CN103969949B - Photosensitive composition - Google Patents
Photosensitive composition Download PDFInfo
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- CN103969949B CN103969949B CN201410042815.6A CN201410042815A CN103969949B CN 103969949 B CN103969949 B CN 103969949B CN 201410042815 A CN201410042815 A CN 201410042815A CN 103969949 B CN103969949 B CN 103969949B
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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
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- 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
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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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
-
- 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
- G03F7/20—Exposure; Apparatus therefor
-
- 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
- G03F7/20—Exposure; Apparatus therefor
- G03F7/2002—Exposure; Apparatus therefor with visible light or UV light, through an original having an opaque pattern on a transparent support, e.g. film printing, projection printing; by reflection of visible or UV light from an original such as a printed image
Abstract
The invention discloses a kind of photosensitive composition, the composition includes：Red stain, alkali soluble resins, photopolymerizable compound, antioxidant, Photoepolymerizationinitiater initiater and solvent, wherein, the alkali soluble resins has 30mg KOH/g to 170mg KOH/g acid number；The antioxidant includes the antioxidant functional group based on phenol and the antioxidant functional group based on phosphorus or the antioxidant functional group based on phenol and the antioxidant functional group based on sulphur；The Photoepolymerizationinitiater initiater includes the compound represented by formula 1, thus said composition can have high developing powder and excellent sensitivity and cohesive to be layered to suppress pattern during developing process, and can have excellent high brightness and contrast using the colour filter manufactured by above-mentioned composition.
Description
Technical field
The present invention relates to a kind of photosensitive composition.
Background technology
Colour filter is widely used in an imaging device, for example, so-called charge coupling device (CCD), liquid crystal display
Device (LCD) etc., and the application of colour filter has rapidly been expanded.Colour filter used is usual in color LCD or CCD
Manufactured by repeating following technique, the technique includes：On to the substrate in the black matrix" thereon with patterning
Photosensitive composition is coated evenly, and said composition includes corresponding respectively to the pigment of red, green and blueness；Heating
The substrate (is commonly referred to as " precalcining ") with drying, to form film；The film is exposed and developed；With on every kind of face
Color, selectively further heating and solidification (being commonly referred to as " rear calcining "), to form the pixel of a variety of colors.
In recent years, widening due to improvement in quality of CCD or LCD and purposes, it is highly desirable big to display panel
Width improves brightness.For this reason, increase blueness, red or green coloring phototonus have been carried out in a different direction
The research of the brightness (Y value) of composition.
At present, it is mainly used in the paratonere 177 (PR 177) and (PR of paratonere 254 of red (R) pixel in colour filter
254) high contrast is presented in combined colors material, but has low brightness (Y value).Therefore, if using has three colors
The colour filter of (R, G, B), then compared with green pixel and blue pixel, the foregoing red pixel containing combined colors material can be with
With relatively low brightness.Therefore, when colour filter is used in liquid crystal display, should be used according to the brightness of red pixel
The backlight of height output, to realize sufficient color rendering, contrast and definition on coloured image.
Korean patent application publication No.2012-112188 discloses a kind of red composition for colour filter, and bag
The colour filter of said composition is included, however, it does not have to propose any alternative for overcoming foregoing problems.
The content of the invention
It is therefore an object of the present invention to provide a kind of for being formed with smaller color change simultaneously with excellent light transmittance
Colour filter photosensitive composition.
It is a further object to provide a kind of with high developing powder and excellent sensitivity and viscosity
Photosensitive composition, so that the layering of pattern not to occur in developing process.
It is a further object to provide it is a kind of be used for formed with high brightness and contrast colour filter
Color sensation photosensitive resin composition.
The above-mentioned purpose of the present invention is realized by following features：
(1) a kind of photosensitive composition, including：Red stain, alkali soluble resins, photopolymerization chemical combination
Thing, antioxidant, Photoepolymerizationinitiater initiater and solvent, wherein, the alkali soluble resins has 30mg KOH/g to 170mg KOH/g
Acid number；The antioxidant includes the antioxidant functional group based on phenol and the antioxidant functional group based on phosphorus or base
In the antioxidant functional group of phenol and antioxidant functional group based on sulphur；The Photoepolymerizationinitiater initiater is included by the table of following formula 1
The compound shown：
[formula 1]
Wherein R1Expression-R4-R5；R2And R3It is that there is 1 to the alkyl of 8 carbon atoms, phenyl, benzyl or diphenyl sulfide respectively
Ether, the alkyl, phenyl, benzyl or diphenyl sulfide ether are unsubstituted or by hydroxyl or have 1 to 8 carbon atom
Alkyl substitutes；R4It is that there is 1 alkylidene to 4 carbon atoms；And R5It is that there is 3 cycloalkyl to 8 carbon atoms.
(2) composition according to above-mentioned (1), wherein, the alkali soluble resins has 50mg KOH/g to 160mg
KOH/g acid number.
(3) composition according to above-mentioned (1), wherein, the antioxidant is selected from 3,5- di-t-butyl -4- hydroxyls
Benzyl phosphoric acid, 6- [3- (3- tertiary butyl-4-hydroxy -5- methyl) propoxyl group] four-tert-butyl groups of -2,4,8,10- dibenzo [d, f]
[1,3,2] double [3- (the 3,5- di-t-butyl -4- hydroxyls of-dioxy phospha cycloheptane (dioxaphosphepine), thio diethylene
Phenyl) propionic ester], 2,2 '-thiobis (6- tert-butyl-4-methyl-Phenols) and 2,4- bis- (dodecylthiomethyl) -6- methyl
At least one of phenol.
(4) composition according to above-mentioned (1), wherein, according to solids content, for the coloring phototonus resin group
The gross weight of compound, comprising the amount of the red stain be 5 weight % (percentage by weight) to 60 weight %, comprising
The alkali soluble resins amount be 10 weight % to 80 weight %, and the amount of the photopolymerizable compound included is
5 weight % to 45 weight %；According to solids content, comprising the Photoepolymerizationinitiater initiater amount account for the alkali soluble resins and
0.1 weight % of the content sum of the photopolymerizable compound to 40 weight %；Comprising the amount of the antioxidant account for
1 weight % of the Photoepolymerizationinitiater initiater content to 100 weight %；And comprising the amount of the solvent account for the coloring
60 weight % of the gross weight of photosensitive polymer combination to 90 weight %.
(5) composition according to above-mentioned (1), wherein, comprising the amount of the compound represented by formula 1 account for
10 weight % of the gross weight of the Photoepolymerizationinitiater initiater to 100 weight %.
(6) composition according to above-mentioned (1), in addition to selected from aceotphenone compound, benzophenone cpd, triazine
At least one of compound, united imidazole and thioxanthone compounds Photoepolymerizationinitiater initiater.
(7) composition according to above-mentioned (1), in addition to selected from amines, carboxylic acid compound and contain sulfydryl
The photopolymerization of at least one of organosulfur compound triggers reinforcing agent.
(8) it is a kind of to use the filter according to made of above-mentioned (1) to the photosensitive composition any one of (7)
Color device.
(9) a kind of liquid crystal display, including the colour filter according to above-mentioned (8).
A kind of colour filter manufactured by photosensitive composition using the present invention has high brightness and contrast
Spend and there is less color change, be derived from excellent light transmittance.
Rapid development can be allowed according to the photosensitive composition of the present invention and there is excellent cohesive, from
And suppress pattern layering during developing process.
Embodiment
The invention discloses a kind of photosensitive composition, the composition includes：Red stain, alkali solubility
Resin, photopolymerizable compound, antioxidant, Photoepolymerizationinitiater initiater and solvent, wherein, the alkali soluble resins has 30mg
KOH/g to 170mg KOH/g acid number；The antioxidant includes the antioxidant functional group based on phenol and resisting based on phosphorus
Oxidant functional group or the antioxidant functional group based on phenol and the antioxidant functional group based on sulphur；The photopolymerization is drawn
Hair agent includes the compound represented by formula 1, and thus said composition can have high developing powder and excellent sensitivity and glue
Conjunction property, to suppress pattern layering in developing process, and, can be had using the colour filter manufactured by above-mentioned composition excellent
High brightness and contrast.
Hereinafter, the present invention will be described in further detail.
Red stain, alkali soluble resins, photopolymerization may include according to the photosensitive composition of the present invention
Compound, antioxidant, Photoepolymerizationinitiater initiater and solvent.
<Red stain>
According to the present invention, red be red color spectrum adopted name rather than with particular color index unique one
Kind color.
Pigment and dyestuff may include according to the red stain of the present invention.
Any organic pigment that pigment used in the present invention may include to commonly use in the related art, inorganic pigment or its
Mixture.
Organic pigment is not particularly limited, but can include, any general face for marking ink, ink-jet ink etc.
Material, more specifically, water-soluble azo pigment, AZOpigments not soluble in water, phthalocyanine color, quinacridone pigment, isoindoline
Ketone pigment, isoindoline pigment, perylene pigment, purple cyclic ketones pigment, dioxazines pigment, anthraquinone pigment, dianthraquinone pigment,
Anthrapyrimidine pigment, anthanthrone pigment, indanthrone pigment, yellow scholar's ketone pigment, pyranthrone pigments, pyrrolo-pyrrole-dione pigment
It can be used alone Deng, these pigment or be applied in combination with therein two or more.
Inorganic pigment is not particularly limited, but can include metallic compound (for example, metal oxide or metal complex
Thing) and carbon black, more specifically, the oxidation selected from least one of iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony metal
Thing, it can be used alone or is applied in combination with therein two or more.
Organic pigment and inorganic pigment may include according to colour index (Color Index, by association of dyeing man of Britain
(Society of Dyers and Colorists) announce) classification pigment compound.More specifically, C.I. can be used
Pigment yellow 13,20,24,31,53,83,86,93,94,109,110,117,125,137,138,139,147,148,150,153,
154th, 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 9,97,105,122,123,144,149,166,168,176,177,180,192,208,215,216,224,
242nd, 254,255 and 264 etc..Preferably, C.I. pigment yellow 13s 8,139,150 and 185 can be used；C.I. pigment orange 38；
C.I. pigment red 122,166,177,208,242,254 and 255 etc..These materials can be used alone or with two kinds therein
Or two or more it is applied in combination.
As long as dyestuff dissolves in organic solvent, and can ensure the dissolubility such as in alkaline-based developer, heat resistance, resistance to molten
The reliability of agent etc., then dyestuff is not particularly limited, such as can include：Acidity with acidic group (such as sulfonic acid, carboxylic acid)
Dyestuff；The salt of nitrogen-containing compound and acid dyes；The sulfonamide of acid dyes and its derivative；Azo-based, xanthene and/
Or the acid dyes of phthalocyanine and their derivative etc..
Dyestuff, which preferably includes, to be classified as according to colour index (by association of dyeing man of Britain (Society of Dyers
And Colorists) announce) dyestuff or the dyestuff listed in The Dye Note (Color Dyeing companies) in it is red
The compound of color dyestuff, blue dyes and cudbear.
Dyestuff is not particularly limited, but can include, for example, C.I. solvent dyes (for example, C.I. solvent red 8s, 45,49,
89th, 111,122,130,132,146,179 etc.) there is the aspect of excellent solubility and in organic solvent, C.I. solvent red 8s,
49th, 89,111,122,132,146 and 179 be preferable, it is highly preferred that using C.I. solvent red 8s, 122 and 132.
In addition, C.I. direct dyess may include, for example, C.I. directly red 79,82,83,84,91,92,96,97,98,99,
105、106、107、172、173、176、177、179、181、182、184、204、207、211、213、218、220、221、222、
232nd, 233,234,241,243,246,250 etc..
In addition, C.I. mordant dyes may include, for example, C.I. mordant rouges 1,2,3,4,9,11,12,14,17,18,19,
22、23、24、25、26、30、32、33、36、37、38、39、41、43、45、46、48、53、56、63、71、74、85、86、88、
90th, 94,95 etc..
These dyestuffs can be used alone or are applied in combination with therein two or more.
The content of dyestuff is not particularly limited, still, for example, according to solids content, for the gross weight of colouring agent, dyestuff
Content range can be from 0.5 weight % to 80 weight %, preferably from 1 weight % to 50 weight %.If the content of dyestuff
Within the above range, then it can prevent the reliability of the elution of such as dyestuff as caused by organic solvent after patterning from becoming
Difference, while keep excellent photonasty.
The content of red stain is not particularly limited, still, for example, according to solids content, for the colored photosensitive
The gross weight of property resin combination, the content of red stain can be from 5 weight % to 60 weight %, it is preferable that from 10 weights
Measure % to 45 weight %.If the content of red stain is within the above range, pixel has sufficient color density and aobvious
The loss of non-pixel portion is not reduced during shadow.Therefore, it is possible to reduce the appearance of residue.
Red stain is added in composition to be uniformly mixed in composition in the form of dispersion.Should
Dispersion can be produced, in addition to red stain, its dispersant and solvent for including being generally used for composition.
Dispersant is added to allow decondensation and keep the stability of pigment and dyestuff, dispersant may include in existing skill
The dispersant commonly used in art is without limiting.Preferably, acrylate dispersant can be used, for example, butyl methacrylate
Or methacrylic acid N, N- dimethylaminoethyl (DMAEMA) (BMA)；Polycarboxylate；Unsaturated polyamide；Polycarboxylic acids；Polycarboxylic acids
(part) amine salt；The ammonium salt of polycarboxylic acids；The alkylamine salt of polycarboxylic acids；Polysiloxanes；Long-chain polyaminoamide phosphate；Contain
The polycarboxylate of hydroxyl and its modified product；Pass through the reaction shape of the polyester containing free carboxy and poly- (low-grade alkylidene imines)
Into acid amides or its salt；Water-soluble resin or water-soluble polymeric compounds, for example, (methyl) acrylic-styrene copolymer,
(methyl) acrylic acid-(methyl) acrylate copolymer, styrene-maleic acid copolymer, polyvinyl alcohol or polyvinylpyrrolidine
Alkanone etc.；Polyester；Modified polyacrylate；The addition product of ethylene oxide/propylene oxide；Phosphate etc..These compounds can
To be used alone or be applied in combination with therein two or more.
For example, available commercial dispersants may include in the present invention：DISPER BYK-160、DISPER BYK-161、
DISPER BYK-162、DISPER BYK-163、DISPER BYK-164、DISPER BYK-166、DISPER BYK-171、
DISPER BYK-182、DISPER BYK-184、DISPER BYK-2000、DISPER BYK-2001、DISPER BYK-
2070、DISPER BYK-2150(BYK Chemicals)；EFKA-44、EFKA-46、EFKA-47、EFKA-48、EFKA-
4010、EFKA-4050、EFKA-4055、EFKA-4020、EFKA-4015、EFKA-4060、EFKA-4300、EFKA-4330、
EFKA-4400, EFKA-4406, EFKA-4510, EFKA-4800 (BASF AG)；SOLSPERS-24000、SOLSPERS-
32550th, NBZ-4204/10 (Lubirzol companies)；HINOACT T-6000、HINOACT T-7000、HINOACT T-8000
(Kawaken Fine Chemical companies)；AJISPER PB821、AJISPER PB822、AJISPER PB823
(Ajinomoto companies)；FLORENE DOPA-17HF、FLORENE DOPA-15BHF、FLORENE DOPA-33、FLORENE
DOPA-44 (Kyoeisha Chemicals) etc., these dispersants can be used alone or with two kinds therein or two kinds with
On be applied in combination.
The content of dispersant is not particularly limited, still, for example, according to solids content, for the pigment of 100 parts by weight,
The content of dispersant can be from 5 parts by weight to 60 parts by weight, it is preferable that from 15 parts by weight to 50 parts by weight.If dispersant
Within the above range, pigment is suitably formed subparticle to content and red stain can have required viscosity.
<Alkali soluble resins>
When including ethylenically unsaturated monomers with carboxyl, alkali soluble resins is polymerize.Ethylenic with carboxyl
Unsaturated monomer is the component for assigning solubility property to alkaline developer used in developing process when the patterning is performed.
Ethylenically unsaturated monomers with carboxyl are not particularly limited, but can include, such as：Monocarboxylic acid (such as third
Olefin(e) acid, methacrylic acid, butenoic acid etc.)；Dicarboxylic acids (such as fumaric acid, mesaconic acid (methaconic acid) and itaconic acid etc.
And its acid anhydrides)；There is list (methyl) acrylate of the polymer of carboxyl and hydroxyl at its both ends, such as ω-carboxyl gathers oneself
Acid lactone list (methyl) acrylate etc., it is preferable that acrylic acid and methacrylic acid, these materials can be used alone or with
Therein two or more is applied in combination.
The acid value of alkali soluble resins can be from 30mg KOH/g to 170mg KOH/g, it is preferable that from 50mg KOH/g
To 160mg KOH/g.If the acid number of alkali soluble resins is within the above range, resin is more compatible to prevent dyestuff from analysing with dyestuff
Go out, photosensitive composition there can be excellent storage stability to keep required viscosity and sufficient development speed
Degree.
In order to ensure the further developing performance of alkali soluble resins, the resin can have hydroxyl.
The method that hydroxyl is provided to alkali soluble resins is not particularly limited, but can include, such as：In the same of resin polymerization
When further addition with hydroxyl ethylenically unsaturated monomers；Resin reacts with the compound with glycidyl；Pass through
The copolymer polymerizeing with the ethylenically unsaturated monomers of hydroxyl is added in addition to react with the compound with glycidyl
Deng.
Ethylenically unsaturated monomers with hydroxyl are not particularly limited, but can include, for example, (methyl) acrylic acid-
2- hydroxy methacrylates, (methyl) 2-hydroxypropyl acrylate, (methyl) acrylic acid -4- hydroxybutyls, 2- hydroxyl -3- phenoxy groups third
Base (methyl) acrylate, N- hydroxyethyl acrylamides etc., it is preferable that (methyl) 2-Hydroxy ethyl acrylate.These materials
It can be used alone or be applied in combination with therein two or more.
Compound with glycidyl is not particularly limited, but can include, for example, butyl glycidyl ether, third
Base glycidol ether, phenyl glycidyl ether, 2- hexyl glycidyl ethers, glycidyl butyl ester, glycidyl first
Ether, ethyl ether, isopropyl glycidyl ether, tertiary butyl glycidyl ether, benzyl glycidyl ether, 4- tert-butyl benzenes
Formic acid ethylene oxidic ester, stearic acid glycidyl ester, arylolycidyl ethers, GMA etc., preferably
Butyl glycidyl ether, arylolycidyl ethers and GMA.These materials can be used alone or
It is applied in combination with therein two or more.
It can be polymerize according to the alkali soluble resins of the present invention, while also include can be copolymerized with aforementioned monomer at least one
The other monomer of kind.For example, aromatic ethenyl compound, for example, styrene, vinyltoluene, methyl styrene, to chlorobenzene
Ethene, o-methoxystyrene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, a vinyl benzyl first
Ether, to vinyl benzyl methyl ether, adjacent vinylbenzyl glycidyl ether, a vinylbenzyl glycidyl ether, to vinyl benzyl
Glycidol ether etc.；The maleimide compound of N- substitutions, such as N- N-cyclohexylmaleimides, N- benzyl maleimides
Hydroxyphenyl-maleimides, N- para hydroxybenzenes between amine, N-phenylmaleimide, N- o-hydroxy-phenyls maleimide, N-
Methylphenylmaleimide, N- p-methylphenyls Malaysia acyl between base maleimide, N- o-methyl-phenyls maleimide, N-
Imines, N- o-methoxyphenyls maleimide, N- m-methoxyphenyls maleimide, N- p-methoxyphenyl maleimides
Amine etc.；(methyl) alkyl acrylate, such as (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) acrylic acid are just
Propyl ester, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) acrylic acid are secondary
Butyl ester, (methyl) tert-butyl acrylate etc.；Alicyclic (methyl) acrylate, such as (methyl) acrylic acid ring pentyl ester, (methyl)
Cyclohexyl acrylate, 2- methylcyclohexyls (methyl) acrylate, three rings [5.2.1.0.2.6] decane -8- bases (methyl) propylene
Acid esters, 2- bicyclopentyl oxygen ethyl (methyl) acrylate, isobornyl (methyl) acrylate etc.；(methyl) acrylic acid aryl
Ester, such as (methyl) phenyl acrylate, (methyl) benzyl acrylate etc.；Unsaturated oxetane compound, for example, 3-
(methacryloxymethyl) oxetanes, 3- (methacryloxymethyl) -3- Ethyloxetanes, 3- (first
Base acryloyloxymethyl) -2- trifluoromethyls oxetanes, 3- (methacryloxymethyl) -2- phenyl oxa- ring fourths
Alkane, 2- (methacryloxymethyl) oxetanes, 2- (methacryloxymethyl) -4- trifluoromethyl oxa- ring fourths
Alkane etc., these materials can be used alone or are applied in combination with therein two or more.
The content of alkali soluble resins is not particularly limited, but for example according to solids content, for the coloring phototonus
The gross weight of resin combination, the content range of alkali soluble resins can be from 10 weight % to 80 weight %, it is preferable that from 10 weights
Measure % to 70 weight %.If the content of alkali soluble resins is within the above range, it can have enough molten in a developer
Performance is solved can easily form pattern, and can prevent the film during development in the pixel portion of exposed portion from reducing, from
And cause the reduction of non-pixel portion loss.
The embodiment of the preparation method of alkali soluble resins is described below.
By aforementioned monomer, relative to content of monomer 0.5 solvent to 20 times and the mole relative to monomer 0.1% again
Polymerization initiator to 10% is added to the burning provided with agitator, thermometer, backflow cooling tube, titration outfit and nitrogen introduction pipe line
In bottle, then substituted with nitrogen.Then, it is stirred 1 hour to 10 hours at 40 DEG C to 140 DEG C.
Above-mentioned solvent used herein can be any common solvent for radical polymerization, for example, it includes：Choosing
From tetrahydrofuran, dioxane, ethylene glycol dimethyl ethyl, diethylene glycol dimethyl ethyl, acetone, methyl ethyl ketone, methyl
Isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ethyl acetate, 3- methoxybutyls acetic acid esters, first
Alcohol, ethanol, propyl alcohol, n-butanol, ethylene glycol single methyl ether, propylene glycol monomethyl ether, toluene, dimethylbenzene, ethylbenzene, chloroform and diformazan
Any of sulfoxide, these materials can be used alone or used with their mixture.
Polymerization initiator can be any initiator conventional in the related art without especially limitation.More specifically
Ground, it can include：Organic peroxide, for example, di-isopropylbenzene hydroperoxide, di-tert-butyl peroxide, benzoyl peroxide,
Tert-butyl peroxide propylene carbonate, peroxidating tertiary pentyl -2- ethyl hexanoates, tert-butyl peroxide -2- ethyl hexanoates etc.；And nitrogen
Compound, such as 2,2'- azodiisobutyronitrile, 2,2'- azos two (2,4- methyl pentane nitrile), dimethyl -2,2'- azo two
(2 Methylpropionic acid ester) etc., these materials can be used alone or are applied in combination with therein two or more.
In order to control the molecular weight in aforementioned process, α-methylstyrenedimer or compound containing sulfydryl can be by
As chain-transferring agent.For the monomer of 100 parts by weight, the use of such α-methylstyrenedimer or the compound containing sulfydryl
Amount can be 0.005 parts by weight to 5 parts by weight.On the condition of polymerization, the heat release value considered according to polymerization or Preparation equipment, enter
Material method or reaction temperature can be controlled suitably.
<Photopolymerizable compound>
Photopolymerizable compound is the component of enhancing pattern intensity, can include Monofunctional monomers, bifunctional monomer
Or polyfunctional monomer etc., preferably bifunctional monomer or polyfunctional monomer.For example, the specific example of these monomers
It can include：Monofunctional monomers, such as nonyl phenyl carbitol acrylate, 2- hydroxyl -3- phenoxypropylacrylates, 2-
Ethylhexyl carbitol acrylate, 2- hydroxy ethyl methacrylates, NVP etc.；Bifunctional monomer, such as 1,
6- hexylene glycols two (methyl) acrylate, two (methyl) acrylic acid glycol esters, neopentyl glycol two (methyl) acrylate, triethylene glycol
Double (acryloyl-oxyethyl) ether, 3- methyl pentanediols two (methyl) acrylate etc. of two (methyl) acrylate, bisphenol-A；
Polyfunctional monomer, such as trimethylolpropane tris (methyl) acrylate, the trimethylolpropane tris (methyl) third of ethoxylation
Olefin(e) acid ester, propenoxylated trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, Ji Wusi
Alcohol four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, pentaerythrite six (methyl) propylene of ethoxylation
Acid esters, propenoxylated dipentaerythritol six (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc., these lists
Body is used alone or is applied in combination with therein two or more.
The content of photopolymerizable compound is not particularly limited, still, such as according to solids content, for described color sensation
The gross weight of photosensitive resin composition, the content range of photopolymerizable compound can be from 5 weight % to 45 weight %, preferably
Ground, from 7 weight % to 45 weight %.If the content of photopolymerizable compound is within the above range, pixel portion can have
Favourable intensity or smoothness.
<Antioxidant>
Antioxidant used in the present invention can include the antioxidant functional group based on phenol and resisting based on phosphorus
Oxidant functional group or the antioxidant functional group based on phenol and the antioxidant functional group based on sulphur.By including so
Antioxidant, color change can be prevented, excellent light transmittance can be obtained and photosensitive reduction can be suppressed, thus
Suppress the layering of the pattern in developing process.
Antioxidant with the antioxidant functional group based on phenol and the antioxidant functional group based on phosphorus is without spy
Do not limit, but may include, for example, 3,5- di-t-butyl -4- hydroxybenzyl phosphates, 6- [3- (3- tertiary butyl-4-hydroxies -5-
Methyl) propoxyl group] -2,4,8,10- tetra--tert-butyl group dibenzo [d, f] [1,3,2]-dioxy phospha cycloheptane etc..Commercially available prod
Specific example may include IRGANOX 1425 (BASF AG's manufacture), Sumilizer GP (Sumitomo Chemicals companies
Manufacture) etc..
It is not particularly limited with the antioxidant functional group based on phenol and the antioxidant functional group based on sulphur, still
It may include, for example, thio diethylene double [3- (3,5- di-t-butyl -4- hydroxy phenyls) propionic ester], 2,2 '-thiobis (uncle 6-
Butyl -4- methylphenols), double (dodecylthiomethyl) -6- methylphenols of 2,4- etc..The specific example of commercially available prod may include
IRGANOX 1035 (BASF AG's manufacture), IRGANOX 1081 (BASF AG's manufacture), (BASF AG's systems of IRGANOX 1726
Make) etc..
These antioxidants as described above can be used alone or with two or more combination therein
Use.
The content of antioxidant is not particularly limited, still, such as according to solids content, for containing for Photoepolymerizationinitiater initiater
Amount, the content range of antioxidant can be from 1 weight % to 100 weight %, preferably from 2 weight % to 50 weight %.It is if anti-
The content of oxidant within the above range, then can reduce color change while keep high photosensitivity, and then improve light transmittance.
<Photoepolymerizationinitiater initiater>
The compound represented by following formula 1 may include according to the Photoepolymerizationinitiater initiater of the present invention：
[formula 1]
Wherein, R1Expression-R4-R5；R2And R3It is that there is 1 to the alkyl of 8 carbon atoms, phenyl, benzyl or hexichol respectively
Thioether group, the alkyl, phenyl, benzyl or diphenyl sulfide ether are that unsubstituted either by hydroxyl or have 1 to 8 carbon original
The alkyl substitution of son；R4It is that there is 1 alkylidene to 4 carbon atoms；And R5It is that there is 3 cycloalkyl to 8 carbon atoms.
As caused by can preventing due to dyestuff the Photoepolymerizationinitiater initiater that formula 1 represents sensitivity reduce, thus provide including
The effective optical polymerism energy of the photosensitive composition of dyestuff.Therefore, if Photoepolymerizationinitiater initiater with according to this hair
Bright antioxidant combination uses, then the suppression of the decline to sensitivity can be maximized suppresses aobvious so as to further improve
The effect that pattern is layered during shadow.
In addition to the Photoepolymerizationinitiater initiater represented by formula 1, photosensitive composition of the invention may also include
Conventional at least one Photoepolymerizationinitiater initiater in the related art.For example, it can include：Aceotphenone compound, benzophenone
Compound, triaizine compounds, united imidazole, thioxanthone compounds etc..These compounds can be used alone or with wherein
Two or more be applied in combination.
Aceotphenone compound is not particularly limited, but may include, such as diethoxy acetophenone, 2- hydroxy-2-methyls-
1- phenyl -1- acetone, benzyl dimethyl ketal, 2- hydroxyls -1- [4- (2- hydroxyl-oxethyls) phenyl] -2- methyl isophthalic acids-acetone, 1-
Hydroxycyclohexylphenylketone, 2- methyl isophthalic acids-(4- methyl thio phenyls) -2- morpholinyl -1- acetone, 2- benzyl -2- dimethylaminos -1-
(4- morpholino phenyls) -1- butanone, 2- hydroxy-2-methyls -1- [4- (1- methyl ethylenes) phenyl] -1- acetone, 2- (4- methyl
Benzyl) -2- (dimethylamino) -1- (4- morpholino phenyls) -1- butanone etc..
Benzophenone cpd is not particularly limited, but may include, such as benzophenone, o-benzoyl methyl benzoic acid
Ester, 4- phenyl benzophenones, 4- benzoyl -4'- dimethyl diphenyl sulfides, 3,3', 4,4'- tetra- (tert-butyl hydroperoxide carbonyl)
Benzophenone, 2,4,6- tri-methyl benzophenones etc..
Triaizine compounds are not particularly limited, but may include, such as double (trichloromethyl) -6- (the 4- methoxybenzenes of 2,4-
Base) -1,3,5- triazines, double (trichloromethyl) -6- (4- methoxyl groups the naphthyl) -1,3,5- triazines of 2,4-, 2,4- double (trichloromethyls) -
Double (trichloromethyl) -6- (4- the methoxyl-styrenes) -1,3,5- triazines of 6- piperonyl -1,3,5- triazines, 2,4-, 2,4- are double
Double (trichloromethyl) -6- [2- (furans of (trichloromethyl) -6- [2- (5- methylfuran -2- bases) vinyl] -1,3,5- triazines, 2,4-
Mutter -2- bases) vinyl] -1,3,5- triazines, double (trichloromethyl) -6- [2- (4- lignocaine -2- aminomethyl phenyls) ethene of 2,4-
Base] -1,3,5- triazines, double (trichloromethyl) -6- [2- (3,4- Dimethoxyphenyls) the vinyl] -1,3,5- triazines of 2,4- etc..
United imidazole is not particularly limited, but may include, such as double (the 2- chlorphenyls) -4,4', 5,5'- of 2,2'-
Double (2,3- dichlorophenyls) -4,4 ', the 5,5'- tetraphenyls bisglyoxalines of tetraphenyl bisglyoxaline, 2,2'-, 2,2'- double (2- chlorphenyls) -
Double (2- the chlorophenyls) -4,4', 5,5'- tetra- (tri-alkoxy phenyl) of 4,4', 5,5'- tetra- (alkoxyl phenyl) bisglyoxaline, 2,2'-
Double (2,6- dichlorophenyls) -4,4 ', the 5,5'- tetraphenyl -1,2'- bisglyoxalines of bisglyoxaline, 2,2- have in aforesaid compound
In any imidazolium compounds for the phenyl that 4,4', 5,5' positions are substituted by alkyl carbonyl base, it is preferable that 2,2'- double (2- chlorobenzenes
Base) -4,4', 5,5'- tetraphenyls bisglyoxaline, 2,2'- double (2,3- dichlorophenyls) -4,4', 5,5'- tetraphenyls bisglyoxaline, 2,2-
Double (2,6- dichlorophenyls) -4,4', 5,5'- tetraphenyl -1,2'- bisglyoxalines etc..
Thioxanthone compounds are not particularly limited, but may include, such as ITX, 2,4- diethyl thioxanthenes
Ketone, the clopenthixal ketones of 2,4- bis-, the chloro- 4- propoxythioxanthones of 1- etc..
The content of Photoepolymerizationinitiater initiater is not particularly limited, still, such as according to solids content, for alkali soluble resins and
The summation of the content of photopolymerizable compound, the content range of Photoepolymerizationinitiater initiater can be excellent from 0.1 weight % to 40 weight %
Selection of land, from 1 weight % to 30 weight %.If the content of Photoepolymerizationinitiater initiater is within the above range, coloring phototonus resin
The sensitivity of composition is uprised to reduce the time for exposure, so as to improve productivity ratio and keep high resolution ratio.In addition, institute's shape
Into pixel portion can have favourable intensity, and good smoothness can be realized on the surface of pixel portion.
In the Photoepolymerizationinitiater initiater as described above, the content of the compound represented by formula 1 is not particularly limited, but
Be, such as the gross weight for Photoepolymerizationinitiater initiater, the content range of the compound represented by formula 1 can from 10 weight % to
100 weight %, it is preferable that from 20 weight % to 100 weight %.If the content of the compound represented by formula 1 is in above-mentioned model
In enclosing, then photosensitive improvement can be maximized.
<Photopolymerization triggers reinforcing agent>
The photosensitive composition of the present invention may also include photopolymerization and trigger reinforcing agent to improve photonasty.
Photopolymerization triggers reinforcing agent to be not particularly limited, but may include, such as amines, carboxylic acid compound or has
Organosulfur compound of sulfydryl etc., these materials can be used alone or made with two or more combination therein
With.
Amines is not particularly limited, but can include, such as aliphatic amine, as triethanolamine, methyl diethanolamine,
Triisopropanolamine etc.；Aromatic amine, such as 4- dimethylaminobenzoic acids methyl esters, 4- dimethyl ethyl aminobenzoates, 4- dimethylaminos
Isoamyl benzoate, 4- dimethylaminobenzoic acid 2- ethylhexyls, 2- dimethylaminoethyls benzoic ether, N, N- dimethyl is to first
Double (dimethylamino) benzophenone of aniline, 4,4'-, double (lignocaine) benzophenone of 4,4'- etc..
Carboxylic acid compound is not particularly limited, but may include, such as the miscellaneous acetic acid of aromatic series, such as phenyl acetic acid, methyl
Phenyl acetic acid, ethylphenyl thioacetic acid, Methylethyl phenyl thioacetic acid, 3,5-dimethylphenyl thioacetic acid, methoxyl group
Phenyl acetic acid, dimethoxyphenylthio acetic acid, chlorophenylthio acetic acid, dichlorophenyl thioacetic acid, N- phenyl aminos
Acetic acid, phenoxyacetic acid, naphthylthio acetic acid, N- naphthyl-aminos acetic acid, naphthoxy acetic acid etc..
Organosulfur compound with sulfydryl is not particularly limited, but may include, for example, 2-mercaptobenzothiazole, Isosorbide-5-Nitrae-
Double (3- sulfydryls butyryl acyloxy) butane, 1,3,5- tri- (3- sulfydryls butoxyethyl group) -1,3,5- triazines -2,4,6 (1H, 3H, 5H) -
Triketone, trimethylolpropane tris (3-thiopropionate), pentaerythrite four (3- mercaptobutylates), (the 3- sulfydryls of pentaerythrite four
Propionic ester), dipentaerythritol six (3-thiopropionate), tetraethylene glycol double (3-thiopropionate) etc..
Photopolymerization triggers the content of reinforcing agent to be not particularly limited, still, such as according to solids content, for colored photosensitive
Property resin combination gross weight, photopolymerization trigger reinforcing agent content range can be from 0.1 weight % to 40 weight %, preferably
From 1 weight % to 30 weight %.If photopolymerization triggers the content of reinforcing agent within the above range, coloring phototonus resin group
The photonasty of compound can be further enhanced, so as to improve productivity ratio.
<Solvent>
As long as the solvent used in the present invention can dissolve aforementioned component, then the solvent used in the present invention does not limit particularly
System, but may include, such as ether, aromatic hydrocarbon, ketone, alcohol, ester etc., these materials can be used alone or with two kinds therein or
Two or more is applied in combination.
The specific example of solvent may include：Ethylene glycol monoalkyl ether, for example, glycol monoethyl ether, ethylene glycol monoethyl ether, second
Glycol monopropyl ether, ethylene glycol monobutyl ether etc.；It is ether, such as diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol (DEG) dipropyl ether, two sweet
Alcohol butyl oxide, methyl glycol acetate, ethyl cellosolve acetate, dihydroxypropane single-ether acetate, propylene glycol monopropyl ether vinegar
Acid esters, methoxybutyl acetate, methoxypentyl acetate etc.；Aromatic hydrocarbon, for example, benzene,toluene,xylene, mesitylene
Deng；Ketone, for example, methyl ethyl ketone, acetone, methylpentanone, methyl iso-butyl ketone (MIBK), cyclohexanone etc.；Alcohol, for example, ethanol, propyl alcohol,
Butanol, hexanol, cyclohexanol, glycol, glycerine etc.；Ester, for example, 3- ethoxyl ethyl propionates, 3- methoxy methyl propionates, γ-fourth
Lactone etc., it is preferable that can use propylene glycol monomethyl ether acetate, dihydroxypropane single-ether acetate, cyclohexanone, ethyl lactate,
Butyl lactate, 3- ethoxyl ethyl propionates, 3- methoxy methyl propionates.
On in terms of the applicability and drying property, solvent is preferably the organic solvent with 100 DEG C to 200 DEG C of boiling point.
The content of solvent is not particularly limited, but for example, the solvent may include the solvent included in colorant dispersion,
For the gross weight of photosensitive composition, the total content scope of the solvent can from 60 weight % to 90 weight %,
It is preferred that from 70 weight % to 85 weight %.If the content of solvent is within the above range, favourable applicability can be obtained.
<Additive>
The photosensitive composition of the present invention may also include lives selected from alternative polymerizable compound, curing agent, surface
Any additive of property agent, adhesion enhancer, UV absorbents and anti-coagulants etc..
The alternative polymerizable compound is not particularly limited, but may include, such as curable resin, such as epoxy resin,
Maleimide resin etc., thermoplastic resin, such as polyvinyl alcohol, polyacrylic acid, polyalkylene glycol monoalkyl ether, poly- fluoroalkyl third
Olefin(e) acid ester, polyester, polyurethane etc..
The curing agent is not special for the stage curing component with increase mechanical strength of depth, the species of the curing agent
Limitation, but may include, such as epoxide, many functional group isocyanates' compound, melamine compound, oxetanes
Compound etc..
Epoxide is not particularly limited, but may include, for example, bisphenol A epoxide resin, hydrogenated bisphenol A epoxy resin,
Bisphenol F epoxy resin, A Hydrogenated Bisphenol A F epoxy resin, novolac epoxy resin, other aromatic epoxy resins, aliphatic ring oxygen tree
Fat, glycidyl ester type resin, the brominated derivative of glycidic amine type resin or epoxy resin；Except epoxy resin and its bromine
Change aliphatic, alicyclic or aromatic epoxy compound, the butadiene (co) polymer epoxides outside derivative；It is different
Pentadiene (co) polymer epoxides；Glycidyl (methyl) acrylate (co) polymer；Triglycidyl group isocyanide
Acid esters etc..
Oxetane compound is not particularly limited, but may include, for example, dioxetane carbonic ester, dimethylbenzene
Dioxetane, dioxetane adipate ester, dioxetane terephthalate, cyclohexane dicarboxylic acid dioxa
Cyclobutane etc..
Curing agent can be with being capable of the epoxy radicals of ring-opening polymerisation epoxide or the oxa- ring of oxetane compound
The auxiliary curing agent compound of butane main chain is compatible.
Auxiliary curing agent compound is not particularly limited, but may include, such as polyvalent carboxylic acid, polyvalent carboxylic acid's acid anhydride, acid producing agent
Deng.Polyvalent carboxylic acid's acid anhydride may include any epoxy curing agent that in the market can be bought.
These Commercial epoxy resins curing agent that can be used in the present invention are not particularly limited, but may include, for example,
Adekahadona EH-700 (trade name, being manufactured by Adeka Engineering Co., Ltds), Likashitdo HH (commodity
Name, by New Japan Chemicals Co., Ltds manufacture), MH-700 (trade name, it is limited by New Japan Chemicals
Company manufactures) etc..
Surfactant is the component for the coated molded property for improving photosensitive resin composition, and its species is not particularly limited,
But it may include, for example, fluorine surfactant, silicon surface active agent or its mixture.
Silicon surface active agent is not particularly limited, but can include commercially available prod, such as：By Dow-corning Doray
DC3PA, DC7PA, SH11PA, SH21PA, SH8400 of the manufacture of Silicon companies etc.；By GE Toshiba Silicon companies
TSF-4440, TSF-4300, TSF-4445, TSF-4446, TSF-4460, TSF-4452 of manufacture etc..
Fluorine surfactant is not particularly limited, but can include commercially available prod, such as：By Dainippon Ink
Mega pieces F-470, F-471, F-475, F-482, F-489 etc. of Chemical Industries manufactures.
The species of adhesion enhancer is not particularly limited, but can include, such as vinyltrimethoxy silane, vinyl
Triethoxysilane, vinyl three (2- methoxy ethoxies) silane, N- (2- aminoethyls) -3- aminopropyltriethoxy dimethoxy silicon
Alkane, N- (2- aminoethyls) -3- aminopropyl trimethoxysilanes, 3- aminopropyl triethoxysilanes, 3- glycidol ethers epoxide third
Base trimethoxy silane, 3- glycydoxies dimethoxysilane, 2- (3,4- epoxycyclohexyl) ethyl trimethoxy
Base silane, 3- chloropropylmethyldimethoxysilanes, 3- r-chloropropyl trimethoxyl silanes, 3- methacryloxypropyl front threes
TMOS, 3-mercaptopropyi trimethoxy silane, 3- isocyanates propyl trimethoxy silicane, the second of 3- isocyanates propyl group three
TMOS etc., these materials can be used alone or are applied in combination with therein two or more.
The content of adhesion enhancer is not particularly limited, still, such as according to solids content, for coloring phototonus resin
The gross weight of composition, the content range of adhesion enhancer can be from 0.01 weight % to 10 weight %, it is preferable that from 0.05 weight
Measure % to 2 weight %.
The species of UV absorbents is not particularly limited, but can include, for example, 2- (the 3- tert-butyl group -2- hydroxy-5-methyl bases
Phenyl) -5- chlorobenzotriazoles, alkoxy benzophenone etc..
Anti-coagulants is not particularly limited, but may include, such as Sodium Polyacrylate.
<The preparation of photosensitive composition>
It can be included according to the preparation method of the photosensitive composition of the present invention, such as：By colouring agent and divide
Powder is added in solvent and disperseed to prepare the colorant dispersion with single-size size；Dissolve in a solvent
Alkali soluble resins, photopolymerizable compound, Photoepolymerizationinitiater initiater and other additives if needed, by these materials with it is upper
State colorant dispersion mixing；And alternatively, it is additionally added new solvent.
<Colour filter>
In addition, the invention provides the colour filter manufactured using above-mentioned photosensitive composition.
Colour filter includes substrate and the color layer formed at the top of substrate.
Substrate can be the part for being provided with colour filter of the original substrate either display for colour filter in itself,
Therefore, substrate is not particularly limited.Substrate can be glass, silicon (Si), silica (SiOx) or polymeric substrates, polymer matrix
Plate can be made up of polyether sulfone (PES), makrolon (PC) etc..
Dyed layer is the layer of the photosensitive composition containing the present invention, can be by being coloured to coating on the layer
Photosensitive polymer combination, exposure, development and then the coating heat cure is made with forming required pattern.
Colour filter with above-mentioned this substrate and dyed layer can also include being formed in each colored pattern and/or black
Dividing plate between matrix.In addition, colour filter can include the protective layer formed at the top of dyed layer.
<Liquid crystal display>
In addition, the invention provides a kind of liquid crystal display with this colour filter as described above.
In addition to above-mentioned this colour filter, it can be included according to the liquid crystal display of the present invention of the present invention
Known technical configuration in correlation technique, and it is not particularly limited.
Hereinafter, in order to more thoroughly understand the present invention, preferred embodiment will be described.However, for ability
The technical staff in domain is evident that such embodiment is provided and will to appended right for exemplary purposes
Book is asked to be not particularly limited, various modifications and changes are feasible without departing from the scope and spirit of the present invention, and
And such modifications and changes are fully included in the present invention such as appended claim restriction.
Embodiment
The preparation of preparation example-colorant dispersion
Preparing for red colored agent dispersion is as follows：The C.I. pigment of 14 parts by weight is mixed and disperseed by bead mill
Red 254, the AJISPER PB821 as dispersant of 6 parts by weight (pass through AJINOMOTO Fine Techno Co., Ltds system
Make) and propylene glycol monomethyl ether acetate and the solvent of the cyclohexanone of 20 parts by weight including 60 parts by weight, continue 12 hours.
The synthesis of synthesis example-alkali soluble resins
(1) synthesis example 1
By 120 parts of propylene glycol monomethyl ether acetates, 80 parts of propylene glycol monomethyl ethers, 2 parts of azodiisobutyronitriles (AIBN), 13.0
Part acrylic acid, 10 parts of benzyl methacrylates, 57.0 parts of 4- methyl styrenes, 20 parts of methyl methacrylates and 3 parts positive 12
Alkyl hydrosulfide is incorporated into the flask provided with agitator, thermometer, backflow cooling tube, titration outfit and nitrogen introduction pipe line, and
Change the air in flask into nitrogen.Then reaction 6 hours is carried out while temperature is increased into 110 DEG C and stirred.Institute
The alkali soluble resins of synthesis has 100.2mg KOH/g (solid content) acid number and surveyed by gel permeation chromatography (GPC)
About 15,110 weight average molecular weight Mw of amount.
(2) synthesis example 2
By 120 parts of propylene glycol monomethyl ether acetates, 80 parts of propylene glycol monomethyl ethers, 2 parts of AIBN, 3.5 parts of acrylic acid, 10 parts of first
Base benzyl acrylate, 66.5 parts of 4- methyl styrenes, 20 parts of methyl methacrylates and 3 parts of n-dodecyl mercaptans are incorporated into and set
In the flask for having agitator, thermometer, backflow cooling tube, titration outfit and nitrogen introduction pipe line, and the air in flask is changed
Into nitrogen.Then, reaction 6 hours is carried out while temperature is increased into 110 DEG C and stirred.Synthesized alkali soluble resins
Acid number with 26.5mg KOH/g (solid content) and about 16,070 as measured by GPC weight average molecular weight Mw.
(3) synthesis example 3
By 120 parts of propylene glycol monomethyl ether acetates, 80 parts of propylene glycol monomethyl ethers, 2 parts of AIBN, 22.5 parts of acrylic acid, 10 parts
Benzyl methacrylate, 47.5 parts of 4- methyl styrenes, 20 parts of methyl methacrylates and 3 parts of n-dodecyl mercaptans are incorporated into
Provided with agitator, thermometer, backflow cooling tube, titration outfit and nitrogen introduction pipe line flask in, and by the air in flask
Change nitrogen into.Then, reaction 6 hours is carried out while temperature is increased into 110 DEG C and stirred.Synthesized alkali solubility tree
Fat has 172.3mg KOH/g (solid content) acid number and the about 14,850 weight average molecular weight Mw as measured by GPC.
Embodiment 1
Preparing for photosensitive composition is as follows：Mix 17.1 parts of colorant dispersions, 0.6 part of acid red 52
(being manufactured by TCI u s companys), 14.7 parts of synthetic resin in synthesis example 1,4.9 parts of KAYARAD DPHA are (by Nippon
Chemical companies manufacture), 0.3 part of Irgacure 907 (being manufactured by BASF AG), 0.7 part have formula 2 represent structure
TR-PBG-305 (being manufactured by TRONLY companies), 0.2 part of the Irganox 1035 as antioxidant (by BASF AG's system
Make), 25.5 parts of propylene glycol monomethyl ether acetates and 36.0 parts of propylene glycol monomethyl ethers.
[formula 2]
Embodiment 2
Preparing for photosensitive composition is as follows：Mix 17.1 parts of colorant dispersions, 0.6 part of acid red 52
(being manufactured by TCI u s companys), 14.7 parts of synthetic resin in synthesis example 1,4.9 parts of KAYARAD DPHA are (by Nippon
Chemical companies manufacture), 0.3 part of Irgacure 907 (being manufactured by BASF AG), 0.7 part have formula 2 represent structure
TR-PBG-305 (being manufactured by TRONLY companies), 0.2 part of the Sumilizer GP as antioxidant (pass through Sumitomo
Chemical companies manufacture), 25.5 parts of propylene glycol monomethyl ether acetates and 36.0 parts of propylene glycol monomethyl ethers.
Comparative example 1
Preparing for photosensitive composition is as follows：Mix 17.1 parts of colorant dispersions, 0.6 part of C.I. acid red
52 (being manufactured by TCI u s companys), the synthetic resin in 14.7 parts of synthesis examples 1,4.9 parts of KAYARAD DPHA are (by Nippon
Chemical companies manufacture), 0.3 part of Irgacure 907 (being manufactured by BASF AG), 0.7 part have formula 2 represent structure
TR-PBG-305 (being manufactured by TRONLY companies), 25.5 parts of propylene glycol monomethyl ether acetates and 36.2 parts of propylene glycol monomethyl ethers.
Comparative example 2
Preparing for photosensitive composition is as follows：Mix 17.1 parts of colorant dispersions, 0.6 part of C.I. acid red
52 (being manufactured by TCI u s companys), the synthetic resin in 14.7 parts of synthesis examples 1,4.9 parts of KAYARAD DPHA are (by Nippon
Chemical companies manufacture), 0.3 part of Irgacure 907 (being manufactured by BASF AG), 0.7 part have formula 2 represent structure
TR-PBG-305 (being manufactured by TRONLY companies), 0.2 part of antioxidant IRGANOX 3114 based on phenol (by BASF AG
Manufacture), 25.5 parts of propylene glycol monomethyl ether acetates and 36.0 parts of propylene glycol monomethyl ethers.
Comparative example 3
Preparing for photosensitive composition is as follows：Mix 17.1 parts of colorant dispersions, 0.6 part of C.I. acid red
52 (being manufactured by TCI u s companys), the synthetic resin in 14.7 parts of synthesis examples 1,4.9 parts of KAYARAD DPHA are (by Nippon
Chemical companies manufacture), 0.3 part of Irgacure 907 (being manufactured by BASF AG), 0.7 part have formula 2 represent structure
TR-PBG-305 (being manufactured by TRONLY companies), 0.2 part of antioxidant IRGAFOS 168 based on phosphorus (by BASF AG's system
Make), 25.5 parts of propylene glycol monomethyl ether acetates and 36.0 parts of propylene glycol monomethyl ethers.
Comparative example 4
Preparing for photosensitive composition is as follows：Mix 17.1 parts of colorant dispersions, 0.6 part of C.I. acid red
52 (being manufactured by TCI u s companys), the synthetic resin in 14.7 parts of synthesis examples 1,4.9 parts of KAYARAD DPHA are (by Nippon
Chemical companies manufacture), 0.3 part of Irgacure 907 (being manufactured by BASF AG), 0.7 part have formula 2 represent structure
TR-PBG-305 (being manufactured by TRONLY companies), 0.2 part of IRGANOX 3114 (being manufactured by BASF AG), 0.2 part of IRGAFOS
168 (being manufactured by BASF AG), 25.5 parts of propylene glycol monomethyl ether acetates and 35.8 parts of propylene glycol monomethyl ethers.
Comparative example 5
Preparing for photosensitive composition is as follows：Mix 17.1 parts of colorant dispersions, 0.6 part of C.I. acid red
52 (being manufactured by TCI u s companys), the synthetic resin in 14.7 parts of synthesis examples 1,4.9 parts of KAYARAD DPHA are (by Nippon
Chemical companies manufacture), 0.3 part of Irgacure 907 (being manufactured by BASF AG), 0.7 part have formula 2 represent structure
TR-PBG-305 (being manufactured by TRONLY companies), 0.2 part of antioxidant STAB AO-412S based on sulphur (by ADEKA companies
Manufacture), 25.5 parts of propylene glycol monomethyl ether acetates and 35.8 parts of propylene glycol monomethyl ethers.
Comparative example 6
Preparing for photosensitive composition is as follows：Mix 17.1 parts of colorant dispersions, 0.6 part of C.I. acid red
52 (being manufactured by TCI u s companys), the synthetic resin in 14.7 parts of synthesis examples 1,4.9 parts of KAYARAD DPHA are (by Nippon
Chemical companies manufacture), 0.3 part of Irgacure 907 (being manufactured by BASF AG), 0.7 part have formula 2 represent structure
TR-PBG-305 (being manufactured by TRONLY companies), 0.2 part of IRGANOX 3114 (being manufactured by BASF AG), 0.2 part of STAB
AO-412S (being manufactured by ADEKA companies), 25.5 parts of propylene glycol monomethyl ether acetates and 35.8 parts of propylene glycol monomethyl ethers.
Comparative example 7
Preparing for photosensitive composition is as follows：Mix 17.1 parts of colorant dispersions, 0.6 part of C.I. acid red
52 (being manufactured by TCI u s companys), the synthetic resin in 14.7 parts of synthesis examples 1,4.9 parts of KAYARAD DPHA are (by Nippon
Chemical companies manufacture), 0.3 part of Irgacure 907 (being manufactured by BASF AG), 0.7 part have following formula 3 represent knot
The Irgacure OXE02 (being manufactured by BASF AG) of structure, 0.2 part of antioxidant Irganox 1035 (being manufactured by BASF AG),
25.5 parts of propylene glycol monomethyl ether acetates and 35.8 parts of propylene glycol monomethyl ethers.
[formula 3]
Comparative example 8
Preparing for photosensitive composition is as follows：Mix 17.1 parts of colorant dispersions, 0.6 part of C.I. acid red
52 (being manufactured by TCI u s companys), the synthetic resin in 14.7 parts of synthesis examples 1,4.9 parts of KAYARAD DPHA are (by Nippon
Chemical companies manufacture), 0.3 part of Irgacure 907 (being manufactured by BASF AG), 0.7 part have formula 3 represent structure
Irgacure OXE02 (being manufactured by BASF AG), 0.2 part of antioxidant Sumilizer GP (by Sumitomo
Chemicals companies manufacture), 25.5 parts of propylene glycol monomethyl ether acetates and 36.0 parts of propylene glycol monomethyl ethers.
Comparative example 9
Preparing for photosensitive composition is as follows：Mix 17.1 parts of colorant dispersions, 0.6 part of C.I. acid red
52 (being manufactured by TCI u s companys), the synthetic resin in 14.7 parts of synthesis examples 2,4.9 parts of KAYARAD DPHA are (by Nippon
Chemical companies manufacture), 0.3 part of Irgacure 907 (being manufactured by BASF AG), 0.7 part have formula 2 represent structure
TR-PBG-305 (being manufactured by TRONLY companies), 0.2 part of antioxidant Irganox 1035 (being manufactured by BASF AG), 25.5
Part propylene glycol monomethyl ether acetate and 36.0 parts of propylene glycol monomethyl ethers.
Comparative example 10
Preparing for photosensitive composition is as follows：Mix 17.1 parts of colorant dispersions, 0.6 part of C.I. acid red
52 (being manufactured by TCI u s companys), the synthetic resin in 14.7 parts of synthesis examples 3,4.9 parts of KAYARAD DPHA are (by Nippon
Chemical companies manufacture), 0.3 part of Irgacure 907 (being manufactured by BASF AG), 0.7 part have formula 2 represent structure
TR-PBG-305 (being manufactured by TRONLY companies), 0.2 part of antioxidant Irganox 1035 (being manufactured by BASF AG), 25.5
Part propylene glycol monomethyl ether acetate and 36.0 parts of propylene glycol monomethyl ethers.
Comparative example 11
Preparing for photosensitive composition is as follows：Mix in 17.1 parts of colorant dispersions, 14.7 parts of synthesis examples 3
Synthetic resin, 4.9 parts of KAYARAD DPHA (being manufactured by Nippon Chemical companies), 0.3 part of Irgacure 907 (by
BASF AG manufactures), the TR-PBG-305 (being manufactured by TRONLY companies) of 0.7 part of the structure that there is formula 2 to represent, 0.2 part it is anti-
Oxidant Irganox 1035 (being manufactured by BASF AG), 25.5 parts of propylene glycol monomethyl ether acetates and 36.0 parts of propane diols list first
Ether.
Experimental example 1
By spin-coating method, the every kind of coloring phototonus resin that will be prepared respectively in embodiment and comparative example at a certain angle
After composition is coated on 2 inches of glass substrate (being manufactured by Corning Co., EAGLE XG), by coated substrate
Placement is kept for 3 minutes on hot plate and at a temperature of being retained in 100 DEG C, to form film.Then, will have 1% to
The pattern of the light transmittance of stepped change and size are the test light of 1 μm to 50 μm of lines/space pattern in the range of 100%
Mask is placed on the thin film, then apart from the progress UV radiation of 100 μm of test photomask place.Here, for UV radiation
Light source is 1KW high-pressure mercury (Hg) lamp, and the high-pressure sodium lamp contains all g rays, h rays and i rays, and with 100mJ/cm2
Radiation intensity light.The film radiated by UV is immersed in the KOH developer solutions that pH value is 10.5, continues 2 minutes, from
It is and developed.After the glass substrate of film is scribbled using distilled water flushing, by being blown into nitrogen to the glass substrate to make
It is dried, and is then heated 25 minutes in 200 DEG C of oven heat.So as to form colour filter.Above-mentioned formed colour filter utensil
There is 2.0 μm of film thickness.
(1) sticky assessment
The pattern formed by observation by light microscope, commented according to the following standard that (picking) is picked up for pattern
Estimate pattern pickup.Evaluation result is as shown in table 1.
○：Do not observe that pattern picks up
△：1 to 3 pattern pickup
X：The pattern pickup of 4 or more
(2) measurement of developing powder
Measure until non-exposed portion is completely dissolved the required time during development, measurement result is as shown in table 1.
Experimental example 2
In addition to no photomask used for test, formed according to the same steps described in experimental example 1
Colour filter.
(1) change and the aberration of contrast are measured
The substrate of the colour filter formed is arranged between two panels polarization plates, and one of polarization plates in front side are revolved
Turn simultaneously illuminated using fluorescent lamp (at 380nm to 780nm wavelength) from rear side, so as to use CS-2000 luminance meters (by
KONICA MINOLTA companies manufacture) measure the maximum intensity and minimum strength for launching light.Then, by maximum intensity divided by most
Value that small intensity is calculated defines contrast.
Aberration be by measure respectively at 200 DEG C colourity before and after in heating furnace continuous heating 25 minutes,
Then the value for the colourity (y) after heating being subtracted into the colourity (y) before heating and being calculated, it is in following ' the △ y ' of mathematical expression 1
Represent.
[mathematical expression 1]
△ y=y (after heating)-y (before heating)
Measurement result is shown in table 1.
(2) measurement of light transmittance
(manufactured using colour difference meter by Olympus companies, OSP-200), measure the light transmittance in visible region.
Measurement result is as shown in table 1.
[table 1]
Referring to upper table 1, it can be seen that in embodiment 1 and embodiment 2 prepared composition there is excellent viscosity and
Being layered of pattern, high developing powder, less aberration, excellent light transmittance and high contrast do not occur.
Find that there are the excellent all spies for including viscosity, developing powder, aberration, contrast and light transmittance by contrast
The colour filter of sign can not be used according to composition (at least one aforementioned properties are poor) prepared in comparative example 1 to 11 to make
Make.
Claims (9)
1. a kind of photosensitive composition, including：Red stain, alkali soluble resins, photopolymerizable compound, antioxygen
Agent, Photoepolymerizationinitiater initiater and solvent, wherein,
The alkali soluble resins has 30mg KOH/g to 170mg KOH/g acid number；
The antioxidant includes the antioxidant functional group based on phenol and the antioxidant functional group based on phosphorus；
The Photoepolymerizationinitiater initiater includes the compound represented by following formula 1：
[formula 1]
Wherein R1Expression-R4-R5；R2And R3It is that there is 1 to the alkyl of 8 carbon atoms, phenyl, benzyl or diphenyl sulfide respectively
Base, the alkyl, phenyl, benzyl or diphenyl sulfide ether are that unsubstituted either by hydroxyl or have 1 to 8 carbon atom
Alkyl substitutes；R4It is that there is 1 alkylidene to 4 carbon atoms；And R5It is that there is 3 cycloalkyl to 8 carbon atoms.
2. composition according to claim 1, wherein, the alkali soluble resins has 50mg KOH/g to 160mg KOH/
G acid number.
3. composition according to claim 1, wherein, the antioxidant is selected from 3,5- di-t-butyl -4- hydroxybenzyls
Phosphoric acid and 6- [3- (3- tertiary butyl-4-hydroxy -5- methyl) propoxyl group] four-tert-butyl groups of -2,4,8,10- dibenzo [d, f] [1,3,
2] at least one of-dioxy phospha cycloheptane.
4. composition according to claim 1, wherein,
With the gross weight meter of the solids content of the photosensitive composition, comprising the red stain amount
Percentage by weight be 5% to 60%,
With the gross weight meter of the solids content of the photosensitive composition, comprising the alkali soluble resins amount
Percentage by weight be 10% to 80%,
With the gross weight meter of the solids content of the photosensitive composition, comprising the photopolymerizable compound
The percentage by weight of amount be 5% to 45%,
By weight percentage, comprising the amount of the Photoepolymerizationinitiater initiater account for the alkali soluble resins and the photopolymerization
The 0.1% to 40% of the solids content sum of compound,
By weight percentage, comprising the antioxidant amount account for the Photoepolymerizationinitiater initiater content 1% to
100%, and
By weight percentage, comprising the amount of the solvent account for the gross weight of the photosensitive composition
60% to 90%.
5. composition according to claim 1, wherein, by weight percentage, comprising describedization represented by formula 1
The amount of compound accounts for the 10% to 100% of the gross weight of the Photoepolymerizationinitiater initiater.
6. composition according to claim 1, in addition to selected from aceotphenone compound, benzophenone cpd, triazine
At least one of compound, united imidazole and thioxanthone compounds Photoepolymerizationinitiater initiater.
7. composition according to claim 1, in addition to selected from amines, carboxylic acid compound and contain the organic of sulfydryl
The photopolymerization of at least one of sulphur compound triggers reinforcing agent.
8. a kind of colour filter, the colour filter uses coloring phototonus resin group according to any one of claim 1 to 7
Compound is made.
9. a kind of liquid crystal display, the liquid crystal display includes colour filter according to claim 8.
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| KR1020130013372A KR101968510B1 (en) | 2013-02-06 | 2013-02-06 | Photosensitive resin composition for forming red pixel pattern |
| KR10-2013-0013372 | 2013-02-06 |
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| KR102047371B1 (en) * | 2013-07-31 | 2019-11-21 | 동우 화인켐 주식회사 | Colored Photosensitive Resin Composition, Color Filter, and Liquid Crystal Display Device Having the Same |
| WO2017043353A1 (en) * | 2015-09-11 | 2017-03-16 | 株式会社Adeka | Novel compound, latent additive, and composition containing said additive |
| US10961284B2 (en) * | 2016-12-21 | 2021-03-30 | Seoul National University R&Db Foundation | Recombinant protein antigen of Orientia tsutsugamushi and vaccine composition using the same |
| KR102027816B1 (en) * | 2017-11-10 | 2019-10-02 | 서울대학교산학협력단 | Epitope Antigens of TSA56 Antigens of Orientia tsutsugamushi and the Use Thereof |
| KR102027817B1 (en) * | 2017-11-10 | 2019-10-02 | 서울대학교산학협력단 | Novel Recombinant Protein Antigens of Orientia tsutsugamushi and the Vaccine Composition Using the Same |
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| JP4590893B2 (en) * | 2004-03-23 | 2010-12-01 | Ｊｓｒ株式会社 | Liquid curable resin composition for adhesives |
| CN101057181B (en) * | 2004-11-11 | 2011-01-12 | 旭化成电子材料株式会社 | Photosensitive resin composition for flexographic printing |
| KR101047703B1 (en) * | 2007-02-20 | 2011-07-08 | 동우 화인켐 주식회사 | Colored photosensitive resin composition and color filter |
| CN101565472B (en) * | 2009-05-19 | 2011-05-04 | 常州强力电子新材料有限公司 | Ketoxime ester photoinitiator |
| JP2012058728A (en) * | 2010-08-10 | 2012-03-22 | Sumitomo Chemical Co Ltd | Photosensitive resin composition |
| KR20120021752A (en) * | 2010-08-16 | 2012-03-09 | 동우 화인켐 주식회사 | A colored photosensitive resin composition, color filter and liquid crystal display device having the same |
| CN101923287B (en) * | 2010-08-31 | 2011-11-30 | 常州强力电子新材料有限公司 | Photosensitive composition containing photoinitiator of diphenyl sulfide based ketoxime esters and application thereof |
| JP5942368B2 (en) * | 2010-09-13 | 2016-06-29 | 三菱化学株式会社 | Colored resin composition, color filter, liquid crystal display device and organic EL display device |
| JP5121912B2 (en) * | 2010-11-24 | 2013-01-16 | 富士フイルム株式会社 | Colored photosensitive resin composition, pattern forming method, color filter manufacturing method, color filter, and display device including the same |
| JP5981159B2 (en) * | 2011-02-22 | 2016-08-31 | 東京応化工業株式会社 | Photosensitive resin composition, and color filter and display device using the same |
| JP6009774B2 (en) * | 2011-02-22 | 2016-10-19 | 東京応化工業株式会社 | Photosensitive resin composition, and color filter and display device using the same |
| CN103370342A (en) * | 2011-02-25 | 2013-10-23 | 昭和电工株式会社 | Curable composition and cured substance thereof |
| JP5659858B2 (en) * | 2011-02-28 | 2015-01-28 | 東洋インキＳｃホールディングス株式会社 | Photosensitive coloring composition and color filter |
| TWI494378B (en) | 2011-03-29 | 2015-08-01 | Toyo Ink Sc Holdings Co Ltd | Red coloring composition for color filter, and color filter |
| CN102778814B (en) * | 2012-07-05 | 2014-04-23 | 常州强力先端电子材料有限公司 | Photo-sensitive composition containing ketoximes ester type photoinitiator and application thereof |
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