CN102385252A - Dyeing photosensitive resin combination, colorful color filter and liquid crystal display apparatus with colorful color filter - Google Patents
Dyeing photosensitive resin combination, colorful color filter and liquid crystal display apparatus with colorful color filter Download PDFInfo
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- CN102385252A CN102385252A CN2011102495912A CN201110249591A CN102385252A CN 102385252 A CN102385252 A CN 102385252A CN 2011102495912 A CN2011102495912 A CN 2011102495912A CN 201110249591 A CN201110249591 A CN 201110249591A CN 102385252 A CN102385252 A CN 102385252A
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- PVXVPZKMUQTVJG-PCLIKHOPSA-N CCCCC(CC)C[n]1c(ccc([N+]([O-])=O)c2)c2c2c1ccc(/C(/C)=N/OC(C)=O)c2 Chemical compound CCCCC(CC)C[n]1c(ccc([N+]([O-])=O)c2)c2c2c1ccc(/C(/C)=N/OC(C)=O)c2 PVXVPZKMUQTVJG-PCLIKHOPSA-N 0.000 description 1
- XXBBWHFNWOBOQE-SGWCAAJKSA-N CC[n](c(cc1)c2cc1[N+]([O-])=O)c(cc1)c2c(C)c1/C(/CSc1nc2ccccc2[s]1)=N/OC(C)=O Chemical compound CC[n](c(cc1)c2cc1[N+]([O-])=O)c(cc1)c2c(C)c1/C(/CSc1nc2ccccc2[s]1)=N/OC(C)=O XXBBWHFNWOBOQE-SGWCAAJKSA-N 0.000 description 1
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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
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
- G03F7/0295—Photolytic halogen compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/56—Ring systems containing three or more rings
- C07D209/80—[b, c]- or [b, d]-condensed
- C07D209/94—[b, c]- or [b, d]-condensed containing carbocyclic rings other than six-membered
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B11/00—Diaryl- or thriarylmethane dyes
- C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane dyes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- 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
- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
Abstract
The present invention relates to a dyeing photosensitive resin combination, a colorful color filter and a liquid crystal display apparatus with the colorful color filter, wherein the dyeing photosensitive resin combination contains a dyeing material (A), a bonder resin (B), a photopolymerization compound (C), a photopolymerization initiator (D) and a dissolvent (E), and the photopolymerization initiator (D) contains a compound with at least two photoactivity oxime ester rameworks contained by one molecule. The dyeing photosensitive resin combination can not appear pattern deficiency and transparence decrease under low exposure degree, thereby being capable of providing an excellent colorful color filter and a liquid crystal display apparatus with the colorful color filter.
Description
Technical field
The present invention relates to a kind of photosensitive composition, colored filter and have the liquid crystal indicator of this colored filter, said photosensitive composition is used for driving at the color liquid crystal display arrangement of thin film transistor (TFT) (TFT) mode and forms the dyed layer that contains the color liquid crystal display arrangement pixel on substrate.
Background technology
Colored filter is widely used in image-forming component, the liquid crystal indicator (LCD) etc., and its range of application sharply enlarges.Colored filter used in color liquid crystal display arrangement, the image-forming component etc. makes with following method usually.Be formed with on the substrate of black matrix pattern; Evenly be coated with photosensitive composition through the rotary coating mode, said photosensitive composition contains and is equivalent to redness, green and blue versicolor pigment, and heat drying (below be called " pre-burned ") forms and films then; With the exposure of filming that forms, development; Further be heating and curing as required (below be called " afterwards firing "), every kind of color is carried out aforesaid operations repeatedly, form versicolor pixel.
Many when using pigment and resin glue as this photosensitive composition, use optical polymerism compound and Photoepolymerizationinitiater initiater, when forming black matrix", also use the photosensitive polymer combination that contains black pigment.
Recently,, pursue the rerum natura of photosensitive composition,, and have excellent attaching property even make it under exposure seldom, also can have excellent light sensitivity through the high grade of transparency in order to improve the yield on the photosensitive composition operation.
Therefore; In the prior art; The method that adopts the content that improves polyfunctional monomer in the photosensitive composition to improve degree of crosslinking improves light sensitivity; But this method can be when developing in non-exposure portion residual residue, the development type is advanced, because the developing pattern disappearance causes demonstration bad to peel-away type.
Recently, in photosensitive composition, import the Photoepolymerizationinitiater initiater that contains the excellent photolytic activity oxime ester base of light sensitivity and improve light sensitivity, promptly import the compound that a molecule contains a photolytic activity oxime ester skeleton.But, when the content that contains the Photoepolymerizationinitiater initiater of photolytic activity oxime ester base surpasses appropriate level, can cause brightness to descend, exist color characteristics bad and pollute the problem of exposure machine, people are seeking the solution to the problems referred to above.
Summary of the invention
The technical matters that the present invention will solve
Therefore, the object of the present invention is to provide a kind of photosensitive composition, it even under low exposure, can not cause the pattern disappearance, can not reduce transparency yet when being used for colored filter, therefore demonstrate excellent light sensitivity.
Another object of the present invention is to provide a kind of colored filter that uses said photosensitive composition to make.
A purpose more of the present invention is to provide a kind of liquid crystal indicator with said colored filter.
The technological means of technical solution problem
In order to realize said purpose, the present invention provides a kind of photosensitive composition, it is characterized in that, it contains coloured material (A), resin glue (B), optical polymerism compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E); Said Photoepolymerizationinitiater initiater (D) contains the compound that in a molecule, has at least two photolytic activity oxime ester skeletons.
The present invention also provides a kind of colored filter that contains color layer, said color layer is after photosensitive composition of the present invention is formed predetermined pattern, through exposure and develop and form.
The present invention also provides the liquid crystal indicator with colored filter of the present invention.
The invention effect
When photosensitive composition of the present invention is used for colored filter,, can not reduce transparency, therefore demonstrate excellent light sensitivity even under low exposure, can not cause the pattern disappearance yet.Excellent high-quality colored filter can be provided and have the liquid crystal indicator of this colored filter.
Description of drawings
Fig. 1 a～1h is for forming the operation generalized schematic of colored filter with photosensitive composition of the present invention.
Description of reference numerals:
Embodiment
Below, the present invention is elaborated.
Photosensitive composition of the present invention comprises coloured material (A), resin glue (B), optical polymerism compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E); Said Photoepolymerizationinitiater initiater (D) contains the compound that in a molecule, has at least two photolytic activity oxime ester skeletons.
[coloured material (A)]
Said coloured material (A) is conventional pigment, is preferably the organic pigment or the inorganic pigment that are generally used for pigment dispersion inhibitor.Said coloured material (A) can also use dyestuff as required.
The metallic compounds such as metal oxide or metallic complex salt of having given an example as inorganic pigment, the oxide of the metals such as iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, barium, calcium of specifically giving an example or composite metal oxide etc.In addition, can also comprise carbon black.
As said organic pigment and inorganic pigment; The compound of specifically giving an example and in color index (Britain's dyeing and finishing and division color association (The society of Dyers and Colourists) publish), classifying with pigment; More specifically; The pigment of the following color index (C.I.) of giving an example numbering, but needn't be defined in this.
C.I. pigment yellow 20,24, and 31,53,83,86,93,94,109,110,117,125,137,138,139,147,148,150,153,154,166,173,180 and 185;
C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65 and 71;
C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,215,216,224,242,254,255 and 264;
C.I. pigment violet 14,19, and 23,29,32,36,37 and 38;
C.I. pigment blue 15 (15:3,15:4,15:6 etc.), 21,28,60,64 and 76;
C.I. pigment Green 7,10,15,25,36,47 and 58;
C.I. pigment brown 28;
C.I. pigment black 1 and 7 etc.
These coloured materials (A) can use separately separately, also can two or more combinations use.
The content of said coloured material (A) accounts for 5～60 quality % of solid constituent in the photosensitive composition in mass percent, is preferably 10～50 quality %.If the content of coloured material (A) is in 5～60 quality % scopes of above-mentioned standard, even form film, the colour saturation of pixel is also enough abundant, does not reduce the deciduous of non-pixel portions when developing, and is difficult to produce residue, and is therefore preferred.
Among the present invention, solid constituent is meant the summation of removing the composition after desolvating in the so-called photosensitive composition.
When coloured material is pigment, makes it contain pigment dispersing agent and carry out dispersion treatment, thereby can access pigment is homogeneously dispersed state in solution dispersible pigment dispersion.
As said pigment dispersing agent; For example can use surfactants such as silicon class, fluorine class, polyesters, polyamines class, PP type, cationic, anionic species, nonionic class, the positive; These pigment dispersing agents can use separately, also can two or more combinations use.
When using pigment dispersing agent, when coloured material is 1 mass parts in the color sensation photosensitive resin composition, the consumption of pigment dispersing agent preferably below 1 mass parts, 0.05 mass parts～0.5 mass parts more preferably.If the consumption of pigment dispersing agent can obtain the pigment of homogeneously dispersed state in said scope, therefore preferred said pigment dispersing agent uses in said scope.
[resin glue (B)]
Said resin glue (B) has reactivity and the alkali dissolution property that causes because of light or heat effect usually, as the dispersion medium of coloured material.The resin glue (B) that is contained in the photosensitive composition of the present invention is as the resin glue to coloured material (A); So long as can be dissolved in, all can use to the resin glue of preparation colored filter in the employed alkaline-based developer of development phase.
Preferably; Said resin glue (B) is preferably the multipolymer that the copolyreaction through following compound obtains, and said compound contains the ENB framework compound (B1) shown in the following Chemical formula 1, aromatic ethylene compound or N-substituted maleimide amines (B2) and has carboxyl and the compound of unsaturated link (B3).Preferred, said resin glue (B) for the above-mentioned multipolymer that makes further with a molecule in have unsaturated link and an epoxy radicals compound (B4) react the resin that contains unsaturated group make.
Chemical formula 1
In the above-mentioned chemical formula, n is 0 or 1; R
1, R
2Contain or do not contain heteroatomic aliphatics, aromatic hydrocarbon for hydrogen, carbon number 1～12 independently of one another according to the position; R
3, R
4, R
5, R
6Contain or do not contain heteroatomic aliphatics, aromatic hydrocarbon for hydrogen, carbon number 1～30 independently of one another according to the position; From R
3, R
4, R
5, R
6In select two be the chain that couples together or do not link together dendritic.
The photosensitive composition that contains following resin glue is demonstrating excellent characteristic aspect heat, the chemical resistance, said resin glue contains the ENB framework compound (B1) shown in the said Chemical formula 1.
More specifically, the ENB framework compound (B1) shown in the said Chemical formula 1 can contain at least one that from the compound with following Chemical formula 2～17 structural formulas, select.
< Chemical formula 2>< chemical formula 3>< chemical formula 4 >
< chemical formula 5>< chemical formula 6>< chemical formula 7 >
< chemical formula 8>< chemical formula 9>< Chemical formula 10 >
< Chemical formula 11>< Chemical formula 12>< Chemical formula 13 >
< Chemical formula 14>< Chemical formula 15>< Chemical formula 16>< Chemical formula 17 >
On the other hand, (methyl) acrylic ester of being put down in writing in this instructions is meant acrylic ester and/or methacrylate.
For example be described below as said aromatic ethylene compound or the concrete spendable compound of N-substituted maleimide amines (B2).At first; As aromatic ethylene compound be styrene, vinyltoluene, AMS, to chlorostyrene, O-methoxy styrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, a vinyl benzyl methyl ether, to vinyl benzyl methyl ether, adjacent vinyl benzyl glycidyl ether, a vinyl benzyl glycidyl ether, to vinyl benzyl glycidyl ether, indenes etc.; From development property, the excellent aspect of operation property, preferred vinyl toluene.In addition; As N-substituted maleimide amines is aminomethyl phenyl maleimide, N-p-methylphenyl maleimide, N-o-methoxyphenyl maleimide, N-m-methoxyphenyl maleimide, N-p-methoxyphenyl maleimide etc. between hydroxy phenyl maleimide, N-p-hydroxybenzene maleimide, N-o-methyl-phenyl-maleimide, N-between N-cyclohexyl maleimide, N-benzyl maleimide, N-phenylmaleimide, N-o-hydroxy-phenyl maleimide, N-; From development property, the excellent aspect of operation property, preferred N-benzyl maleimide.Above-claimed cpd can use separately separately, also can two or more combinations use.
As said compound (B3) with carboxyl and unsaturated link, get final product so long as have the carboxylic acid compound of polymerisable unsaturated double-bond, restriction as concrete instance, does not for example have acrylic acid, methacrylic acid etc.Acrylic acid, methacrylic acid can use separately separately, also can two or more combinations use.In addition, on the basis of these acrylic acid, methacrylic acid, can also use more than one other acid.As other acid, crotonic acid, itaconic acid, maleic acid, fumaric acid etc. are specifically arranged, can also and use more than one the carboxylic acid of from other unsaturated carboxylic acids, selecting.In addition, can also and with α-(methylol) acrylic acid etc., with the monomer that comprises hydroxyl and carboxyl in a part.
Based on the present invention; In the multipolymer that said (B1)～(B3) copolymerization makes (the present invention also comprises the situation that the monomer that further contains except that B1～B3 carries out copolymerization); Ratio from the constituent of (B1)～(B3) derive respectively; Total mole number with the constituent that constitutes said multipolymer is a benchmark, in molar percentage, preferably in following ranges.
The structural unit of deriving from (B1): 2～30 moles of %.
The structural unit of deriving from (B2): 2～95 moles of %.
The structural unit of deriving from (B3): 2～70 moles of %.
Especially, from the ratio of the constituent of said (B1)～(B3) derive respectively, be benchmark with the total mole number of the constituent that constitutes said photopolymer, in molar percentage, further preferably in following ranges.
The structural unit of deriving from (B1): 5～30 moles of %.
The structural unit of deriving from (B2): 5～80 moles of %.
The structural unit of deriving from (B3): 5～65 moles of %.
As stated, if from the ratio of the constituent of (B1)～(B3) derive respectively in above-mentioned scope, then therefore balanced good between development property, solubility and the thermotolerance can obtain preferred multipolymer.
In an embodiment of the invention, (B1)～(B3) copolymerization is obtained under the situation of said multipolymer, can make through following method copolymerization.
In flask with stirring machine, thermometer, reflux condensing tube, tap funnel and nitrogen conduit, add (B1) simultaneously and be the solvent of 0.5～20 times of amount of standard with (B1)～(B3) gross mass, be nitrogen with the air displacement in the flask.Then; After solvent is warming up to 40～140 ℃; Be standard and the solution (stirring and dissolving under room temperature or heating condition) that accounts for the polymerization initiator of 0.1～10 mole of % of (B1)～(B3) total mole number for the solvent of 0～20 times of amount of this standard and with mole percentage with (B2) that added ormal weight and (B3), in (B1)～(B3) gross mass; Be added drop-wise in the above-mentioned flask from tap funnel; 0.1～8 hour dropping time, said polymerization initiator is azoisobutyronitrile, tert-butyl hydroperoxide-2-ethylhexyl carbonic ester etc., further stirs 1 hour～10 hours down at 40～140 ℃.
In said operation, can in flask, add the part or all of of polymerization initiator, also can in flask, add the part or all of of (B1)～(B3).During with (B4) polymerization, in this process, can add the surplus of (B1)～(B3) at the multipolymer that said (B1)～(B3) copolymerization is made.
As employed solvent in said operation; The solvent that when Raolical polymerizable, uses usually can be used, tetrahydrofuran, dioxan, glycol dinitrate benzyl ethyl ether, diethylene glycol dimethyl ethyl ether, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl nitrate, nitric acid butyl ester, propylene glycol monomethyl ethylhexoate, 3-methoxyl butylacetic acid ester, methyl alcohol, ethanol, propyl alcohol, normal butyl alcohol, glycol monomethyl methyl ether, propylene glycol monomethyl ether, toluene, xylene, ethylbenzene, chloroform, dimethyl sulfoxide (DMSO) etc. can be used particularly.These solvents can use separately, also can two or more and usefulness.
In addition, can use common employed polymerization initiator, not special restriction as employed polymerization initiator in the said operation.Can use DIBHP, di-tert-butyl peroxide, benzoyl peroxide, tert-butyl peroxide isopropyl carbonic ester, peroxidating tertiary pentyl-2 ethyl hexanoic acid ester, tert-butyl peroxide-organic peroxides such as 2-ethylhexyl carbonic ester particularly; And 2; 2 '-azo two (isobutyronotrile), 2; 2 '-azo two (2, the 4-methyl pentane nitrile), dimethyl 2,2 '-azo two nitrogen-containing compounds such as (2 Methylpropionic acid esters).These polymerization initiators can use separately, also can two or more and usefulness.
In addition, for control molecular weight and molecular weight distribution in polymerization process, the multipolymer that said (B1)～(B3) copolymerization is made can also use α-Jia Jibenyixierjuwu or compounds containing thiol groups as chain-transferring agent.In mass percent, the consumption of α-Jia Jibenyixierjuwu or compounds containing thiol groups is 0.005～5 quality % of (B1)～(B3) gross mass.In addition, consider thermal value that is caused by manufacturing equipment and polymerization etc., said polymerizing condition can also suitably be regulated input method and temperature of reaction.
According to one embodiment of present invention; Resin glue through by contain the ENB framework compound (B1) shown in the above-mentioned Chemical formula 1, aromatic ethylene compound or N-substituted maleimide amines (B2) and have carboxyl and the compound of the compound of unsaturated link (B3) in the multipolymer that copolyreaction makes; Add the compound (B4) that has unsaturated link and epoxy radicals in the molecule, can give resin glue light/Thermocurable.
The compound (B4) that has unsaturated link and epoxy radicals in the said molecule; Concrete example is if any (methyl) glycidyl acrylate, 3; 4-epoxycyclohexyl (methyl) acrylic ester, 3,4-epoxycyclohexyl methyl (methyl) acrylic ester, (methyl) acrylic acid methyl ethylene oxidic ester etc.Wherein preferably use (methyl) glycidyl acrylate.These can distinguish independent use, also can two or more combinations use.
The compound (B4) that has unsaturated link and epoxy radicals in the said molecule; In mole percentage; Be preferably 5～80 moles of % of the constituent that derives by the compound with carboxyl and unsaturated link (B3) in the said multipolymer, more preferably 10～80 moles of %.As long as the compound (B4) with unsaturated link and epoxy radicals can obtain sufficient photo-curable or Thermocurable in above-mentioned scope, have good light sensitivity and pencil hardness simultaneously, reliability is excellent, and is therefore preferred.
In an embodiment of the invention, resin glue (B) can make multipolymer with said (B1)～(B3) copolymerization through for example following method, makes with (B4) reaction again.
When making the multipolymer of (B1)～(B3) through said method; With the nitrogen replacement in the flask is air; To account for (B4) of 5～80 moles of % of the constituent that derives by the compound with carboxyl and unsaturated link (B3) in the said multipolymer in mole percentage, account in mass percent (B1)～(B4) gross mass 0.01～5 quality % carboxyl and epoxy radicals catalysts (for example; Three (dimethylamino methyl) phenol), the polymerization inhibitor that accounts for (B1)～(B4) gross mass 0.001～5 quality % in mass percent (for example; P-dihydroxy-benzene) joins in the flask; Reacted 1～10 hour down at 60～130 ℃, can make said multipolymer and (B4) reaction.In addition, identical with polymerizing condition, consider thermal value that causes because of manufacturing equipment and polymerization etc., can suitably regulate input method and temperature of reaction.
In an embodiment of the invention, preferably it converts poly weight-average molecular weight in 3000～100000 scope to resin glue (B), more preferably in 5000～50000 scopes.Reduce if the weight-average molecular weight of resin glue (B) in 3000～100000 scope, is difficult to take place film when developing, the deciduous of non-pixel portion is good during development, and is therefore preferred.
The acid number of resin glue (B) is benchmark with the solid constituent, preferably in the scope of 30～150mgKOH/g.Acid number is during less than 30mgKOH/g, to the development property reduction of alkaline water, may be on substrate residual residue; When acid number surpasses 150mgKOH/g, cause the disengaging of pattern probably.
The molecular weight distribution of resin glue (B) [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is preferably 1.5～6.0, more preferably 1.8～4.0.If molecular weight distribution [weight-average molecular weight (Mw)/number-average molecular weight (Mn)] is 1.5～6.0, then development property excellence is therefore preferred.
The content of resin glue (B) is in mass percent, and 5～90 quality % for solid constituent in the photosensitive composition are preferably in the scope of 10～70 quality %.If the content of resin glue (B) is at 5～90 quality % of said benchmark; Dissolubility to developer solution is abundant, is difficult to produce the development residue on the substrate of non-pixel portion, and the pixel portion of exposure portion is difficult to take place the film minimizing during development; The deciduous of non-pixel portion is good, and is therefore preferred.
[optical polymerism compound (C)]
The optical polymerism compound (C) that is contained in the photosensitive composition of the present invention for light and after can polymeric compounds under the effect of the Photoepolymerizationinitiater initiater stated, the monofunctional monomer of having given an example, bifunctional monomer, other polyfunctional monomers etc.
In order to improve facing to the development property of color sensation official property resin combination, light sensitivity, attaching property, cosmetic issue etc.; Employed optical polymerism compound (C) can mix use structure of functional groups or the different two or more optical polymerism compounds of number of functional groups among the present invention, and its scope is restriction not.
As the object lesson of monofunctional monomer, the nonyl phenyl carbitol acrylic ester of having given an example, 2-hydroxyl-3-phenoxy propyl acrylic ester, 2-ethylhexyl carbitol acrylic ester, 2-hydroxy ethyl methacrylate, N-vinyl pyrrolidone etc.
Concrete example as bifunctional monomer; Given an example 1, two (acryloxy ethyl) ethers of 6-hexanediol two (methyl) acrylic ester, ethylene glycol bisthioglycolate (methyl) acrylic ester, neopentyl glycol two (methyl) acrylic ester, triethylene glycol two (methyl) acrylic ester, bisphenol-A, 3-methyl pentanediol two (methyl) acrylic ester etc.
As the concrete example of other polyfunctional monomers, the trimethylolpropane tris of having given an example (methyl) acrylic ester, ethoxylated trimethylolpropane three (methyl) acrylic ester, propoxylation trimethylolpropane tris (methyl) acrylic ester, pentaerythrite three (methyl) acrylic ester, pentaerythrite four (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, ethoxylation dipentaerythritol six (methyl) acrylic ester, propoxylation dipentaerythritol six (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester etc.
Wherein, preferably use the above polyfunctional monomer of difunctionality.
Optical polymerism compound (C) is generally 1～60 quality % of solid constituent in the photosensitive composition in mass percent, is preferably 5～50 quality %.If optical polymerism compound (C) is in 1～60 quality % scope of said standard, then the intensity of pixel portions, flatness are good, therefore preferred.
[Photoepolymerizationinitiater initiater (D)]
The Photoepolymerizationinitiater initiater (D) that is contained in the photosensitive composition of the present invention is included in the compound that has two above photolytic activity oxime ester skeletons in the molecule.Be preferably the compound shown in the following Chemical formula 18 as the said compound that in a molecule, has two above photolytic activity oxime ester skeletons and pass through R
1Or R
2The dimer that dimerization obtains.
Chemical formula 18
In the said chemical formula, R
1, R
2And R
3Represent R independently of one another
11, OR
11, COR
11, SR
11, CONR
12R
13Or CN, R
4And R
5Represent R independently of one another
11, OR
11, SR
11, COR
11, CONR
12R
13, NR
12COR
11, OCOR
11, COOR
11, SCOR
11, OCSR
11, COSR
11, CSOR
11, CN, halogen atom or hydroxyl, a and b represent 0～3 independently of one another.
R
11, R
12, R
13Represent the alkyl of hydrogen atom, carbon number 1～20, the aryl of carbon number 6～30, the aryl alkyl of carbon number 7～30 or the heterocyclic radical of carbon number 2～20 independently of one another; At this, the hydrogen atom of alkyl, aryl, aryl alkyl and heterocyclic radical can also be by R
21, OR
21, COR
21, SR
21, NR
22R
23, CONR
22R
23,-NR
22-OR
23,-NCOR
22-OCOR
23,-C (=N-OR
21)-R
22,-C (=N-OCOR
21)-R
22, CN, halogen atom ,-CR
21=CR
22R
23,-CO-CR
21=CR
22R
23, OCO-CR
21=CR
22R
23, O-C
1-6Alkylidene-OCOR
21, COOR
21, epoxy radicals replaces; R
21, R
22, R
23Represent the alkyl of hydrogen atom, carbon number 1～20, the aryl of carbon number 6～30, the aryl alkyl of carbon number 7～30 or the heterocyclic radical of carbon number 2～20 independently of one another; Said R
11, R
12, R
13, R
21, R
22And R
23The methylene of shown substituent alkylene moiety can also be interrupted 1～5 time by unsaturated link, ehter bond, thioether bond, ester bond, thioester bond, amido link or urethane bonds; Said substituent moieties can also be side chain, also can be cyclic alkyl; Said substituent alkyl end can also be unsaturated link; In addition, R
12And R
13And R
22And R
23Can also distinguish common formation ring, R
3Can also form ring jointly with the phenyl ring of adjacency.R
4And R
5Represent R independently of one another
11, OR
11, SR
11, COR
11, CONR
12R
13, NR
12COR
11, OCOR
11, COOR
11, SCOR
11, OCSR
11, COSR
11, CSOR
11, CN, halogen atom or hydroxyl; A and b represent 0～3 independently of one another.
Preferably, as R in the said Chemical formula 18
11, R
12, R
13, R
21, R
22And R
23Shown alkyl for example has methyl, ethyl, propyl group, isopropyl, butyl, isobutyl, sec-butyl, the tert-butyl group, amyl group, isopentyl, tertiary pentyl, hexyl, heptyl, octyl group, iso-octyl, 2-ethylhexyl, uncle's octyl group, nonyl, different nonyl, decyl, isodecyl, undecyl, dodecyl, myristyl, cetyl, octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexyl methyl, vinyl, allyl, butenyl group, ethinyl, propinyl, methoxy ethyl, ethoxyethyl group, propoxyl group ethyl, amoxy ethyl, octyloxy ethyl, methoxyethoxyethyl, ethoxy ethoxy ethyl, propoxyl group ethoxyethyl group, methoxy-propyl, 2-methoxyl-1-Methylethyl etc.As R
11, R
12, R
13, R
21, R
22And R
23Shown aryl for example has phenyl, tolyl, xylyl, ethylbenzene base, chlorphenyl, naphthyl, anthryl, phenanthryl, by a substituted phenyl of the above alkyl, xenyl, naphthyl, anthryl etc.As R
11, R
12, R
13, R
21, R
22And R
23Shown aryl alkyl, preference is if any benzyl, benzyl chloride base, α-Jia Jibianji, α, α-Er Jiajibianji, phenylethyl, styryl etc.As R
11, R
12, R
13, R
21, R
22And R
23Shown heterocyclic radical for example has 5～7 yuan of heterocycles such as pyridine radicals, pyrimidine radicals, furyl, thienyl, tetrahydrofuran base, dioxane, benzoxazoles-2-base, THP trtrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, thiazolidinyl, isothiazole alkyl, oxazolidinyl, isoxazole alkyl, piperidyl, piperazinyl, morpholinyl.In addition, as R
12And R
13The ring that can form jointly, R
22And R
23The ring that can form jointly, and R
3Ring with the phenyl ring of adjacency can form jointly for example has 5～7 yuan of rings such as cyclopentane ring, cyclohexane ring, cyclopentene ring, phenyl ring, piperidine ring, morpholine ring, lactonic ring, lactam nucleus.In addition, as instead R
11, R
12, R
13, R
21, R
22And R
23Halogen atom and R
4, R
5The halogen atom of expression for example has fluorine, chlorine, bromine, iodine.
The methylene of said substituent alkylene moiety can be interrupted 1～5 time by unsaturated link, ehter bond, thioether bond, ester bond, thioester bond, amido link or urethane bonds, and at this moment, the key base of interruption can be one or more; If the group that can interrupt continuously also can interrupt more than two continuously.In addition, said substituent moieties can be side chain, also can be cyclic alkyl, and said substituent alkyl end can also be unsaturated link.
In the oxime ester compound of the present invention, in said Chemical formula 18, R
1Alkyl, the aryl of carbon number 6～30, the aryl alkyl of carbon number 7～30, the heterocyclic radical of carbon number 2～20, OR for carbon number 11～20
11, COR
11, SR
11, CONR
12R
13Or the compound of CN, perhaps R
3For interrupt alkyl, the alkyl of carbon number 13～20, the OR of 1～5 time carbon number 1～12 with ehter bond or ester bond
11, COR
11, SR
11, CONR
12R
13Or the compound of CN; Especially R
1Be the compound of the aryl of the alkyl of carbon number 11～20 or carbon number 6～30, perhaps R
3For the methylene of the alkylene moiety of alkyl can be interrupted 1～5 time carbon number by ehter bond or ester bond can be at the methylene of the alkylene moiety of the branched alkyl 8 or more, alkyl by the compound of the carbon number of ehter bond or ester bond interruption 1～5 time at the alkyl more than 13; R
3For interrupted the compound of 1～5 time alkyl by ehter bond; R
3For interrupted the compound of 1～5 time alkyl by ester bond; Because it is synthetic easily, cross-linking density is high; This is external when the Photoepolymerizationinitiater initiater; In as the propylene glycol-1-monomethyl ether-2-acetic acid esters of solvent or cyclohexane, more than the solubilized 1 quality %, satisfy requirement as Photoepolymerizationinitiater initiater, therefore preferred.
Oxime ester compound of the present invention shown in following Chemical formula 19 and Chemical formula 20, is preferably that compound passes through R shown in the Chemical formula 18
1Or R
2Carry out the dimer of dimerization.
Chemical formula 19
Chemical formula 20
In said chemical formula, R
1～R
5, a and b be identical with the definition of said Chemical formula 18.
As the preferred concrete example of the oxime ester compound of the present invention shown in the said Chemical formula 18, the compound of the following Chemical formula 2 1～27 of giving an example.But following compound does not carry out any restriction to the present invention.
Chemical formula 21
Chemical formula 22
Chemical formula 23
Chemical formula 24
Chemical formula 25
Chemical formula 26
Chemical formula 27
As the preferred concrete example of the oxime ester compound of the present invention shown in the said Chemical formula 20, the compound of the following Chemical formula 28 of giving an example.But following compound does not carry out any restriction to the present invention.
Chemical formula 28
The said compound that in a molecule, has two above photolytic activity oxime ester skeletons can use the commercially available prod, particularly, gives an example as the commercially available prod NCI-831 ((strain) Ai Dike (ADEKA)) with said compound 28 structures.
The said compound that in a molecule, has two above photolytic activity oxime ester skeletons is benchmark with the solid constituent, counts with mass percent more than the 10 quality % of Photoepolymerizationinitiater initiater in the photosensitive composition, is preferably 20～80 quality %.When the said compound that in a molecule, has two above photolytic activity oxime ester skeletons of the present invention contains said benchmark in Photoepolymerizationinitiater initiater 10 quality % are above; Demonstrate ISO to light; Even under low exposure, also have high crosslink density, excellent to the attaching property of substrate, pattern can not take place in developing process to be peeled off; Excellent heat stability, therefore preferred.
The Photoepolymerizationinitiater initiater (D) that is contained in the photosensitive composition of the present invention is not restriction except that the above-mentioned compound that in a molecule, has two above photolytic activity oxime ester skeletons, but can use more than one the compound that is selected from compound in triazine class, acetophenone compounds, two glyoxaline compound and the oxime compound simultaneously.The photosensitive composition that contains said Photoepolymerizationinitiater initiater (D) has ISO, uses the formed film of said composition, and the intensity and the surface smoothing property of its pixel portions are good.
As said compound in triazine class, for example have 2, two (the trichloromethyl)-6-(4-methoxyphenyl) of 4--1,3,5-triazines, 2; Two (the trichloromethyl)-6-(4-methoxyl naphthyl) of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-piperonyls-1,3 of 4-; 5-triazine, 2, two (the trichloromethyl)-6-(4-methoxyl-styrene) of 4--1,3,5-triazines, 2, two (the trichloromethyl)-6-[2-(5-methylfuran-2-yl) vinyl]-1 of 4-; 3,5-triazine, 2, two (the trichloromethyl)-6-[2-(furans-2-yl) vinyl]-1,3 of 4-; 5-triazine, 2, two (the trichloromethyl)-6-[2-(4-diethylamine-2-tolyl) vinyl] of 4--1,3,5-triazines, 2; Two (the trichloromethyl)-6-[2-(3, the 4-Dimethoxyphenyl) vinyl] of 4--1,3,5-triazines etc.
In addition; As said acetophenone compounds, the oligomer of diethoxy acetophenone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, benzyl dimethyl ketal, 2-hydroxyl-1-[4-(2-hydroxyl-oxethyl) phenyl]-2-methylpropane-1-ketone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-methyl thio-phenyl)-2-morpholine morpholine propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl) butane-1-ketone, 2-hydroxy-2-methyl-1-[4-(1-methyl ethylene) phenyl] propane-1-ketone etc. is for example arranged.
In addition, as other spendable acetophenone compounds except that above-mentioned acetophenone compounds, the compound shown in the for example useful following Chemical formula 29.
Chemical formula 29
In said Chemical formula 29, R
1～R
4Represent independently of one another hydrogen atom, halogen atom, hydroxyl, can by the substituted phenyl of the alkyl of carbon number 1～12, can be by the substituted benzyl of the alkyl of carbon number 1～12 or can be by the substituted naphthyl of the alkyl of carbon number 1～12.
The object lesson of the compound shown in the said Chemical formula 29, amino (4-morpholinyl phenyl) ethane of the 2-methyl of having given an example-2--1-ketone, amino (4-morpholinyl phenyl) ethane of 2-ethyl-2--1-ketone, amino (4-morpholinyl phenyl) ethane of 2-propyl group-2--1-ketone, amino (4-morpholinyl phenyl) ethane of 2-butyl-2--1-ketone, amino (4-morpholinyl phenyl) propane of 2-methyl-2--1-ketone, amino (4-morpholinyl phenyl) butane of 2-methyl-2--1-ketone, amino (4-morpholinyl phenyl) propane of 2-ethyl-2--1-ketone, amino (4-morpholinyl phenyl) butane of 2-ethyl-2--1-ketone, 2-methyl-2-methylamino (4-morpholinyl phenyl) propane-1-ketone, 2-methyl-2-dimethylamino (4-morpholinyl phenyl) propane-1-ketone, 2-methyl-2-dimethylamino (4-morpholinyl phenyl) propane-1-ketone etc.
As said pair of glyoxaline compound, 2,2 '-two (2-chlorphenyl)-4,4 ', 5 for example arranged, 5 '-tetraphenyl double imidazole, 2; 2 '-two (2, the 3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole, 2,2 '-two (2-chlorphenyls)-4; The two imidazoles of 4 ', 5,5 '-four (alkoxyl phenyls), 2,2 '-two (2-chlorphenyl)-4,4 '; The two imidazoles of 5,5 '-four (tri-alkoxy phenyls) or 4,4 ', 5,5 ' phenyl is by substituted imidazolium compounds of alkoxy carbonyl group etc.Wherein, preferably use 2,2 '-two (2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole or 2,2 '-two (2, the 3-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl double imidazole.
As said oxime compound, adjacent ethoxy carbonyl-α-oximido-1-phenyl-propane-1-ketone, and the compound shown in the following chemical formula 30～32 etc.
Chemical formula 30
Chemical formula 31
Chemical formula 32
In addition, only otherwise damage effect of the present invention, can also append and with common employed other Photoepolymerizationinitiater initiaters in this area etc.As other Photoepolymerizationinitiater initiaters, styrax compounds, benzophenone compound, thioxanthones compounds, anthracene compounds etc. are for example arranged.These Photoepolymerizationinitiater initiaters can use separately, also can two or more combinations use.
As said styrax compounds, styrax, styrax methyl ether, styrax ethylether, benzoin isobutyl propyl group ether, benzoin isobutyl butyl ether etc. are for example arranged.
As said benzophenone compound, benzophenone, methyl o-benzoylbenzoate, 4-phenyl benzophenone, 4-benzoyl-4 '-methyldiphenyl base sulfuric ester, 3,3 ' are for example arranged; 4; 4 '-four (tert-butyl hydroperoxide carbonyl) benzophenone, 2,4,6-tri-methyl benzophenone etc.
As said thioxanthones compounds, 2-isopropyl thioxanthone, 2 is for example arranged, 4-diethyl thioxanthone, 2,4-two clopenthixal ketones, 1-chloro-4-propoxyl group thioxanthones etc.
As said anthracene compounds, for example have 9,10-dimethoxy anthracene, 2-ethyl-9,10-dimethoxy anthracene, 9,10-diethoxy anthracene, 2-ethyl-9,10-diethoxy anthracene etc.
In addition,, can also give an example 2,4,6-trimethylbenzene formyl diphenyl phosphine oxide, 10-butyl-2-chloro-acridine ketone, 2-EAQ, benzyl, 9,10-phenanthrenequione, camphorquinone, phenyl glyoxalic acid methylester, two cyclopentadiene titanium compounds etc. as other Photoepolymerizationinitiater initiaters.
In addition, can also make up the use photopolymerization in the Photoepolymerizationinitiater initiater (D) and cause auxiliary agent (D-1).If in Photoepolymerizationinitiater initiater (D) and with photopolymerization, cause auxiliary agent (D-1), the photosensitive composition that then contains it has higher light sensitivity, can increase productivity when using said composition to form colored filter, and is therefore preferred.
Cause auxiliary agent (D-1) as photopolymerization and preferably use amines, carboxylic acid compound.
Photopolymerization causes in the auxiliary agent (D-1); Object lesson as amines; Fatty amine compound, 4-dimethylaminobenzoic acid methyl esters, 4-dimethylaminobenzoic acid ethyl ester, 4-dimethylaminobenzoic acid isopentyl ester, 4-dimethylaminobenzoic acid 2-ethylhexyl, benzoic acid 2-dimethyl aminoethyl ester, N such as triethanolamine, methyldiethanolamine, triisopropanolamine have given an example; N-dimethyl-p-toluidine, 4; Michaelis ketone), aromatic amines compound such as 4,4 '-two (diethylamino) benzophenone 4 '-two (dimethylamino) benzophenone (is commonly called as:.As amines, preferably use aromatic amines compound.
As the object lesson of carboxylic acid compound, aromatic series such as the phenyl thioacetic acid of having given an example, aminomethyl phenyl thioacetic acid, ethylphenyl thioacetic acid, Methylethyl phenyl thioacetic acid, 3,5-dimethylphenyl thioacetic acid, methoxyphenyl thioacetic acid, Dimethoxyphenyl thioacetic acid, chlorphenyl thioacetic acid, dichlorophenyl thioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthyl thioacetic acid, N-naphthyl glycocoll, the naphthoxy acetic acid acetate class of mixing.
The consumption of Photoepolymerizationinitiater initiater (D) is benchmark with the solid constituent, is generally 0.1～40 quality % of resin glue (B) and optical polymerism compound (C) total amount in mass percent, is preferably 1～30 quality %; Photopolymerization causes the consumption of auxiliary agent (D-1), under said benchmark, is generally 0.1～5 quality %, is preferably 1～40 quality %.
If the consumption of Photoepolymerizationinitiater initiater (D) is in said scope, then photosensitive composition has ISO, and the flatness on the intensity of the pixel portions that the use said composition forms, this pixel portions surface is good, and is therefore preferred.In addition,, then can further improve the light sensitivity of photosensitive composition, can improve the yield-power of using said composition to form optical filter if photopolymerization causes the consumption of auxiliary agent (D-1) in above-mentioned scope, therefore preferred.
[solvent (E)]
The not special restriction of the solvent (E) that is contained in the photosensitive composition of the present invention can be used the various organic solvents of in the photosensitive composition field, being used always.As the object lesson of solvent, ethylene glycol monoalkyl ether classes such as the glycol monomethyl methyl ether of having given an example, ethylene glycol monomethyl ether, glycol monomethyl propyl ether, ethylene glycol monobutyl ether; Diethylene glycol dialkyl ether classes such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ethers; Monoethylene glycol such as methylcellosolve acetate, ethyl cellosolve acetate alkyl ether acetate esters; Aklylene glycol alkyl ether acetate esters such as propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, propylene glycol list propyl ether acetic acid esters, methoxyl butylacetic acid ester and methoxyl amyl group acetic acid esters; Benzene,toluene,xylene, sym-trimethyl benzene etc. are aromatic hydrocarbon based; Ketones such as methyl ethyl ketone, acetone, methyl amyl ketone, methyl isobutyl ketone, cyclohexanone; Alcohols such as ethanol, propyl alcohol, butanols, hexanol, cyclohexanol, monoethylene glycol, glycerine; Ester classes such as 3-ethoxyl ethyl propionate, 3-methoxypropionic acid methyl esters; Cyclic ester classes such as gamma-butyrolacton etc.
In the above-mentioned solvent, from coating, drying property aspect, preferably above-mentioned solvent mid-boiling point is at 100 ℃～200 ℃ organic solvent.Aklylene glycol alkyl ether acetate esters more preferably, ketone, ester classes such as 3-ethoxyl ethyl propionate, 3-methoxypropionic acid methyl esters.Further preferably propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, cyclohexanone, 3-ethoxyl ethyl propionate, 3-methoxypropionic acid methyl esters etc.These solvents (E) can be distinguished independent use, also can two or more mixing use.
The content of solvent in the photosensitive composition of the present invention (E) is counted 60～90 quality % of the photosensitive composition full dose that contains it with mass percent, be preferably 70～85 quality %.If the content of solvent (E) is in the scope of 60～90 quality % of said benchmark; When then using apparatus for coating such as roll coater, rotary coating machine, slit and rotary coating machine, slit type coater (being also referred to as the mould coating machine sometimes), ink-jet printer to be coated with; Coating is good, and is therefore preferred.
[adjuvant (F)]
In photosensitive composition of the present invention, as required can also be also with adjuvants (F) such as filler, other macromolecular compounds, hardening agent, pigment dispersing agent, attaching promoter, anti-oxidant, ultraviolet light absorber, deflocculants.
As the object lesson of filler, the glass of having given an example, silicon dioxide, aluminium oxide etc.
As other macromolecular compounds, the curable resins such as epoxy resin, maleimide resin of specifically having given an example; Polyvinyl alcohol (PVA), polyacrylic acid, polyalkylene glycol monoalkyl ether, gather thermoplastic resins such as fluoroalkyl acrylic ester, polyester, polyurethane etc.
Hardening agent is for deeply-curing and improve physical strength and use, as hardening agent given an example epoxy compound, polyfunctional isocyanate's compound, melamine compound, oxetane compound etc.
In said hardening agent; As epoxy compound bisphenol-A based epoxy resin, hydrogenated bisphenol A based epoxy resin, Bisphenol F based epoxy resin, A Hydrogenated Bisphenol A F based epoxy resin, phenol aldehyde type epoxy resin, other aromatic series based epoxy resins, alicyclic based epoxy resin, diglycidyl esters resin, diglycidyl amine resins are for example arranged; Or the bromo derivative of this epoxy resin, except that epoxy resin and the aliphatics the bromo derivative thereof, alicyclic or aromatic epoxy compound, butadiene (being total to) polymer ring oxide, isoprene (being total to) polymer ring oxide, glycidyl (methyl) acrylic ester (being total to) polymkeric substance, triglycidyl group isocyanuric acid ester etc.
In said hardening agent,, carbonic ester dioxygen heterocycle butane, xylene dioxygen heterocycle butane, hexane diacid dioxygen heterocycle butyl ester, terephthalic acid (TPA) dioxygen heterocycle butyl ester, cyclohexane diacid dioxygen heterocycle butyl ester etc. are for example arranged as oxetane compound.
In said hardening agent, can also contain the auxiliary compounds that the oxetanes skeleton ring-opening polymerization of epoxy radicals, the oxetane compound of epoxy compound is formed with hardening agent.As solidifying auxiliary compounds, polybasic carboxylic acid class, polybasic acid anhydride class, acid producing agent etc. are for example arranged.
Can use as the commercially available product of epoxy curing agent as carboxylic acid anhydrides.As this epoxy curing agent trade name (ADEKA HARDENER EH-700) (ADEKA industry (strain) is produced), trade name (LIKASITO HH) (new Japanese physics and chemistry (strain) production), trade name (MH-700) (new Japanese physics and chemistry (strain) production) etc. are for example arranged.Said hardening agent can use separately, also can two or more mixing use.
Can use commercially available surfactant as said pigment dispersing agent, for example surfactants such as silicon class, fluorine class, polyesters, polyamines class, PP type, cationic, anionic species, nonionic class, the positive.These can distinguish independent use, also can two or more combinations use.As said surfactant, polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether class, polyethylene glycol di class, Span class, fatty acid modified polyesters, tertiary amine modified polyurethane, polyethyleneimine quasi-polyethylene imines class etc. are for example arranged; In addition, also can give an example trade name KP (SHIN-ETSU HANTOTAI's chemical industry (strain) production), POLYFLOW (common prosperity society chemical industry (strain) production), EFTOP (production of Tohkem products (ト one ケ system プ ロ ダ Network Star) company), MEGAFAC (big Japanese ink chemical industry (strain) is produced), Flourad (Sumitomo 3M (strain) productions), Asahi guard, Surflon (above be Asahi Glass (strain) production), SOLSPERSE (Zeneca (ゼ ネ カ) (strain) production), EFKA (production of EFKA chemical company), PB821 (aginomoto (strain) production) etc.
As said attaching promoter; Vinyltrimethoxy silane, VTES, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-aminopropyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330,3-aminopropyltriethoxywerene werene, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxy propyl group methyl dimethoxysilane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, 3-sulfydryl propyl trimethoxy silicane, 3-isocyanates propyl trimethoxy silicane, 3-isocyanates propyl-triethoxysilicane etc. are for example arranged.
These attach promoter can distinguish independent use, perhaps also can two or more combinations use.In mass percent, account for 0.01～10 quality % of the solid constituent of photosensitive composition, preferably contain 0.05～2 quality %.
As said anti-oxidant, specifically given an example 2,2 '-thiobis (4-methyl-6-tert butyl phenol), 2,6 di tert butyl 4 methyl phenol etc.
As said ultraviolet light absorber, the 2-that specifically given an example (the 3-tert-butyl group-2-hydroxy-5-methyl base phenyl)-5-chlorobenzotriazole, alkoxy benzophenone etc.
As the said deflocculant sodium polyacrylate etc. of specifically having given an example.
In photosensitive composition of the present invention, can prepare through for example following method.Coloured material (A) is mixed with solvent (E) in advance, make the mean grain size of coloured material be dispersed to below the 0.2 μ m with ball mill etc. about.At this moment, can use pigment dispersing agent as required, in addition, also can add part or all of resin glue (B) sometimes.In the dispersion liquid that makes (below be also referred to as comminuting matter sometimes), further add remaining resin glue (B), optical polymerism compound (C) and Photoepolymerizationinitiater initiater (D); Add other compositions that need use as required; Append solvent as required to normal concentration, obtain the target product photosensitive composition.
Colored filter also is provided among the present invention and has the liquid crystal indicator of this colored filter, after said colored filter contains photosensitive composition with the invention described above and forms predetermined pattern, through exposure and the color layer that develops and form.
Below, with Fig. 1 the step of using said photosensitive composition of the present invention to form colored filter is described.
Use photosensitive composition of the present invention; With COA (Color Filter on Array) when mode prepares colored filter, film and directly form red, green, blue various pattern of pixels a on the TFT layer c substrate of b being formed with SiNx (protective seam).Said pattern of pixels a is formed at the said SiNx b that films and goes up that (Fig. 1 a).
Be used for forming in the step that conducts the road between TFT layer c and common electrode (IZO layer) f,, making positive photosensitive resin film e form pattern (Fig. 1 b) with mask in order to remove SiNx (protective seam) b that films.
To be positioned at below the said positive photosensitive resin film e SiNx (protective seam) of (the conducting the road) b that films carries out dry-etching (dryetching) and forms and conduct road (Fig. 1 c).
In order to remove the positive photosensitive resin film e on the pattern of pixels a that remains in Fig. 1 c, remove positive photosensitive resin film e (Fig. 1 d) with peeling off developer solution.
Vapor deposition IZO layer f is used as common electrode (IZO layer) f (Fig. 1 e) with TFT layer c.
In order to form common electrode (IZO layer) f, form erect image photosensitive resin film e (Fig. 1 f) on the top of common electrode (IZO layer) f.
The exposed portion of formed positive photosensitive resin film e (part of exposing IZO layer f) is removed (Fig. 1 g) through wet etching (wetetching).
In order to remove the last positive photosensitive resin film e of common electrode (IZO layer) f that remains in Fig. 1 g, remove positive photosensitive resin film e (Fig. 1 h) with peeling off developer solution.
Even the colored filter that makes through said method can not produce the pattern disappearance yet under low exposure, therefore the liquid crystal indicator of excellent quality can be provided with high yield.
Below, explain in more detail based on embodiments of the invention, but following disclosed embodiment of the present invention only is an example that the scope of the invention is not limited to these embodiments.Scope of the present invention shown in claims, further comprise be equal to the record of claims meaning and scope in whole distortion.And in following examples, comparative example, " % " of expression content reaches " part ", do not have to specify, all representes quality % or mass parts with respect to photosensitive composition.
< the synthetic example of resin glue: resin (B) >
In flask with stirring machine, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe; Mix and import 90g propylene glycol monomethyl ether, 90g propylene glycol monomethyl ether and 11.0g 2-ENB (2-norbornene) (0.10mol); After air displacement in the flask is nitrogen; Be warming up to 80 ℃; From tap funnel, drip following solution to flask; Dripped 2 hours, said solution is in the potpourri that contains 70.5g benzyl methacrylate (0.4mol), 45.0g methacrylic acid (0.5mol) and 136g propylene glycol monomethyl ether, to add 3.2g tert-butyl hydroperoxide 2-ethylhexyl carbonic ester, continues to stir 5 hours down at 100 ℃.Then; With the nitrogen replacement in the flask is air; 30g GMA [0.2mol (being the 40mol% of the carboxyl of employed methacrylic acid among the present invention)], 0.9g three (dimethylaminomethyl) phenol and 0.145g p-dihydroxy-benzene are joined in the flask; Continue reaction 6 hours down at 110 ℃, the acid number that obtains solid constituent is the resin B of 100mgKOH/g.Measure through GPC, the poly weight-average molecular weight that converts is 31000, and molecular weight distribution (Mw/Mn) is 2.3.
At this moment, in the mensuration of the weight-average molecular weight (Mw) of said resin glue and number-average molecular weight (Mn), use HLC-8120GPC (eastern Cao (strain) production) device, post uses TSK-GELG4000HXL and TSK-GELG2000HXL for series connection; 40 ℃ of column temperatures, mobile phase solvent are tetrahydrofuran, flow velocity 1.0mL/ minute; Injection rate IR 50 μ L use the RI detecting device, and working sample concentration is 0.6 quality % (solvent=tetrahydrofuran); Fixing with standard substance use TSK STANDARD POLYSTYRENE F-40, F-4, F-1; A-2500, A-500 (eastern Cao (strain) production).
< embodiment 1～4 and comparative example 1～5 >
In each composition shown in the below table 1; To be mixed to the 20 quality % that its total amount accounts for pigment, pigment dispersing agent and propylene glycol monomethyl ether mixing total amount in Quality Percentage as pigment of (A) coloured material and the pigment dispersing agent of conduct (F) other adjuvants in advance; With ball mill pigment is fully disperseed; Then pearl is separated, further add to mix and contain all the other compositions that remain propylene glycol monomethyl ether, obtain photosensitive composition.
Table 1
Employed each constituent is described below in the said table 1.
Coloured material (A1): blue pigment dispersion liquid (C.I. naphthol green 58).
Coloured material (A2): yellow uitramarine dispersion liquid (C.I. pigment yellow 150).
Optical polymerism compound (C): dipentaerythritol acrylate (KAYARAD DPHA; Japan's chemical drug (strain) is produced).
Initiating agent (D1): Chemical formula 28 [NCI-831 production company: (strain) ADEKA＞].
Initiating agent (D2): ethyl ketone-1-[9-ethyl-6-(2-methyl-4-tetrahydro-pyran oxy benzoyl)-9H-cyclodextrin-3-yl]-1-(O-acetyl oxime) (Irgacure OXE02; Ciba (Ciba Specialty Chemical) company produces).
Initiating agent (D3): 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-(Irgacure 369 for butane-1-ketone; Ciba company produces).
Initiating agent (D4): 4,4 '-two (diethylamino) benzophenone (EAB-F; Hodogaya chemical (strain) is produced).
Solvent (E): propylene glycol monomethyl ether.
Adjuvant (F1): acrylic compounds pigment dispersing agent (Disperbyk-2009; BYK company produces).
Adjuvant (F2): 3-methacryloxypropyl trimethyl silane.
< measuring the preparation of print >
(healthy and free from worry (Corning) company produces, and #1737) uses neutral lotion, water and washing with alcohol successively, and is dry then with 2 square inches glass substrates.On this glass substrate with above-mentioned photosensitive composition (table 1) at 100mJ/cm
2Down exposure of exposure (365nm), rotary coating when omitting development step after thickness after firing be 3.2 μ m, then in dustless baking box in 100 ℃ predrying 3 minutes down.After the cooling; The interval that makes the substrate that has been coated with this photosensitive composition and quartzy system photomask (having the pattern of the transmissivity of making stepped variation in 1～100% scope and line/space pattern of 1 μ m to 50 μ m) is at 100 μ m; The extra-high-pressure mercury vapour lamp (trade name USH-250D) that uses Ushio motor (strain) to produce; Under atmospheric atmosphere, with 100mJ/cm
2Exposure (365nm) carry out photoscanning.Then, in the aqueous developer solution that contains 0.12% non-ionic surfactant and 0.06% potassium hydroxide, said filming developed after the immersion stipulated time down at 26 ℃, washing then, drying is 60 minutes under 230 ℃.On the pixel portions that obtains, there is not the table of discovery surface roughness.In addition, on non-pixel portions, the development residue does not appear on the substrate.
Table 2
* 1: after the development, for avoid in L/S, occurring pattern lack needed minimum must exposure be zero when 20mJ is following; When surpassing 20mJ be *.
* 2: with identical (x, the transmissivity (Y) that y) embodiment 1 forms on the chromaticity coordinates is 100% o'clock, the composition of embodiment and comparative example is zero when its transmissivity is low to moderate less than 5%; 5% when above be *.
Shown in said table 2; Based on the present invention; Contain and contain the embodiment 1～embodiment 4 of the Compound D 1 of two above photolytic activity oxime ester skeletons at a molecule as Photoepolymerizationinitiater initiater; Compare with the comparative example that does not contain this Compound D 1 1～5, even under low exposure, also can guarantee not occur pattern disappearance and transparency reduction.
Claims (6)
1. a photosensitive composition is characterized in that, it contains coloured material (A), resin glue (B), optical polymerism compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E); Said Photoepolymerizationinitiater initiater (D) contains the compound that in a molecule, has at least two photolytic activity oxime ester skeletons;
The said compound that in a molecule, has at least two photolytic activity oxime ester skeletons is that the compound shown in the following Chemical formula 18 passes through R
1Or R
2The dimer that dimerization obtains;
Chemical formula 18
In the said chemical formula, R
1, R
2And R
3Represent R independently of one another
11, OR
11, COR
11, SR
11, CONR
12R
13Or CN;
R
4And R
5Represent R independently of one another
11, OR
11, SR
11, COR
11, CONR
12R
13, NR
12COR
11, OCOR
11, COOR
11, SCOR
11, OCSR
11, COSR
11, CSOR
11, CN, halogen atom or hydroxyl,
A and b represent 0～3 independently of one another;
R
11, R
12, R
13Represent the alkyl of hydrogen atom, carbon number 1～20, the aryl of carbon number 6～30, the aryl alkyl of carbon number 7～30 or the heterocyclic radical of carbon number 2～20 independently of one another; At this, the hydrogen atom of alkyl, aryl, aryl alkyl and heterocyclic radical can also be by R
21, OR
21, COR
21, SR
21, NR
22R
23, CONR
22R
23,-NR
22-OR
23,-NCOR
22-OCOR
23,-C (=N-OR
21)-R
22,-C (=N-OCOR
21)-R
22, CN, halogen atom ,-CR
21=CR
22R
23,-CO-CR
21=CR
22R
23, OCO-CR
21=CR
22R
23, O-C
1-6Alkylidene-OCOR
21, COOR
21, epoxy radicals replaces;
R
21, R
22, R
23Represent the alkyl of hydrogen atom, carbon number 1～20, the aryl of carbon number 6～30, the aryl alkyl of carbon number 7～30 or the heterocyclic radical of carbon number 2～20 independently of one another;
Said R
11, R
12, R
13, R
21, R
22And R
23The methylene of shown substituent alkylene moiety can also be interrupted 1～5 time by unsaturated link, ehter bond, thioether bond, ester bond, thioester bond, amido link or urethane bonds; Said substituent moieties can also be side chain, also can be cyclic alkyl; Said substituent alkyl end can also be unsaturated link;
In addition, R
12And R
13And R
22And R
23Can also distinguish common formation ring, R
3Can also form ring jointly with the phenyl ring of adjacency.
2. photosensitive composition as claimed in claim 1 is characterized in that, the said compound that in a molecule, has at least two photolytic activity oxime ester skeletons is the compound shown in following Chemical formula 19 and the Chemical formula 20;
Chemical formula 19
Chemical formula 20
In said chemical formula, R
1～R
5, defined identical in a and b and the claim 1.
3. photosensitive composition as claimed in claim 1 is characterized in that, the said compound that in a molecule, has at least two photolytic activity oxime ester skeletons is the compound shown in the following Chemical formula 28;
Chemical formula 28
4. photosensitive composition as claimed in claim 1; It is characterized in that; The content of said Photoepolymerizationinitiater initiater (D) is benchmark with the solid constituent, accounts for 0.1～40 quality % of said resin glue (B) and said optical polymerism compound (C) total amount in mass percent;
The said compound that in a molecule, has two above photolytic activity oxime ester skeletons is benchmark with the solid constituent, counts with mass percent more than the 10 quality % of Photoepolymerizationinitiater initiater described in the said photosensitive composition (D).
5. a colored filter is characterized in that it contains color layer, said color layer be with any described photosensitive composition of claim 1-4 after forming predetermined pattern on the substrate, through exposure and develop formed.
6. the liquid crystal indicator that has the said colored filter of claim 5.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020100082917A KR20120019619A (en) | 2010-08-26 | 2010-08-26 | A colored photosensitive resin composition, color filter and liquid crystal display device having the same |
| KR10-2010-0082917 | 2010-08-26 |
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| Publication Number | Publication Date |
|---|---|
| CN102385252A true CN102385252A (en) | 2012-03-21 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN2011102495912A Pending CN102385252A (en) | 2010-08-26 | 2011-08-25 | Dyeing photosensitive resin combination, colorful color filter and liquid crystal display apparatus with colorful color filter |
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| Country | Link |
|---|---|
| JP (1) | JP2012048241A (en) |
| KR (1) | KR20120019619A (en) |
| CN (1) | CN102385252A (en) |
| TW (1) | TW201300947A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105785719A (en) * | 2015-01-13 | 2016-07-20 | 东友精细化工有限公司 | Self emission type photosensitive resin composition and display device comprising color conversion layer prepared thereby |
| CN108475019A (en) * | 2016-03-29 | 2018-08-31 | 株式会社艾迪科 | Black-colored photosensitive resin composition |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5236587B2 (en) * | 2009-07-15 | 2013-07-17 | 太陽ホールディングス株式会社 | Photocurable resin composition |
| JP2013047816A (en) * | 2012-10-01 | 2013-03-07 | Taiyo Holdings Co Ltd | Photosetting resin composition for printed wiring board |
| JP2013047818A (en) * | 2012-10-01 | 2013-03-07 | Taiyo Holdings Co Ltd | Photosetting resin composition |
| JP5536167B2 (en) * | 2012-10-01 | 2014-07-02 | 太陽ホールディングス株式会社 | Photo-curable resin composition for solder resist |
| KR20140052233A (en) * | 2012-10-23 | 2014-05-07 | 동우 화인켐 주식회사 | Curable resin composition and optical film prepared by using the same |
| JP2015041104A (en) * | 2013-08-22 | 2015-03-02 | 東友ファインケム株式会社 | Colored photosensitive resin composition, and color filter and display device including the same |
| KR102122403B1 (en) * | 2013-12-16 | 2020-06-12 | 엘지디스플레이 주식회사 | Color Filter Photo Resist |
| JP2015172664A (en) * | 2014-03-12 | 2015-10-01 | 株式会社タムラ製作所 | photosensitive resin composition |
| CN104076606B (en) | 2014-07-15 | 2019-12-03 | 常州强力电子新材料股份有限公司 | A kind of photosensitive composite and its application containing oxime ester lightlike initiating agent |
| CN106019839A (en) * | 2015-03-30 | 2016-10-12 | 住友化学株式会社 | Colored curable resin composition |
| JP6421161B2 (en) * | 2015-11-27 | 2018-11-07 | 株式会社タムラ製作所 | Photosensitive resin composition |
| KR102025359B1 (en) * | 2016-03-08 | 2019-09-25 | 삼성에스디아이 주식회사 | Photosensitive resin composition, black column spacerusing the same and color filter |
| JP6665692B2 (en) * | 2016-06-01 | 2020-03-13 | 三菱ケミカル株式会社 | Photopolymerization initiator, photosensitive resin composition, cured product, color filter, and image display device |
| JP7219378B1 (en) | 2021-12-09 | 2023-02-08 | 東洋インキＳｃホールディングス株式会社 | Photosensitive coloring composition, optical filter, image display device, and solid-state imaging device |
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| CN101528694A (en) * | 2006-12-27 | 2009-09-09 | 株式会社艾迪科 | Oxime ester compound and photopolymerization initiator containing the compound |
| CN102754031A (en) * | 2010-02-08 | 2012-10-24 | 太阳控股株式会社 | Layered structure and light-sensitive dry film used in same |
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| JP2005215378A (en) * | 2004-01-30 | 2005-08-11 | Toyo Ink Mfg Co Ltd | Photosensitive colored composition and color filter |
| JP2009192664A (en) * | 2008-02-13 | 2009-08-27 | Toppan Printing Co Ltd | Color filter and liquid crystal display device using the same |
| JP2011095355A (en) * | 2009-10-28 | 2011-05-12 | Toray Ind Inc | Photosensitive resin composition |
| JP5461259B2 (en) * | 2010-03-18 | 2014-04-02 | 太陽ホールディングス株式会社 | Photocurable resin composition, dry film, cured product, and printed wiring board |
-
2010
- 2010-08-26 KR KR1020100082917A patent/KR20120019619A/en not_active Application Discontinuation
-
2011
- 2011-08-25 JP JP2011183724A patent/JP2012048241A/en active Pending
- 2011-08-25 CN CN2011102495912A patent/CN102385252A/en active Pending
- 2011-08-26 TW TW100130827A patent/TW201300947A/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101528694A (en) * | 2006-12-27 | 2009-09-09 | 株式会社艾迪科 | Oxime ester compound and photopolymerization initiator containing the compound |
| CN102754031A (en) * | 2010-02-08 | 2012-10-24 | 太阳控股株式会社 | Layered structure and light-sensitive dry film used in same |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105785719A (en) * | 2015-01-13 | 2016-07-20 | 东友精细化工有限公司 | Self emission type photosensitive resin composition and display device comprising color conversion layer prepared thereby |
| CN105785719B (en) * | 2015-01-13 | 2021-06-15 | 东友精细化工有限公司 | Self-luminous photosensitive resin composition and display device containing color conversion layer produced from same |
| CN108475019A (en) * | 2016-03-29 | 2018-08-31 | 株式会社艾迪科 | Black-colored photosensitive resin composition |
| CN108475019B (en) * | 2016-03-29 | 2022-02-11 | 株式会社艾迪科 | Black photosensitive resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TW201300947A (en) | 2013-01-01 |
| KR20120019619A (en) | 2012-03-07 |
| JP2012048241A (en) | 2012-03-08 |
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