparation is provided.Can be prepared as follows light blocking layer.
(1) uses with film and form
Adopt spin-coating method or slot coated method, rolling method, silk screen print method, applicator method (to apply the device method; Applicator method) etc.; The aforementioned lights photosensitive resin composition is coated in through on the predetermined pretreated substrate, reaches the thickness of expectation, like the thickness of 0.5 to 25 mu m range.Desolvate to remove through the substrate that applies 1 to 10 minute with the heating of the temperature of 70 to 110 ℃ of scopes then.
(2) exposure
After placement had the mask of reservation shape, the film that the dynamic rays with 190 to 500nm (active ray) irradiation obtains was to form the pattern of expectation.Through using light source such as low pressure, high pressure or ultrahigh pressure mercury lamp, metal halide lamp, argon laser etc. to carry out irradiation.Yet, according to circumstances also can use X ray, electron beam etc.
When using high-pressure sodium lamp, exposure technology is used, as, 500mJ/cm
2Or light dosage still less (using the 365nm sensor).Yet light dosage can depend on kind, its combination ratio and the build of every kind of component of photosensitive resin composition and change.
(3) develop
After the exposure process, use alkaline aqueous solution, through dissolving and removing the unnecessary part (redundance, unnecessary part) outside the exposed portion, the film of the exposure of developing is to form picture pattern (image model, image pattern).
Developing solution can be organic solvent type and alkali-developable (alkali-developing type).Organic solvent type solution can cause environmental pollution and harmful.Therefore, aspect environment, alkali-developable solution is preferred.According to an embodiment, environment for use close friend's alkaline aqueous solution is as developing solution.The alkaline aqueous solution neutralization is present in the carboxylic acid in the cardo base resin, and therefore dissolves cardo base resin.
(4) aftertreatment
In order to realize thermotolerance, photostability, the tight excellent specific property of aspects such as contact performance, anti-fragility, chemical resistance, high strength, storage stability, can heat once more or the picture pattern that develops through irradiation such as dynamic rayses is cured.
Therefore, the aforementioned lights photosensitive resin composition can produce the insulativity and the optical density of the required excellence of light blocking layer.
Hereinafter, will illustrate in greater detail the present invention with reference to embodiment.Yet these are illustrative embodiments of the present invention, and nonrestrictive.
The preparation of preparation instance 1:cardo base resin
(1) 29.8g pentaerythritol triacrylate (Sigma-Aldrich Co.) and 35.43g propylene glycol methyl ether acetate (Daicel Chemical Industries Ltd.) are placed reactor, and be heated to 50 ℃.Then, wherein add a small amount of 6.8g caustic alcohol (sodium ethoxide) (Sigma-Aldrich Co.) 30 minutes introversions, and to wherein adding 9.3g chloropropylene oxide (3-chloro-1,2-epoxypropane, epichlorohydrine) (Sigma-Aldrich Co.).With this mixture heated to 80 ℃, and kept 3 hours, then, filter the compound that this potpourri is represented with synthetic following chemical formula 6-1 at uniform temp.
[chemical formula 6-1]
(2) with 35g 9; 9 '-two (4-hydroxyphenyl) fluorenes (Hearchem Co.; Ltd.), the compound, 0.23g benzyltriethylammoinium chloride (the Daejung Chemicals & Metals Co. that represent of the above-mentioned chemical formula 6-1 of 141.6g; Ltd.) and 0.23g triphenylphosphine (Sigma-Aldrich Co.) place reactor, be heated to 90 ℃ and under uniform temp, keep the compound represented with synthetic following chemical formula 6-2 in 12 hours then.
[chemical formula 6-2]
(Mitsubishi Gas Chemical Co. Ltd.) places reactor with 1.1g tetrabydrophthalic anhydride (Sigma-Aldrich Co.) for compound, 2.1g biphenyl tetracarboxylic dianhydride that the above-mentioned chemical formula 6-2 of 30g is represented.(weight-average molecular weight is 5 to the compound that keeps with this mixture heated to 120 ℃ and under uniform temp representing with synthetic following chemical formula 6-3 in 2 hours, 400g/mol).
[chemical formula 6-3]
Preparation instance 2: the preparation of red dispersion
With 15g C.I. red 254 (Ciba-Geigy Ltd.), 4g DISPERBYK-163 (BYKAdditives & Instruments), 3g acrylic acid/benzyl methacrylate multipolymer (Miwon Commercial Co; Ltd., NPR8000) and the 78g propylene glycol methyl ether acetate in reactor, mix.(Asada Iron Works Co. Ltd.) disperseed this potpourri 12 hours, preparation red dispersion soln to use coating stirrer (paint-shaker).
Preparation instance 3: the preparation of mineral black dispersion
With 15g carbon black (Cabot Co.), 4g DISPERBYK-163 (BYK Additives &Instruments), 3g acrylic acid/benzyl methacrylate multipolymer (NPR8000; Miwon Commercial Co, Ltd.) and the 78g propylene glycol methyl ether acetate place reactor.(Asada Iron Works Co. Ltd.) disperseed this potpourri 12 hours, preparation mineral black dispersion soln to use the coating stirrer.
Preparation makes them comprise the following component that provides in the following table 1 according to embodiment 1 and 2 and the various photosensitive resin compositions of comparative example 1 to 4.
Especially, initiating agent is dissolved in the solvent.At room temperature agitating solution is 2 hours.Then, in solution, add adhesive resin and active unsaturated compound.At room temperature stirred this potpourri 2 hours.Then, will join in the reactant according to the red dispersion soln of preparation instance 1 or according to the mineral black dispersion soln and the silane coupling agent that prepare instance 2.The potpourri that stirring at room temperature obtains 1 hour.Then, filter this product three times to remove impurity, the preparation photosensitive resin composition.
(A) adhesive resin
(A-1) use compound that the chemical formula 6-3 according to preparation instance 1 representes as cardo base resin.
(A-2) (NPR8000, Miwon Commercial Co is Ltd.) as acrylic based resin to use acrylic acid/benzyl methacrylate multipolymer.
(A-3), use the V259ME of Nippon Steel Chemical Co. preparation as for cardo base resin.
(B) active unsaturated compound
Use dipentaerythritol acrylate.
(C) pigment dispersing solution
(C-1) use according to the red dispersion soln for preparing instance 2.Here, based on the total amount of red dispersion soln, the amount of included pigment solids is 15wt%.
(C-2) use according to the mineral black dispersion soln for preparing instance 3.Here, based on the total amount of mineral black dispersion soln, the amount of included pigment solids is 15wt%.
(D) initiating agent
Use the IRGACURE OXE02 of Ciba Geigy Ltd. preparation.
(E) solvent
Use propylene glycol methyl ether acetate.
(F) adjuvant
Use γ-glycidoxypropyltrimewasxysilane (S-510, Chisso Co) as silane coupling agent.
(table 1)
(unit: wt%)
Mark * representes based on (C-1) the red dispersion soln or (C-2) amount of the pigment solids of mineral black dispersion soln total amount.
Estimate 1: developing property
With spinner (KDNS; K-Spin8) silicon chip (silicon wafer) (LG Siltron) go up to apply according to embodiment 1 and 2 and every kind of photosensitive resin composition of comparative example 1-4 reach the thickness of 0.8 μ m; Then, with exposer (Nikon, I10C) exposure 350ms.Then; Use developer (developer) (SSP-200; SVS Corp.); With (TMAH) WS product that develops and made public of the tetramethylammonium hydroxide (tetramethylammonium hydroxide) of 0.2wt%, when applying this WS and when coated film begins to develop, reference time difference evaluation developing property.In the following table 2 result is provided.
< developing property evaluation >
Zero: less than 20 seconds
△: greater than 20 seconds and less than 30 seconds
*: greater than 30 seconds
Estimate 2: residue
Upward apply the thickness that reaches 0.8 μ m according to every kind of photosensitive resin composition of embodiment 1, comparative example 1 and comparative example 3 with spinner (K-Spin8, KDNS Inc.) at silicon chip (LG Siltron Inc.), and with exposer (I10C, Nikon Co.) exposure 350ms.Then, use developer (SSP-200, SVS Corp.), develop the film that made public with the formation pattern with tetramethylammonium hydroxide (TMAH) WS of 0.2wt%.Then, use CD scanning electron microscope analysis appearance (8100XP, KLA-Tencor Co.) to check whether these patterns have residue to estimate it.In the following table 2 result is provided.In addition,, whether have residue, estimate the film that is developed through checking it through the CD electron scanning micrograph among Fig. 1 to 3.
Fig. 1 is the electron scanning micrograph that illustrates according to the residue of the photosensitive resin composition of embodiment 1; Fig. 2 is the electron scanning micrograph that illustrates according to the residue of the photosensitive resin composition of comparative example 3, and Fig. 3 is the electron scanning micrograph that illustrates according to the residue of the photosensitive resin composition of comparative example 1.
< residue evaluation >
Zero: smooth pattern as shown in fig. 1
△: small amount of residue as shown in Figure 2
*: abundant residues thing as shown in Figure 3
Referring to figs. 1 through 3, has the smooth surface of no residue according to the photosensitive resin composition of embodiment 1.Photosensitive resin composition according to comparative example 1 and 3 has residue.
Estimate 3: pattern forms characteristic
Use spinner, on glass substrate, apply according to embodiment 1 with 2 and the photosensitive resin composition of comparative example 1 to 4 reach the height of 1.5 μ m, then, use patterned mask and exposer (USHIO Inc.) are exposed to 45mJ/cm with it
2Light under.Down develop coated glass 1 minute of the WS of 1wt% potassium hydroxide is arranged at 23 ℃, use pure water (pure water, pure water) cleaning 1 minute then with dilution.The high pattern of this 1.5 μ m of heating 30 minutes is to be cured in 220 ℃ baking oven.Use the shape of scanning electronic microscope examination institute cured pattern.Among following table 2 and Fig. 4 to 7 result is provided.
Fig. 4 illustrates the electron scanning micrograph that forms characteristic according to the pattern of the photosensitive resin composition of embodiment 2; Fig. 5 illustrates the electron scanning micrograph that forms characteristic according to the pattern of the photosensitive resin composition of embodiment 1; Fig. 6 illustrates the electron scanning micrograph that forms characteristic according to the pattern of the photosensitive resin composition of comparative example 3, and Fig. 7 illustrates the electron scanning micrograph that forms characteristic according to the pattern of the photosensitive resin composition of comparative example 2.
< pattern formation characteristic >
◎: excellent pattern as shown in Figure 4 forms characteristic
Zero: good pattern as shown in Figure 5 forms characteristic
△: the pattern of difference as shown in Figure 6 forms characteristic
*: as shown in Figure 7 do not have a pattern
With reference to Fig. 4 to 7, form excellent pattern according to the photosensitive resin composition of embodiment 1 and 2, then do not form good pattern according to those of comparative example 2 and 3.
Estimate 4: thread pattern forms evaluating characteristics
Forming under the identical condition of characteristic with being used for evaluation pattern generating, using photosensitive resin composition to form pattern according to embodiment 2 and comparative example 2 and 4.Use the light microscopy pattern to estimate its minimum dimension.Among following table 2 and Fig. 8 to 10 result is provided.
Fig. 8 is the optical microscope photograph that illustrates according to the pattern dimension of the photosensitive resin composition of embodiment 2; Fig. 9 is the optical microscope photograph that illustrates according to the pattern dimension of the photosensitive resin composition of comparative example 2, and Figure 10 is the optical microscope photograph that illustrates according to the pattern dimension of the photosensitive resin composition of comparative example 4.
With reference to Fig. 8 to 10, have the minimum pattern size of 7 μ m according to the photosensitive resin composition of embodiment 2, then have the minimum pattern size of 9 μ m according to those of comparative example 2 and 4.
(table 2)
| Developing property | Residue | Pattern forms characteristic | Minimum pattern size (μ m) | |
| |
○ | ○ | ○ | - |
| Embodiment 2 | ○ | ○ | ◎ | 7 |
| Comparative example 1 | × | × | ○ | - |
| Comparative example 2 | × | × | × | 9 |
| Comparative example 3 | ○ | △ | △ | - |
| Comparative example 4 | △ | ○ | ○ | 9 |
With reference to table 2 and Fig. 1 to 10; With compare with 2 photosensitive resin compositions and have with the photosensitive resin composition of cardo base resins of the cardo that uses of institute base resin different structure among the embodiment 1 and 2 through use through using the acrylic based resin preparation according to comparative example 1 according to comparative example 3 and 4, demonstrate developing property, residue and the pattern formation characteristic of excellence with 2 through the photosensitive resin compositions that use the basic resins of cardo according to embodiment 1.
Although described disclosure of the present invention with reference to being considered to put into practice exemplary embodiment at present; But be to be understood that; The invention is not restricted to disclosed embodiment; On the contrary, the present invention is intended to contain various modifications and is equal to arrangement, and they include in the spirit and scope of accompanying claims.Aforementioned embodiments is exemplary, limits never in any form.
Claims (11)
1. photosensitive resin composition comprises:
(A) comprise the cardo base resin of the repetitive that following Chemical formula 1 is represented;
(B) active unsaturated compound;
(C) pigment;
(D) initiating agent; With
(E) solvent:
[Chemical formula 1]
Wherein, in Chemical formula 1,
R
3And R
4Identical or different, and be hydrogen, halogen or replacement or unsubstituted C1 to C20 alkyl,
R
1And R
2Identical or different, and be hydrogen or CH
2OCH
2CR
6R
7R
8, wherein, R
6To R
8Identical or different, be hydrogen or replacement or unsubstituted (methyl) acrylic ester, condition is R
1And R
2In at least one be CH
2OCH
2CR
6R
7R
8, wherein, R
6To R
8Identical or different, be hydrogen or replacement or unsubstituted (methyl) acrylic ester, and R
6To R
8In at least one be to replace or unsubstituted (methyl) acrylic ester,
Z
1Be singly-bound, O, CO, SO
2, CR
9R
10, SiR
11R
12, or at least one linking group of representing to 2-11 by following Chemical formula 2-1, wherein, R
9To R
12Identical or different, and be hydrogen or replacement or unsubstituted C1 to C20 alkyl,
Z
2Be acid anhydrides residue or acid dianhydride residue,
m
1And m
2Be the integer of scope 0 to 4 independently, and n is 1 to 1000 integer,
[Chemical formula 2-1]
[Chemical formula 2-2]
[Chemical formula 2-3]
[Chemical formula 2-4]
[Chemical formula 2-5]
Wherein, in Chemical formula 2-5,
R
aBe hydrogen, ethyl, C
2H
4Cl, C
2H
4OH, CH
2CH=CH
2Or phenyl,
[Chemical formula 2-6]
[Chemical formula 2-7]
[Chemical formula 2-8]
[Chemical formula 2-9]
[Chemical formula 2-10]
[Chemical formula 2-11]
2. photosensitive resin composition according to claim 1, wherein, said cardo base resin has 1,000 to 50, the weight-average molecular weight of 000g/mol.
3. photosensitive resin composition according to claim 1 wherein, comprises the end group of following chemical formula 4 expressions at least one in two ends of said cardo base resin:
[chemical formula 4]
Wherein, in chemical formula 4,
Z
3Be at least one linking group of representing by following chemical formula 5-1 to 5-7:
[chemical formula 5-1]
Wherein, in chemical formula 5-1, R
bAnd R
cIdentical or different, and be hydrogen, replacement or unsubstituted C1 to C20 alkyl, ester group or ether,
[chemical formula 5-2]
[chemical formula 5-3]
[chemical formula 5-4]
[chemical formula 5-5]
Wherein, in chemical formula 5-5, R
dBe O, S, NH, replacement or unsubstituted C1 to C20 alkyl, C1 to C20 alkylamino radical or C2 to C20 allyl amido,
[chemical formula 5-6]
[chemical formula 5-7]
4. photosensitive resin composition according to claim 1, wherein, said photosensitive resin composition comprises:
1 to 30wt% said cardo base resin (A);
1 to 30wt% said active unsaturated compound (B);
1 to 30wt% said pigment (C);
0.01 said initiating agent (D) to 10wt%; And
The said solvent (E) of surplus.
5. photosensitive resin composition according to claim 1, wherein, said photosensitive resin composition also comprises acrylic based resin.
6. photosensitive resin composition according to claim 5; Wherein, Said acrylic based resin comprises the multipolymer of first ethylenically unsaturated monomers and second ethylenically unsaturated monomers, and wherein first ethylenically unsaturated monomers is (methyl) acrylic acid, maleic acid, itaconic acid, fumaric acid or their combination; Second ethylenically unsaturated monomers is a styrene; AMS; Vinyltoluene; The vinyl benzyl methyl ether; (methyl) methyl acrylate; (methyl) ethyl acrylate; (methyl) butyl acrylate; (methyl) acrylic acid 2-hydroxy methacrylate; (methyl) acrylic acid 2-hydroxyl butyl ester; (methyl) benzyl acrylate; (methyl) cyclohexyl acrylate; (methyl) phenyl acrylate; (methyl) acrylic acid 2-amino ethyl ester; (methyl) acrylic acid 2-dimethylamino ethyl ester; Vinyl acetate; Vinyl benzoate; (methyl) glycidyl acrylate; (methyl) vinyl cyanide; (methyl) acrylic amide; Or their combination.
7. photosensitive resin composition according to claim 5, wherein, said acrylic based resin has 3,000 to 40, the weight-average molecular weight of 000g/mol.
8. photosensitive resin composition according to claim 5, wherein, the included said cardo base resin and the weight ratio of said acrylic based resin are 99: 1 to 30: 70.
9. photosensitive resin composition according to claim 1, wherein, said initiating agent comprises Photoepolymerizationinitiater initiater, radical polymerization initiator or their combination.
10. photosensitive resin composition according to claim 1, wherein, based on the said photosensitive resin composition of 100 weight portions, said photosensitive resin composition comprises the epoxy compound of 0.01 to 20 weight portion.
11. use light blocking layer according to each described photosensitive resin composition preparation in the claim 1 to 10.
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| KR1020100099925A KR101319919B1 (en) | 2010-10-13 | 2010-10-13 | Photosensitive resin composition and black matrix using the same |
| KR10-2010-0099925 | 2010-10-13 |
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| CN104570604A (en) * | 2013-10-23 | 2015-04-29 | 第一毛织株式会社 | Photosensitive Resin Composition and Light Blocking Layer Using the Same |
| CN112859521A (en) * | 2019-11-28 | 2021-05-28 | 德山新勒克斯有限公司 | Photosensitive resin composition and display device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9341946B2 (en) | 2012-05-25 | 2016-05-17 | Lg Chem, Ltd. | Photosensitive resin composition, pattern formed using same and display panel comprising same |
| CN103885291A (en) | 2012-12-21 | 2014-06-25 | 第一毛织株式会社 | Photosensitive resin composition and light blocking layer using the same |
| KR101767082B1 (en) | 2014-11-17 | 2017-08-10 | 삼성에스디아이 주식회사 | Photosensitive resin composition, photosensitive resin film using the same and color filter |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1606597A (en) * | 2002-01-25 | 2005-04-13 | 住友电木株式会社 | Transparent composite composition |
| WO2010038978A2 (en) * | 2008-09-30 | 2010-04-08 | Kolon Industries, Inc. | Photopolymer resin composition |
| CN101770172A (en) * | 2008-12-31 | 2010-07-07 | 第一毛织株式会社 | Organic layer photosensitive resin composition and organic layer fabricated using same |
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| TWI397769B (en) * | 2006-11-30 | 2013-06-01 | Nippon Steel Chemical Co | Alkali-soluble resin and method for producing the same, and a photosensitive resin composition, a hardened product and a color filter using an alkali-soluble resin |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1606597A (en) * | 2002-01-25 | 2005-04-13 | 住友电木株式会社 | Transparent composite composition |
| WO2010038978A2 (en) * | 2008-09-30 | 2010-04-08 | Kolon Industries, Inc. | Photopolymer resin composition |
| CN101770172A (en) * | 2008-12-31 | 2010-07-07 | 第一毛织株式会社 | Organic layer photosensitive resin composition and organic layer fabricated using same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104570604A (en) * | 2013-10-23 | 2015-04-29 | 第一毛织株式会社 | Photosensitive Resin Composition and Light Blocking Layer Using the Same |
| CN112859521A (en) * | 2019-11-28 | 2021-05-28 | 德山新勒克斯有限公司 | Photosensitive resin composition and display device |
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| CN102445842B (en) | 2014-10-29 |
| KR20120045076A (en) | 2012-05-09 |
| TWI414539B (en) | 2013-11-11 |
| KR101319919B1 (en) | 2013-10-22 |
| TW201215630A (en) | 2012-04-16 |
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