CN108089401A - Photosensitive composition, colour filter and image display device - Google Patents

Photosensitive composition, colour filter and image display device Download PDF

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Publication number
CN108089401A
CN108089401A CN201711063207.3A CN201711063207A CN108089401A CN 108089401 A CN108089401 A CN 108089401A CN 201711063207 A CN201711063207 A CN 201711063207A CN 108089401 A CN108089401 A CN 108089401A
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Prior art keywords
mentioned
methyl
photosensitive composition
acid
weight
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Inventor
尹秀珍
金兑昱
田浚豪
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Dongwoo Fine Chem Co Ltd
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Dongwoo Fine Chem Co Ltd
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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
    • G03F7/0275—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with dithiol or polysulfide compounds
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
    • C07C319/02—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols
    • C07C319/12—Preparation of thiols, sulfides, hydropolysulfides or polysulfides of thiols by reactions not involving the formation of mercapto groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/334—Polymers modified by chemical after-treatment with organic compounds containing sulfur
    • C08G65/3344—Polymers modified by chemical after-treatment with organic compounds containing sulfur containing oxygen in addition to sulfur
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133514—Colour filters
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/0048—Photosensitive materials characterised by the solvents or agents facilitating spreading, e.g. tensio-active agents
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
    • G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
    • 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
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J17/00—Gas-filled discharge tubes with solid cathode
    • H01J17/38—Cold-cathode tubes
    • H01J17/48—Cold-cathode tubes with more than one cathode or anode, e.g. sequence-discharge tube, counting tube, dekatron
    • H01J17/49—Display panels, e.g. with crossed electrodes, e.g. making use of direct current

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Optics & Photonics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Nonlinear Science (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)

Abstract

The present invention provides photosensitive composition, colour filter and image display device.The photosensitive composition of the present invention is characterized in that, include the mercaptan system acrylate photopolymerizable compound represented by chemical formula 1, in following chemical formula 1, R1 is same or different to each other, and it is the linear chain or branch chain alkylidene of 2~carbon number of carbon number 40 comprising 1 or more oxygen, R2 is hydrogen or methyl, n is 1~20 integer, compared with whole 100 parts by weight of photosensitive composition solid constituent, the content of above-mentioned mercaptan system acrylate photopolymerizable compound is 10~30 parts by weight.[chemical formula 1]

Description

Photosensitive composition, colour filter and image display device
Technical field
The present invention relates to photosensitive composition, utilize the colour filter and image display device of its manufacture.
Background technology
Colour filter is widely used in the various display devices such as photographing element, liquid crystal display device (LCD), and application range is just Expanding rapidly.Especially colour filter is one of most important component of reproducing colors, for putting forward large-duty process and system The manufacturing method of product colour filter of excellent in reliability is also being studied always.
In recent years, in order to realize high color purity, there are the photosensitive compositions used in the manufacture of colour filter The tendency that persistently becomes higher of pigment concentration, and in order to improve process throughput and yield, it is desirable that with rapid development speed Also there is the photosensitive composition of excellent sensitivity and reliability even if under few light exposure simultaneously.
But fast show is guided improving the acid value of above-mentioned photosensitive composition in order to improve productivity In the case of shadow speed, there are the following problems：Adaptation declines and the mistake of pattern easily occurs in development, utilizes color sensation Photosensitive resin composition and the surface roughness of coated film that is formed become larger.Especially with photosensitive composition the bottom of at The dyed layer that portion is formed has the serious problems that pattern is unable to maintain that under few light exposure due to the pigment of high concentration.
KR published patent the 2009-0034774th is related to the black resist containing multi-functional thiol's compound with photosensitive Property resin combination, colour filter black matrix and colour filter using it, and disclose on black resist with photonasty tree The content of oil/fat composition, the black resist photosensitive polymer combination contains (A) alkali soluble resins, (B) has 1 or more The photopolymerization monomer of ethylene unsaturated bond, (C) Photoepolymerizationinitiater initiater, (D) lead to formula (I) represented by multi-functional thiol's chemical combination Object and (E) are selected from one or more of black organic pigment, colour mixture organic pigment and light screening material coloured material as must be into Point, but countermeasure regarding to the issue above is not disclosed, it is most important that existing can not asking applied to the pattern layer of colour filter Topic.
Therefore, demand exploitation sensitivity is well and even if be easily formed the coloring phototonus resin of pattern with low light exposure Composition.
Prior art literature
Patent document
Patent document 1：KR published patent the 2009-0034774th (2009.04.08.)
The content of the invention
Problem to be solved
It is excellent it is an object of the present invention to provide sensitivity and the colored photosensitive of pattern is easily formed under low light exposure Property resin combination.
It is further an object that excellent adhesion is provided and the colour filter of high-quality can be manufactured and image is shown The photosensitive composition of showing device.
It is further an object that it provides using above-mentioned photosensitive composition and is not happened at pixel The surface that portion occurs is bad, and chemical resistance, flatness or colour filter and image display device of excellent in reliability.
The method to solve the problem
Photosensitive composition for reaching the present invention of above-mentioned purpose is characterized in that, includes following chemistry Mercaptan system acrylate photopolymerizable compound represented by formula 1, it is whole compared with photosensitive composition solid constituent 100 parts by weight of body, the content of above-mentioned mercaptan system acrylate photopolymerizable compound is 10~30 parts by weight.
[chemical formula 1]
In above-mentioned chemical formula 1,
R1 is same or different to each other, and is the linear chain or branch chain of 2~carbon number of carbon number 40 comprising 1 or more oxygen Alkylidene,
R2 be hydrogen or methyl,
N is 1~20 integer.
In addition, the present invention provides the colour filter of the solidfied material comprising above-mentioned photosensitive composition and includes the filter The image display device of color device.
Invention effect
The photosensitive composition of the present invention with certain content comprising specific mercaptan system acrylate light by being gathered Conjunction property compound has the advantages that be easily formed pattern under low light exposure so as to which sensitivity is excellent.
In addition, the photosensitive composition of the present invention has the advantages that surface cure degree is excellent.
In addition, the colour filter and image display device that are manufactured using the photosensitive composition of the present invention are had It is bad not occur surface in pixel portion, and chemical resistance, flatness or it is of excellent in reliability the advantages of.
Specific embodiment
Hereinafter, it is described in more detail for the present invention.
In the present invention, when point out a certain component be located at another component " on " when, not only include a certain component and another structure The situation of part contact, further includes between two components and there is a situation where other components.
In the present invention, when pointing out a certain inscape of certain a part of "comprising", it means that as long as no especially opposite Record, then can further include other inscapes rather than exclude other inscapes.
<Photosensitive composition>
One embodiment of the present invention is related to a kind of photosensitive composition, and it includes represented by following chemical formula 1 Mercaptan system acrylate photopolymerizable compound, compared with whole 100 weight of photosensitive composition solid constituent Part, the content of above-mentioned mercaptan system acrylate photopolymerizable compound is 10~30 parts by weight.
[chemical formula 1]
In above-mentioned chemical formula 1,
R1 is same or different to each other, and is the linear chain or branch chain of 2~carbon number of carbon number 40 comprising 1 or more oxygen Alkylidene,
R2 be hydrogen or methyl,
N is 1~20 integer.
Mercaptan system acrylate photopolymerizable compound
The photosensitive composition of the present invention is characterized in that, compared with above-mentioned photosensitive composition Whole 100 parts by weight of solid constituent, the content of the mercaptan system acrylate photopolymerizable compound represented by following chemical formula 1 are 10~30 parts by weight.
[chemical formula 1]
In above-mentioned chemical formula 1,
R1 is same or different to each other, and is the linear chain or branch chain of 2~carbon number of carbon number 40 comprising 1 or more oxygen Alkylidene,
R2 be hydrogen or methyl,
N is 1~20 integer.
In the present invention, above-mentioned alkylidene can apply the explanation of alkyl in addition to it is divalent, and abovementioned alkyl can be straight Although chain or branch, carbon number are not particularly limited, but preferably 2~40, more preferably carbon number 2~9.As specific Example, have ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tertiary butyl, sec-butyl, 1- methyl-butvls, 1- Ethyl-butyls, N-pentyl, isopentyl, neopentyl, tertiary pentyl, n-hexyl, 1- methyl amyls, 2- methyl amyls, 4- methyl -2- amyls, 3,3- bis- Methyl butyl, 2- ethyl-butyls, n-heptyl, 1- methylhexyls, n-octyl, t-octyl, 1- methylheptyls, 2- ethylhexyls, 2- Propylpentyl, n-nonyl, 2,2- dimethyl heptyl, 1- Ethyl-propyls, 1,1- Dimethyl-propyls, isohesyl, 2- methyl amyls, 4- methylhexyls, 5- methylhexyls etc., but it is not limited to this.
In the present invention, R1 is same or different to each other.For example, in the case where above-mentioned n is 8, R1 can include by including oxygen Branch propylidene 3 repetitive units formed and 5 repetitive units formed by wrapping oxygen containing straight chain ethylidene.
Mercaptan system acrylate photopolymerizable compound represented by above-mentioned chemical formula 1 is by comprising containing 1 or more oxygen R1, so as to adjust functional group number, photocuring can be carried out, therefore the photosensitive composition of the present invention has The advantages of improving reactivity and adaptation.
In addition, while not wishing to be limited by theory, but including above-mentioned mercaptan system acrylate photopolymerizable compound In the case of, inhibit initiation reaction due to the functional group of mercaptan system of above-mentioned mercaptan system acrylate photopolymerizable compound Oxygen, so as to which laser curing velocity is fast, surface sensitivity increases, and due to above-mentioned mercaptan system acrylate photopolymerizable compound Mercapto and Oxyranyle and surface sensitivity increase, therefore with the development reliabilities such as speckle and solvent resistance can be obtained The advantages of excellent photosensitive composition.
Mercaptan system acrylate photopolymerizable compound represented by above-mentioned chemical formula 1 can be by following chemical formula 2~4 Any one expression, but as long as meet the present invention chemical formula 1 represented by mercaptan system acrylate photopolymerizable compound, then It is not limited to this.
[chemical formula 2]
[chemical formula 3]
[chemical formula 4]
Compared with whole 100 parts by weight of photosensitive composition solid constituent, the sulphur represented by above-mentioned chemical formula 1 The content of alcohol system acrylate photopolymerizable compound can be 10~30 parts by weight.
Above-mentioned mercaptan system acrylate photopolymerizable compound content within the above range in the case of, have energy The advantages of enough obtaining sensitivity, closing force, the photosensitive composition that coating is excellent and dispersion stabilization is excellent. In the case that the content of above-mentioned mercaptan system acrylate photopolymerizable compound is less than above range, sensitivity, closing force may It reduces, in the case larger than the above-mentioned range, the viscosity of photosensitive composition increases and coating may become not It is good, thereby increases and it is possible to can because reactivity due to dispersion stabilization decline occur, it may occur however that Yellowing, thus content be preferably in it is above-mentioned In the range of.
The photosensitive composition of the present invention is by including the mercaptan system acrylate represented by above-mentioned chemical formula 1 Photopolymerizable compound, so as in few light exposure, for example in 40mJ/m2Also pattern can be formed under following light exposure, and And due to above-mentioned mercaptan system acrylate photopolymerizable compound, inhibit oxygen in initiation reaction and make velocity of initiation fast, therefore Have the advantages that and the adaptation of base material, sensitivity and of excellent in reliability.
Colorant
The photosensitive composition of the present invention includes colorant, and above-mentioned colorant can include more than one face Material, more than one dyestuff or their mixture, can preferably include more than one pigment.
Above-mentioned pigment can use the organic pigment or inorganic pigment used generally in the art.In addition, above-mentioned pigment It can implement resin treatment as needed, at the surface using the pigment derivative for being imported with acidic-group or basic group etc. Reason is handled, micronized processing, utilization using sulfuric acid particles method etc. using the grafting of the surface of pigments of high-molecular compound etc. For going at the removal of the ionic impurity of the cleaning treatment of deimpurity organic solvent or water etc. or utilization ion-exchange etc. Reason etc..
Above-mentioned organic pigment can use the various pigment used in printing ink, jetted ink etc., specifically, can To enumerate water-soluble azo pigment, insoluble azo colour, phthalocyanine color, quinacridone pigment, isoindolenone pigments, different Yin Diindyl quinoline pigment, pigment, pyrene ketone pigment, twoPiperazine pigment, anthraquinone pigment, bi-anthraquinone base pigment, anthracene pyrimidine pigment, anthanthrene Quinone (anthanthrone) pigment, indanthrone (indanthrone) pigment, flavanthrone pigment, pyranthrone (pyranthrone) Pigment, diketopyrrolo-pyrrole pigment etc..
In addition, as above-mentioned inorganic pigment, the metallic compounds such as metal oxide or metallic complex salt can be used, it is specific and Speech, can enumerate iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, carbon black, organic mineral black, titanium it is black and by it is red, Green and blueness mix and metal oxide or metal composite oxide of the pigment of black etc. etc. are presented.
Particularly, as above-mentioned organic pigment and inorganic pigment, specifically, colour index (association of dyeing man can be enumerated Will (The society of Dyers and Colourists) is published) in be categorized as the compound of pigment, more specifically, The pigment of following colour index (C.I.) number can be enumerated, but is not necessarily limited to this.
C.I. pigment yellow 1,3,12,13,14,15,16,17,20,24,31,53,83,86,93,94,109,110,117, 125,128th, 137,138,139,147,148,150,153,154,166,173,180,185,194 and 214；
C.I. pigment orange 13,31,36,38,40,42,43,51,55,59,61,64,65,71 and 73；
C.I. Pigment Red 9,97,105,122,123,144,149,166,168,176,177,180,192,209,215, 216th, 224,242,254,264 and 265；
C.I. pigment violet 1,19,23,29,32,36 and 38；
C.I. pigment blue 15 (15:3、15:4、15:6 etc.) and 60；
C.I. pigment Green 7,36,58,59,62 and 63；
C.I. pigment brown 23 and 25；
C.I. 1 and 7 grade pigment of pigment black.
Above-mentioned pigment can individually or be use mixing two or more.
In the case that above-mentioned colorant includes more than one pigment and more than one dyestuff, compared with consolidating in colorant Body ingredient weight, the content of above-mentioned pigment is 15~45 parts by weight, is preferably 20~40 parts by weight.If above-mentioned pigment contains Amount is less than 20 parts by weight, then is difficult to realize colorrendering quality, if it exceeds 40 parts by weight, then under the dissolubility of developer solution Drop, it is difficult to form pattern.Above-mentioned pigment content within the above range in the case of, it is excellent for the dissolubility of developer solution It is different, and can accurately form pattern in development.
Above-mentioned pigment can be used in the form of the dispersible pigment dispersion for disperseing the uniform particle sizes of pigment, as Make the example of uniform particle sizes' process for dispersing of pigment, method that addition pigment dispersing agent carries out decentralized processing etc. can be enumerated.Root According to the above method, the dispersible pigment dispersion for the state that pigment is dispersed in solution can be obtained, but it is not limited to this.
Above-mentioned pigment dispersing agent is in order to which the solution of pigment is coagulated and maintains stability and is added, as the specific of pigment dispersing agent Example can enumerate the surfactant of cationic system, anionic system, nonionic system, amphoteric ion system, Polyester, polyamine system etc. Deng, they can each individually or be used in combination of two or more.
As the concrete example of above-mentioned cationic system surfactant, stearyl amine hydrochloride and lauryl trimethyl can be enumerated The amine salt such as ammonium chloride or quaternary ammonium salt etc..
As the concrete example of above-mentioned anionic surfactant, laruyl alcohol sodium sulfovinate and oleyl sulfate can be enumerated Alkylsurfuric acids salt, the dodecyl benzene sulfonic acid such as the higher alcohol sulfates such as sodium salt, NaLS and Texapon Special Alkylaryl sulfonates class such as sodium and dodecyl sodium naphthalene sulfonate etc..
As the concrete example of above-mentioned nonionic surfactants, polyoxyethylene alkyl ether, polyoxyethylene virtue can be enumerated Base ether, polyoxyethylene alkylaryl ether, polyoxyethylene deriv in addition, ethylene oxide/propylene oxide block copolymer, dehydration Sorbitan fatty acid ester, polyoxyethylene sorbitan aliphatic ester, polyoxyethylene sorbitol aliphatic ester, aliphatic acid Glyceride, polyoxyethylene fatty acid ester and polyoxyethylene alkyl amine etc..
Furthermore, it is possible to enumerate polyoxyethylene alkyl ether class, polyoxyethylene alkyl phenyl ether class, polyethylene glycol di class, mistake Water sorbitan fatty acid esters, fatty acid modified polyesters, tertiary-amine modified polyurethanes and polyethyleneimine amine etc..
In addition, above-mentioned pigment dispersing agent is preferably comprised containing butyl methacrylate (BMA) or methacrylic acid N, N- bis- The acrylic ester dispersant (hereinafter referred to as acrylic ester dispersant) of methylamino ethyl ester (DMAEMA).As above-mentioned third The commercially available product of olefin(e) acid ester system dispersant can enumerate DISPER BYK-2000, DISPER BYK-2001, DISPER BYK- 2070 or DISPER BYK-2150 etc., aforesaid propylene acid ester system dispersant can each individually or be use mixing two or more.
Above-mentioned pigment dispersing agent can also use other resin-bonded pigment dispersants beyond acrylic ester dispersant.Make For other above-mentioned resin-bonded pigment dispersants, well known resin-bonded pigment dispersant, particularly polyurethane can be enumerated, with poly- third Olefin(e) acid ester is the polycarboxylate of representative, the ammonium salt of unsaturated polyamide, polycarboxylic acids, (part) amine salt of polycarboxylic acids, polycarboxylic acids, poly- Alkylamine salt, polysiloxanes, long-chain polyaminoamide phosphate, the ester of hydroxyl polycarboxylic acids and their the modified generation of carboxylic acid Object or the amide or their salt formed with the freely polyester of (free) carboxyl and the reaction of poly- (low-grade alkylidene imines) Such oil dispersant；(methyl) acrylic-styrene copolymer, (methyl) acrylic acid-(methyl) acrylate copolymer, Styrene-maleic acid copolymer, polyvinyl alcohol or water-soluble resin as polyvinylpyrrolidone or water-soluble polymeric materialization Close object；Polyester；Modified polyacrylate；The addition product of ethylene oxide/propylene oxide；With phosphate etc..
It, can be with for cationic system pitch dispersant as the commercially available product of other above-mentioned resin-bonded pigment dispersants Enumerate the trade name of such as BYK (Bi Ke) chemical company：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；The trade name of BASF (BASF) company：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；Lubirzol (the trade names of (Lu Borun) company： SOLSPERS-24000、SOLSPERS-32550、NBZ-4204/10；Grind the trade name for the company of refining in river：HINOACT T- 6000、HINOACT T-7000、HINOACT T-8000；The trade name of aginomoto company：AJISPUR PB-821、AJISPUR PB-822、AJISPUR PB-823；The trade name of chemical company of common prosperity society：FLORENE DOPA-17HF、FLORENE DOPA- 15BHF, FLORENE DOPA-33, FLORENE DOPA-44 etc..
Other resin-bonded pigment dispersants beyond aforesaid propylene acid ester system dispersant can each individually or by two kinds with On be applied in combination, can also be used in combination with acrylic ester dispersant.
Compared with 1 parts by weight of colorant, the content of above-mentioned pigment dispersing agent is more than 0 and is below 1 parts by weight, is preferably 0.05~0.5 parts by weight.If the content of pigment dispersing agent is more than 0 and is below 1 parts by weight, can obtain homodisperse Pigment, therefore preferably.
As long as above-mentioned dyestuff for organic solvent there is dissolubility unlimitedly to use.It is preferable to use both have pair The dye of the reliabilities such as dissolubility and heat resistance for alkaline developer, solvent resistance is may insure again in the dissolubility of organic solvent Material.
As above-mentioned dyestuff, the acid dyes for being selected from the acidic-group with sulfonic acid or carboxylic acid etc., acid dye can be used Material and the salt of nitrogenous compound, acid dyes sulfonamide body etc. and their derivative in substance, in addition, can also Select azo system, xanthene system, the acid dyes and their derivative of phthalocyanine system.Preferably, above-mentioned dyestuff can enumerate color and refer to It is classified as the chemical combination of dyestuff in number (dyeing family's association's will (The society of Dyers and Colourists) is published) Well known dyestuff described in object or dyeing handbook (Se Ran societies).
As the concrete example of above-mentioned dyestuff, for C.I. solvent dyes, can enumerate：
C.I. solvent red 8,45,49,89,111,122,125,130,132,146 and 179；
C.I. solvent blue 5,35,36,37,44,59,67 and 70；
C.I. solvent purple 8,9,13,14,36,37,47 and 49；
C.I. solvent yellow 4,14,15,23,24,38,62,63,68,82,94,98,99 and 162；
C.I. solvent orange 2,7,11,15,26 and 56；
C.I. the green dyestuffs such as 1,3,4,5,7,28,29,32,33,34 and 35 of solvent.
In above-mentioned C.I. solvent dyes, preferably C.I. solvent red 8s, 49,89,111,122,132,146 and 179；C.I. it is molten Agent indigo plant 35,36,44,45 and 70；C.I. solvent violet 13, more preferable C.I. solvent red 8s, 122 and 132.
In addition, for C.I. acid dyes, can enumerate：
C.I. azogeramine, 4,8,14,17,18,26,27,29,31,34,35,37,42,44,50,51,52,57,66, 73、80、87、88、91、92、94、97、103、111、114、129、133、134、138、143、145、150、151、158、176、 182、183、195、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、 270、274、277、280、281、308、312、315、316、339、341、345、346、349、382、383、394、401、412、 417th, 418,422 and 426；
C.I. Indian yellow 1,3,7,9,11,17,23,25,29,34,36,38,40,42,54,65,72,73,76,79,98, 99、111、112、113、114、116、119、123、128、134、135、138、139、140、144、150、155、157、160、 161、163、168、169、172、177、178、179、184、190、193、196、197、199、202、203、204、205、207、 212nd, 214,220,221,228,230,232,235,238,240,242,243 and 251；
C.I. acid orange 6,7,8,10,12,26,50,51,52,56,62,63,64,74,75,94,95,107,108,169 With 173；
C.I. Blue VRS, 7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87, 90、92、96、103、112、113、120、129、138、147、150、158、171、182、192、210、242、243、256、259、 267、278、280、285、290、296、315、324:1st, 335 and 340；
C.I. acid violet 6B, 7,9,17,19 and 66；
C.I. the dyestuffs such as acid green 1,3,5,9,16,25,27,50,58,63,65,80,104,105,106 and 109.
In above-mentioned C.I. acid dyes, preferably for the C.I. acid red 92s that the solubility of organic solvent is excellent；C.I. it is sour Property indigo plant 80,90；With C.I. acid violets 60.
In addition, for C.I. direct dyess, can enumerate：
C.I. directly red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177, 179th, 181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246 and 250；
C.I. directly Huang 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98, 102nd, 108,109,129,136,138 and 141；
C.I. direct orange 34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106 and 107；
C.I. directly indigo plant 38,44,57,70,77,80,81,84,85,86,90,93,94,95,97,98,99,100,101, 106、107、108、109、113、114、115、117、119、137、149、150、153、155、156、158、159、160、161、 162、163、164、166、167、170、171、172、173、188、189、190、192、193、194、196、198、199、200、 207、209、210、212、213、214、222、228、229、237、238、242、243、244、245、247、248、250、251、 252nd, 256,257,259,260,268,274,275 and 293；
C.I. directly 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103 and of purple 104；
C.I. the dyestuffs such as direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79 and 82.
In addition, for C.I. mordant dyes, can enumerate：
C.I. medium Huang 5,8,10,16,20,26,30,31,33,42,43,45,56,61,62 and 65；
C.I. medium red 1,2,3,4,9,11,12,14,17,18,19,22,23,24,25,26,30,32,33,36,37, 38th, 39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94 and 95；
C.I. medium orange 3,4,5,8,12,13,14,20,21,23,24,28,29,32,34,35,36,37,42,43,47 With 48；
C.I. medium indigo plant 1,2,3,7,8,9,12,13,15,16,19,20,21,22,23,24,26,30,31,32,39, 40th, 41,43,44,48,49,53,61,74,77,83 and 84；
C.I. medium purple 1,2,4,5,7,14,22,24,30,31,32,37,40,41,44,45,47,48,53 and 58；
C.I. the green dyestuffs such as 1,3,4,5,10,15,19,26,29,33,34,35,41,43 and 53 of medium.
Above-mentioned dyestuff can each individually or be used in combination of two or more.
Compared with the feline amount in colorant, the content of the dyestuff in above-mentioned colorant is 0.5~80 weight Part, it is preferably 0.5~60 parts by weight, more preferably 1~50 parts by weight.If the content of dyestuff is above-mentioned in above-mentioned colorant 0.5~80 parts by weight can then prevent pattern from forming the reliability decrease problem that rear dyestuff dissolves out due to organic solvent, and sensitive Degree becomes higher.
Compared with the feline amount in photosensitive composition, the content of above-mentioned colorant is 3~60 Weight % is preferably 5~55 weight %.If the content of above-mentioned colorant is above-mentioned 3~60 weight %, when manufacturing colour filter The concentration of color is abundant, can form the sufficient pattern of mechanical strength.
Alkali soluble resins
The photosensitive composition of the present invention can include alkali soluble resins.Above-mentioned alkali soluble resins usually has By the reactivity and alkali solubility of the effect of light or heat, play a role as the decentralized medium of colorant.
Contained alkali soluble resins is as the knot for above-mentioned colorant in the photosensitive composition of the present invention Mixture resin and play a role, as long as manufacture can in the alkaline-based developer used in the development step of colour filter The bonding agent resin of dissolving, then be not particularly limited its species, can be used.
Above-mentioned alkali soluble resins for example can be the monomer comprising carboxyl and can be with the carboxylic monomer copolymerization of above-mentioned bag The copolymer of other monomers etc..
As the carboxylic monomer of above-mentioned bag, specifically, it can be cited for example that unsaturated monocarboxylic, unsaturated dicarboxyl Acid, unsaturated tricarboxylic acids etc. have unsaturated carboxylic acids such as the unsaturated polybasic carboxylic acid of 1 or more carboxyl etc. in the molecule.
As above-mentioned unsaturated monocarboxylic, specifically, it can be cited for example that acrylic acid, methacrylic acid, crotonic acid, α- Chloracrylic acid and cinnamic acid etc..
As above-mentioned unsaturated dicarboxylic, specifically, it can be cited for example that maleic acid, fumaric acid, itaconic acid, citraconic acid With mesaconic acid etc..
Above-mentioned unsaturation polybasic carboxylic acid or acid anhydrides, specifically, it can be cited for example that maleic anhydride, itaconic acid Acid anhydride, citraconic anhydride etc..
In addition, above-mentioned unsaturation polybasic carboxylic acid or its single (2- methacryloxyalkyls) ester, specifically, It can be cited for example that mono succinate (2- acryloyl-oxyethyls) ester, mono succinate (2- methacryloxyethyls) ester, neighbour Phthalic acid list (2- acryloyl-oxyethyls) ester and phthalic acid list (2- methacryloxyethyls) ester etc..
In addition, above-mentioned unsaturation polybasic carboxylic acid can also be list (methyl) propylene for the polymer that its two end is dicarboxyl Acid esters, specifically, it can be cited for example that ω-carboxy-polycaprolactone mono acrylic ester and ω-carboxy-polycaprolactone monomethyl third Olefin(e) acid ester etc..
The above-mentioned carboxylic monomer of bag can each individually or be use mixing two or more.
As can with the other monomers of the carboxylic monomer copolymerization of above-mentioned bag, specifically, it can be cited for example that benzene second Alkene, α-methylstyrene, adjacent vinyltoluene, vinyltoluene, to vinyltoluene, p-chlorostyrene, O-methoxy benzene Ethylene, meta-methoxy styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, vinyl benzyl methyl ether, to second Alkenyl benzyl methyl ether, adjacent vinylbenzyl glycidyl ether, shrink to vinyl benzyl at vinylbenzyl glycidyl ether The aromatic ethenyl compounds such as glycerin ether and indenes；
Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, n-propyl, methyl N-propyl, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, n-BMA, propylene The secondary butyl ester of sour isobutyl ester, Isobutyl methacrylate, sec-butyl acrylate, methacrylic acid, tert-butyl acrylate, metering system Tert-butyl acrylate, acrylic acid 2- hydroxy methacrylates, 2-hydroxyethyl methacrylate, acrylic acid 2- hydroxy propyl esters, methacrylic acid 2- Hydroxy propyl ester, acrylic acid 3- hydroxy propyl esters, methacrylic acid 3- hydroxy propyl esters, acrylic acid 2- hydroxybutyls, methacrylic acid 2- Hydroxybutyl, acrylic acid 3- hydroxybutyls, methacrylic acid 3- hydroxybutyls, acrylic acid 4- hydroxybutyls, methacrylic acid 4- Hydroxybutyl, allyl acrylate, allyl methacrylate, benzyl acrylate, benzyl methacrylate, acrylate Ester, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, acrylic acid 2- methoxy acrylates, methacrylic acid 2- Methoxy acrylate, acrylic acid 2- phenoxy ethyls, methacrylic acid 2- phenoxy ethyls, methoxyl group diethylene glycol acrylate, Methoxyl group diethylene glycol methacrylate, methoxy triethylene acrylate, methoxy triethylene methacrylate, Methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxyl group dipropylene glycol acrylate, methoxyl group two Propylene glycol methyl acrylate, isobornyl acrylate, isobornyl methacrylate, acrylic acid dicyclopentadienyl ester, methyl Acrylic acid dicyclopentadienyl ester, (methyl) acrylic acid adamantane esters, (methyl) acrylic acid norborneol base ester, acrylic acid 2- hydroxyls Base -3- phenoxy-propyls, methacrylic acid 2- hydroxyl -3- phenoxy-propyls, propylene monoglyceride and metering system acid glycerol The unsaturated carboxylate types such as monoesters；
Acrylic acid 2- amino ethyl esters, methacrylic acid 2- amino ethyl esters, acrylic acid 2- dimethylamino ethyl esters, metering system Sour 2- dimethylamino ethyl esters, acrylic acid 2- amino propyl ester, methacrylic acid 2- amino propyl ester, acrylic acid 2- dimethylaminos third Ester, methacrylic acid 2- dimethylaminos propyl ester, acrylic acid 3- amino propyl ester, methacrylic acid 3- amino propyl ester, acrylic acid 3- The unsaturated carboxylic acids aminoalkyl esters such as dimethylamino propyl ester and methacrylic acid 3- dimethylamino propyl ester；
The unsaturated carboxylic acids glycidol esters such as glycidyl acrylate and glycidyl methacrylate；
The generating vinyl carboxylates esters such as vinyl acetate, vinyl propionate, vinyl butyrate and vinyl benzoate；
The unsaturated ethers such as vinyl methyl ether, vinyl ethyl ether and allyl glycidyl ether；
The vinyl cyanides based compound such as acrylonitrile, methacrylonitrile, α-chloro-acrylonitrile and vinylidene cyanide；
Acrylamide, Methacrylamide, α-chloroacrylamide, N-2- hydroxyethyl acrylamides and N-2- hydroxyethyls The unsaturated acyls amine such as Methacrylamide；
The insatiable hungers such as maleimide, benzyl maleimide, N-phenylmaleimide and N- N-cyclohexylmaleimides And acid imide；
The aliphatic conjugated dienes class such as 1,3- butadiene, isoprene and chlorobutadiene；And
Polystyrene, polymethyl acrylate, polymethyl methacrylate, polyacrylic acid N-butyl, polymethylacrylic acid are just Butyl ester and polysiloxanes etc. have the polymeric monomer class of single acryloyl group or monomethacrylate acyl group in the end of polymer molecular chain； Deng.
These monomers can each individually or be use mixing two or more.
In addition, as wrapping carboxylic monomer and can be with the copolymerization of the other monomers of the carboxylic monomer copolymerization of above-mentioned bag The alkali soluble resins of object specifically, can enumerate (methyl) acrylic acid/(methyl) methyl acrylate copolymer, (methyl) third Olefin(e) acid/(methyl) benzyl acrylate copolymer, (methyl) acrylic acid/(methyl) acrylic acid 2- hydroxy methacrylates/(methyl) acrylic acid Benzyl ester copolymer, (methyl) acrylic acid/(methyl) methyl acrylate/polystyrene macromer copolymer, (methyl) acrylic acid/ (methyl) methyl acrylate/poly- (methyl) methyl acrylate polymeric monomer copolymer, (methyl) acrylic acid/(methyl) acrylic acid benzyl Ester/polystyrene macromer copolymer, (methyl) acrylic acid/(methyl) benzyl acrylate/the big list of poly- (methyl) methyl acrylate Precursor copolymer, (methyl) acrylic acid/(methyl) acrylic acid 2- hydroxy methacrylates/(methyl) benzyl acrylate/polystyrene macromer Copolymer, (methyl) acrylic acid/(methyl) acrylic acid 2- hydroxy methacrylates/(methyl) benzyl acrylate/poly- (methyl) acrylic acid first Ester polymeric monomer copolymer, (methyl) acrylic/styrene/(methyl) benzyl acrylate/N-phenylmaleimide copolymer, (methyl) acrylic acid/mono succinate (2- acryloyl-oxies) ester/styrene/(methyl) benzyl acrylate/N-phenylmaleimide Copolymer, (methyl) acrylic acid/mono succinate (2- acryloyl-oxyethyls) ester/styrene/(methyl) allyl acrylate/N- Phenyl maleimide copolymers and (methyl) acrylic acid/(methyl) benzyl acrylate/N-phenylmaleimide/styrene/ Single (methyl) glycerol acrylate copolymer etc..
Wherein, (methyl) acrylic acid/(methyl) benzyl acrylate copolymer, (methyl) acrylic acid/(first can preferably be used Base) benzyl acrylate/styrol copolymer, (methyl) acrylic acid/(methyl) methyl acrylate copolymer and (methyl) propylene Acid/(methyl) methyl acrylate/styrol copolymer.
Above-mentioned alkali soluble resins for wrap carboxylic monomer and can with the carboxylic monomer copolymerization of above-mentioned bag other In the case of the copolymer of monomer, compared with total 100 parts by weight of alkali soluble resins, the content of the above-mentioned carboxylic monomer of bag is 10 ~50 parts by weight are preferably 15~40 parts by weight, more preferably 25~40 parts by weight.If the above-mentioned carboxylic monomer of bag contains It measures as 10~50 parts by weight scopes, then it is excellent for the dissolubility of developer solution, and can accurately form pattern in development.
In addition, above-mentioned alkali soluble resins preferably has the acid value of 20~200mgKOH/g.In above-mentioned acid value, development Dissolubility in liquid improves, and non-exposed portion easily dissolves, and can increase sensitivity, and as a result the pattern of exposure portion is stayed in development Membrane left rate (film remaining ratio) can be improved down.
Above-mentioned acid value be as by acrylic acid series polymeric compounds 1g and when required potassium hydroxide amount (mg) and measure Value, can usually be titrated by using potassium hydroxide aqueous solution and be acquired.
In addition, pass through gel permeation chromatography (GPC；Using tetrahydrofuran as eluting solvent) alkali soluble resins that measures it is poly- Styrene conversion weight average molecular weight (hreinafter referred to as " weight average molecular weight ") is 3,000~200,000, preferably 5,000~ 100,000.If the weight average molecular weight of alkali soluble resins is in the range of above-mentioned 3,000~200,000, then the hardness of film improves And membrane left rate is high, dissolubility is excellent in developer solution for non-exposed portion, can improve resolution ratio.
In the present invention, compared with whole 100 parts by weight of solid constituent in photosensitive composition, alkali solubility tree The content of fat is 10~80 parts by weight, is preferably 20~70 parts by weight.Above range is in the content of above-mentioned alkali soluble resins In the case of interior, the formation of pattern is easy, can improve resolution ratio and membrane left rate.
In the case where the content of above-mentioned alkali soluble resins is less than above range, non-pixel portion may peel off, above-mentioned In the case that the content of alkali soluble resins is more than above range, the decreased solubility in developer solution, it may be difficult to form pattern.
Photopolymerization monomer
The photosensitive composition of the present invention includes photopolymerization monomer.Above-mentioned photopolymerization monomer can be energy The compound polymerizeing enough is acted on by aftermentioned Photoepolymerizationinitiater initiater, in of the invention, with the mercaptan represented by above-mentioned chemical formula 1 It is that acrylate photopolymerizable compound adds respectively.
Above-mentioned photopolymerization monomer can use monofunctional monomer, two functional monomers or polyfunctional monomer, and it is preferable to use two Monomer more than function, more preferably using polyfunctional monomers more than five functions, but it is not limited to this.
As the concrete example of above-mentioned monofunctional monomer, there are nonylphenol acrylate phenyl carbitol ester, acrylic acid 2- hydroxyl -3- benzene Oxygroup propyl ester, acrylic acid 2- ethylhexyls carbitol ester, acrylic acid 2- hydroxy methacrylates or n-vinyl pyrrolidone etc., but not It is limited to this.
As the concrete example of above-mentioned two functional monomer, there are 1,6- hexylene glycols two (methyl) acrylate, two (first of ethylene glycol Base) acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, double (propylene of bisphenol-A Trimethylammonium) ether or 3- methyl pentanediols two (methyl) acrylate etc., but it is not limited to this.
As the concrete example of above-mentioned polyfunctional monomer, there are trimethylolpropane tris (methyl) acrylate, ethoxylation three Hydroxymethyl-propane three (methyl) acrylate, propoxylation trimethylolpropane tris (methyl) acrylate, three (first of pentaerythrite Base) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, two season of ethoxylation Penta tetrol six (methyl) acrylate, (methyl) acrylate of propoxylated dipentaerythritol six or dipentaerythritol six (methyl) Acrylate etc., but it is not limited to this.
Compared with 100 parts by weight of photosensitive composition total solid content of the present invention, above-mentioned optical polymerism list The content of body is 5~50 parts by weight, is preferably 7~45 parts by weight.In above-mentioned 5~50 parts by weight, above-mentioned photopolymerization monomer The intensity of pixel portion or flatness can be made to become good.
In the case where the content of above-mentioned photopolymerization monomer is less than above range, the intensity of pixel portion may decline, In the case that the content of above-mentioned photopolymerization monomer is more than above range, flatness may decline, therefore preferred content is above-mentioned In the range of.
Photoepolymerizationinitiater initiater
The photosensitive composition of the present invention can include Photoepolymerizationinitiater initiater, and above-mentioned Photoepolymerizationinitiater initiater is preferred Include acetophenone based compound.
As above-mentioned acetophenone based compound, specifically, it can be cited for example that diethoxy acetophenone, 2- hydroxyls -2- Methyl-1-phenyl-propane-1- ketone, benzil dimethyl ketal, 2- hydroxyls-1- [4- (2- hydroxyl-oxethyls) phenyl]-2- methyl Propane -1- ketone, 1- hydroxycyclohexylphenylketones, 2- methyl-1s-(4- methylphenyl-sulfanyls) -2- morpholino propane -1- ketone, 2- benzyls Base -2- dimethylaminos -1- (4- morphlinophenyls) butane -1- ketone and 2- hydroxy-2-methyls [4- (1- methyl ethylenes) benzene Base] propane -1- ketone oligomer etc., can preferably enumerate 2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls) butane - 1- ketone etc..
In addition, above-mentioned Photoepolymerizationinitiater initiater can mix acetophenone based compound with other kinds of Photoepolymerizationinitiater initiater It uses.
Above-mentioned other kinds of Photoepolymerizationinitiater initiater can be enumerated through irradiation light to generate the activity of living radical certainly By base producing agent, sensitizer and acid agent etc..
As above-mentioned activating agent free-radical generating agent, specifically, it can be cited for example that benzoin based compound, hexichol first Ketone based compound, thioxanthones based compound and triazine based compound etc..
As above-mentioned benzoin based compound, specifically, it can be cited for example that benzoin, benzoin methylether, benzoin Ether, benzoin iso-propylether and benzoin isobutyl ether etc..
As above-mentioned benzophenone based compound, specifically, it can be cited for example that benzophenone, o-benzoylbenzoic acid Methyl esters, 4- phenyl benzophenones, 4- benzoyl -4'- dimethyl diphenyl sulfides, 3,3', 4,4'- tetra- (tert-butyl hydroperoxide carbonyl) Benzophenone and 2,4,6- tri-methyl benzophenones etc..
As above-mentioned thioxanthones based compound, specifically, it can be cited for example that 2-isopropylthioxanthone, 4- isopropyl thiophenes Ton ketone, 2,4- diethyl thioxanthones, bis- clopenthixal ketones of 2,4- and the chloro- 4- propoxythioxanthones of 1- etc..
As above-mentioned triazine based compound, specifically, it can be cited for example that 2,4- double (trichloromethyl) -6- (4- methoxies Base phenyl) -1,3,5- triazines, double (trichloromethyl) -6- (4- methoxyl groups the naphthalene) -1,3,5- triazines of 2,4-, double (three chloromethanes of 2,4- Base) -6- (4- methoxyl-styrenes) -1,3,5- triazines, double (trichloromethyl) -6- [2- (5- methylfuran -2- bases) second of 2,4- Alkenyl] -1,3,5- triazines, double (trichloromethyl) -6- [2- (furans -2- bases) the vinyl] -1,3,5- triazines of 2,4-, 2,4- be double (trichloromethyl) -6- [2- (4- diethylamino -2- aminomethyl phenyls) vinyl] -1,3,5- triazines and double (three chloromethanes of 2,4- Base) -6- [2- (3,4 Dimethoxyphenyl) vinyl] -1,3,5- triazines etc..
As above-mentioned sensitizer, specifically, can use such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,2,-bis- (Chloro-O-Phenyl) -4,4', 5,5'- tetraphenyl -1,2'- bisglyoxalines, 10- butyl -2- chloro-acridines ketone, 2- ethyl hydrazine, Benzil, 9,10- phenanthrenequione, camphorquinone, methyl benzoylformate and titanocenes compound etc..
As above-mentioned acid agent, specifically, it can be cited for example that 4- hydroxy phenyl dimethyl sulfoniums tosilate, 4- Hydroxy phenyl dimethyl sulfonium hexafluoro antimonate, 4- acetoxyl group phenyl dimethyl sulfoniums tosilate, 4- acetoxyl group phenyl Methylbenzyl sulfonium hexafluoro antimonate, triphenylsulfonium tosilate, triphenylsulfonium hexafluoro antimonate, diphenyl iodineTo first Benzene sulfonate, diphenyl iodineHexafluoro antimonate etc.Salt, nitrobenzyl tosylate class and benzoin toluenesulfonic acid Salt etc..
In addition, as above-mentioned living radical producing agent, in above-claimed cpd there is also generate simultaneously living radical and The compound of acid, for example, triazine system Photoepolymerizationinitiater initiater is also used as acid agent.
Above-mentioned Photoepolymerizationinitiater initiater can individually or be use mixing two or more.
In the present invention, compared with whole 100 parts by weight of solid constituent in photosensitive composition, above-mentioned light gathers The content of initiator is closed as 0.1~20 parts by weight, is preferably 1~10 parts by weight.
Above-mentioned Photoepolymerizationinitiater initiater content within the above range in the case of, above-mentioned coloring phototonus resin combination Object shortens the time for exposure by high-sensitivity, it is thus possible to expect high-resolution while productivity is improved.
In addition, in the present invention, photopolymerization initiator can be further used in Photoepolymerizationinitiater initiater.
Above-mentioned photopolymerization initiator is to promote to trigger the optical polymerism chemical combination of polymerization using Photoepolymerizationinitiater initiater The polymerization of object and the compound used, as photopolymerization initiator, can enumerate amine compound and alkoxy anthracene system chemical combination Object etc..
As above-mentioned amine compound, specifically, it can be cited for example that triethanolamine, methyl diethanolamine, three isopropyls Hydramine, 4- dimethylaminobenzoic acids methyl esters, ethyl 4-dimethylaminobenzoate, 4- dimethylaminobenzoic acids isopentyl ester, Benzoic acid 2- dimethylamino ethyl esters, 4- dimethylaminobenzoic acid 2- ethylhexyls, N, N- dimethyl-p-toluidines, 4,4'- Double (dimethylamino) benzophenone (being commonly referred to as Michler's keton), double (diethylamino) benzophenone of 4,4'- and the double (second of 4,4'- Vlmethyl) benzophenone etc., wherein, it is preferably double (diethylamino) benzophenone of 4,4'-.
As above-mentioned alkoxy anthracene based compound, specifically, it can be cited for example that 9,10- dimethoxy anthracenes, 2- ethyls- 9,10- dimethoxys anthracene, 9,10- diethoxies anthracene and 2- ethyl -9,10- diethoxy anthracenes etc..
In addition, above-mentioned photopolymerization initiator can use commercially available product, as commercially available photopolymerization initiator, Ke Yiju Go out trade name " EAB-F " (manufacturer：Baotugu Chemical Industrial Co., Ltd) etc..
In the case where above-mentioned Photoepolymerizationinitiater initiater and photopolymerization initiator are used in mixed way, combined as preferred, Specifically, it can be cited for example that diethoxy acetophenone and double (diethylamino) benzophenone of 4,4'-；2- methyl -2- Quinoline generation -1- (4- methylphenyl-sulfanyls) propane -1- ketone and double (diethylamino) benzophenone of 4,4'-；2- hydroxy-2-methyls -1- Phenyl-propane -1- ketone and double (diethylamino) benzophenone of 4,4'-；2- hydroxy-2-methyls -1- [4- (2- hydroxyl-oxethyls) Phenyl] double (diethylamino) benzophenone of propane -1- ketone and 4,4'-；1- hydroxycyclohexylphenylketones and the double (diethyls of 4,4'- Base amino) benzophenone；The oligomer and 4 of 2- hydroxy-2-methyls -1- [4- (1- methyl ethylenes) phenyl] propane -1- ketone, Double (diethylamino) benzophenone of 4'-；2- benzyl -2- dimethylaminos -1- (4- morphlinophenyls) butane -1- ketone and 4, Combination of double (diethylamino) benzophenone of 4'- etc. etc., is preferably 2- methyl -2- morpholinoes -1- (4- methylphenyl-sulfanyls) third The combination of alkane -1- ketone and double (diethylamino) benzophenone of 4,4'-.
In the case where using above-mentioned photopolymerization initiator, compared with 1 mole of Photoepolymerizationinitiater initiater, photopolymerization initiation helps Agent generally preferably uses 0.01~5 mole.If it with above-mentioned 0.01~5 mole of scope using photopolymerization initiator The sensitivity of color sensation photosensitive resin composition further improves, and can improve the filter formed using photosensitive composition The productivity of color device.
Solvent
It, then can be with as long as above-mentioned solvent is effective in other compositions dissolving contained in making photosensitive composition Without particular limitation using the solvent used in common photosensitive composition, particularly preferably ethers, second Esters of gallic acid, aromatic hydrocarbon, ketone, alcohols, esters or amides etc..
As above-mentioned ethers, for example, ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol monopropyl ether With the ethylene glycol monoalkyl ethers class such as ethylene glycol monobutyl ether；Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Diethylene glycol dialkyl ethers class such as dipropyl ether and diethylene glycol dibutyl ether etc..
As above-mentioned acetate esters, it can be cited for example that methylcellosolve acetate, ethyl cellosolve acetate, acetic acid second Ester, butyl acetate, pentyl acetate, methyl lactate, ethyl lactate, butyl lactate, 3- methoxybutyls acetic acid esters, 3- methyl -3- Methoxyl group -1- butylacetic acids ester, methoxypentyl acetic acid esters, ethylene glycol acetate, ethylene acetate, 3- methoxy propyls Sour methyl esters, methyl proxitol acetate, 3- methoxyl group -1- butylacetic acids ester, 1,2- propylene-glycol diacetates, ethylene glycol only son Base ether acetic acid ester, diethylene glycol monoethyl ether acetic acid esters, dipropylene glycol methyl ether acetic acid esters, 1,3 butylene glycol diacetate esters, two Ethylene glycol monobutyl ether acetic acid esters, ethylene glycol single methyl ether acetic acid esters, ethylene glycol monomethyl ether acetate, diethylene glycol list acetic acid Ester, diethylene glycol diacetate esters, diethylene glycol monobutyl ether acetic acid esters, Propylene glycol monoacetate, propylene-glycol diacetate, the third two Alcohol monomethyl ether acetate, propylene glycol monoethyl acetic acid esters, ethylene carbonate and propylene carbonate etc..
As above-mentioned aromatic hydrocarbon, for example, benzene,toluene,xylene and mesitylene etc..
As above-mentioned ketone, for example, methyl ethyl ketone, acetone, methylpentanone, methyl iso-butyl ketone (MIBK) and hexamethylene Ketone etc..
As above-mentioned alcohols, for example, ethyl alcohol, propyl alcohol, butanol, hexanol, cyclohexanol, ethylene glycol, glycerine and 4- hydroxyls Base -4-methyl-2 pentanone etc..
As above-mentioned esters, for example, 3- ethoxyl ethyl propionates, 3- methoxy methyl propionates and gamma-butyrolacton Deng.
As above-mentioned amides, it can be cited for example that dimethylformamide (DMF) and n-methyl-2-pyrrolidone (NMP).
Above-mentioned solvent can each individually or be use mixing two or more.
From the aspect of coating and drying property, above-mentioned solvent is 100 DEG C~200 DEG C organic molten it is preferable to use boiling point Agent, for example, propylene glycol monomethyl ether, propylene glycol monoethyl acetic acid esters, cyclohexanone, 3- ethoxy-propionic acids Ethyl ester and 3- methoxy methyl propionates etc..
Compared with whole 100 parts by weight of photosensitive composition, the content of above-mentioned solvent is 60~90 parts by weight, Preferably 70~85 parts by weight.If the content of above-mentioned solvent is within the above range, roll coater, spin coater, slit are utilized When apparatus for coating are coated, coating can for formula spin coater, slit coater (sometimes referred to as die coating machine) and flush coater To become good.
In the case where the content of above-mentioned solvent is less than above range, coating declines, and thus process may become difficult, super In the case of crossing above range, it may occur that the performance of the colour filter formed by above-mentioned photosensitive composition may decline The problem of.
Additive
Above-mentioned additive can be added selectively as needed, such as can be included and be selected from by other macromolecule chemical combination One kind in the group that object, curing agent, surfactant, closely sealed accelerating agent, antioxidant, ultra-violet absorber and anticoagulant form More than.
As the concrete example of other above-mentioned high-molecular compounds, it is solid that epoxy resin, maleimide resin etc. can be enumerated The property changed resin, polyvinyl alcohol, polyacrylic acid, polyalkylene glycol monoalkyl ether, poly- fluoroalkyl, polyester and polyurethane etc. are warm Plastic resin etc..
Above-mentioned curing agent is used to realize deeply-curing and improve mechanical strength, as the concrete example of curing agent, Epoxide, polyfunctional isocyanate compound, melamine compound and oxetane compound etc. can be enumerated.
In above-mentioned curing agent, as the concrete example of epoxide, bisphenol A type epoxy resin, hydrogenated bisphenol A can be enumerated Type epoxy resin, bisphenol f type epoxy resin, A Hydrogenated Bisphenol A F types epoxy resin, phenolic resin varnish type epoxy resin, other aromatic series It is epoxy resin, alicyclic ring family epoxy resin, ethylene oxidic ester system resin, glycidol amine system resin or above-mentioned epoxy resin Brominated derivative, the aliphatic beyond epoxy resin and its brominated derivative, alicyclic or aromatic epoxy compound, fourth two Epoxides, isoprene (co) polymer epoxides, (methyl) glycidyl acrylate (common) of alkene (co) polymer Polymer and triglycidyl isocyanurate etc..
In above-mentioned curing agent, as the concrete example of oxetane compound, can enumerate carbonic ester dioxygen azetidine, Dimethylbenzene dioxygen azetidine, adipate ester dioxygen azetidine, terephthalate dioxygen azetidine and hexamethylene dicarboxyl Sour dioxygen azetidine etc..
Above-mentioned curing agent can be described to help curing compound that make epoxy together with curing agent with curing compound is helped to be used in combination The epoxy group of compound, the oxetanes scaffolds open polymerization of oxetane compound.
It is above-mentioned to help curing compound such as having polybasic carboxylic acid class, polybasic carboxylic acid anhydride, acid agent.Above-mentioned polybasic acid anhydride Class can utilize commercially available epoxy curing agent.As above-mentioned commercially available product, ADEKA HARDENER EH-700 can be enumerated (ADEKA industry (strain) manufacture), RIKACID HH (new Japan Chemical (strain) manufacture) and MH-700 (new Japan Chemical (strain) systems Make) etc..Foregoing illustrative curing agent can individually or be use mixing two or more.
Above-mentioned surfactant can be formed to further improve the envelope of photosensitive composition and used, It is preferred that silicon-type, fluorine system, ester system, cationic system, anionic system, nonionic system, amphoteric surfactant etc. can be used.
Above-mentioned silicone based surfactants for example have the DOW CORNING Dong Li organosilicons company as commercially available product DC3PA, DC7PA, SH11PA, SH21PA and SH8400 etc., TSF-4440, TSF-4300 of organosilicon company of GE Toshiba, TSF-4445, TSF-4446, TSF-4460 and TSF-4452 etc..
Above-mentioned fluorine system surfactant for example has the Me gafac of the big Japanese ink chemical industrial company as commercially available product F-470, F-471, F-475, F-482 and F-489 etc..
In addition, as other workable commercially available products, KP (SHIN-ETSU HANTOTAI's chemical industry (strain)), POLYFLOW can be enumerated (altogether Flourish society is chemical (strain)), EFTOP (Tokheim product companies), MEGAFAC (big Japanese ink chemical industry (strain)), Flourad (Sumitomo 3M (strain)), Asahi guard, Surflon (being made above for Asahi Glass (strain)), SOLSPERSE (are won on road Profit), EFKA (EFKA chemical companies), PB 821 (aginomoto (strain)) and Disperbyk series (Bi Ke chemical) etc..
Foregoing illustrative surfactant can each individually or be used in combination of two or more.
The species of above-mentioned closely sealed accelerating agent is not particularly limited, can be with as the concrete example of workable closely sealed accelerating agent Enumerate vinyltrimethoxysilane, vinyltriethoxysilane, vinyl three (2- methoxy ethoxies) silane, N- (2- Amino-ethyl) -3- amino propyl methyls dimethoxysilane, N- (2- amino-ethyls) -3- TSL 8330s, 3- Aminopropyltriethoxywerene werene, 3- glycidoxypropyltrime,hoxysilanes, 3- glycidoxypropyl dimethoxies Base silane, 2- (3,4- expoxycyclohexyls) ethyl trimethoxy silane, 3- chloropropylmethyldimethoxysilanes, 3- chloropropyls Trimethoxy silane, 3- methacryloxypropyl trimethoxy silanes, 3-mercaptopropyi trimethoxy silane, 3- isocyanic acids Ester group propyl trimethoxy silicane and 3- isocyanate group propyl-triethoxysilicanes etc..
The species of above-mentioned antioxidant is not particularly limited, and can enumerate 2,2'- thiobis (4- methyl-6-tert butyl benzene Phenol), 2,6 di tert butyl 4 methyl phenol etc..
The species of above-mentioned ultra-violet absorber is not particularly limited, and as workable concrete example, can enumerate 2- (uncles 3- Butyl-2-hydroxy -5- aminomethyl phenyls) -5- chlorobenzotriazoles, alkoxy benzophenone etc..
The species of above-mentioned anticoagulant is not particularly limited, and as workable concrete example, can enumerate Sodium Polyacrylate etc..
In the present invention, above-mentioned additive can each individually or be used in combination of two or more, compared with coloring phototonus Whole 100 parts by weight of solid constituent in resin combination, the content of above-mentioned additive can be 0.01~10 parts by weight, preferably It can be 0.05~5 parts by weight, more preferably can be 1~3 parts by weight.
<Colour filter>
The another way of the present invention relates to the use of the colour filter of above-mentioned photosensitive composition manufacture.
Above-mentioned colour filter includes substrate and is formed at the pattern layer on the top of aforesaid substrate.
For aforesaid substrate, above-mentioned colour filter can be in itself substrate or or display device etc. in colour filter Position residing for device, is not particularly limited.Aforesaid substrate can be glass, silicon (Si), silica (SiOx) or polymeric substrate, Above-mentioned polymeric substrate can be polyether sulfone (polyethersulfone, PES) or makrolon (polycarbonate, PC) Deng.
Layer of the above-mentioned pattern layer as the photosensitive composition comprising the present invention can be above-mentioned by being coated with It photosensitive composition and is exposed, develops and heat cure and the layer that is formed in a predetermined pattern.Above-mentioned pattern layer It can be formed by implementing method generally known in the art.
Colour filter comprising substrate as described above and pattern layer can further include be formed between each pattern every Wall can also further include black matrix, and but it is not limited to this.
Further, it is also possible to further include the protective film on the pattern layer top for being formed at above-mentioned colour filter.
Using the photosensitive composition of the mercaptan system acrylate photopolymerizable compound comprising the present invention The colour filter of manufacture has bad surface does not occur and chemical resistance and the excellent feature of flatness in pixel portion.
In addition, the coloring phototonus resin combination of the mercaptan system acrylate photopolymerizable compound comprising the present invention Object is due to sensitivity and excellent adhesion and surface cure degree is high, thus even if carrying out photocuring under the conditions of low light exposure and showing Shadow solvent resistance is also excellent, and shows that the undesirable effect in surface does not occur, thus can effective for light curable inks, Photosensitive printing plate, various photoresists, LCD colour filter photoresists, resin black matrix photoresist or saturating Bright photosensitive material etc..
<Image display device>
In addition, another embodiment of the present invention is related to the image display device for including above-mentioned colour filter.
The colour filter of the present invention can be applied not only to common liquid crystal display device, and can be applied to electroluminescent The various image display devices such as display device, plasm display device, field emission display device.
Mercaptan system acrylate light of the image display device of the present invention represented by including chemical formula 1 with certain content gathers The photosensitive composition of conjunction property compound manufactures, therefore inhibits the oxygen of initiation reaction during colour filter is manufactured And laser curing velocity is fast, thus surface sensitivity increases, and develop speckle and solvent resistance excellent does not occur.
Hereinafter, in order to illustrate this specification, embodiment is enumerated to be described in detail.However, the embodiment of this specification Other variforms can be deformed into, are not necessarily to be construed as limiting for the embodiment that the scope of this specification is described below in detail It is fixed.The embodiment of this specification provides to more completely illustrate to those of ordinary skill in the art.In addition, hereafter In, represent " % " and " part " of content as long as no it is specifically mentioned be then weight basis.
The synthesis of mercaptan system acrylate photopolymerizable compound
Synthesis example 1
In the three neck round bottom flask comprising cooling tube, blender, to polyethylene glycol monoacrylate (2- [2- [2- [2- (2- hydroxyl-oxethyls) ethyoxyl] ethyoxyl] ethyoxyl] ethyl 2- acrylate) 600 weight of toluene is put into 103.0 parts by weight Measure part, stir while put into 4- (dimethylamino) pyridine (4- (Dimethylamino) pyridine) 0.1 parts by weight, 0.1 parts by weight of dicyclohexyl-carbodiimide (dicyclohexyl-carbodiimide), 3- mercaptopropionic acids (3- Mercaptopropionic acid) 32.5 parts by weight.
By back flow reaction continue 12 it is small when, in reaction, confirm to confirm that reaction terminates at any time by TLC, so as to be changed 121 parts by weight of compound of formula 2.
[chemical formula 2]
Synthesis example 2
In the three neck round bottom flask comprising cooling tube, blender, to polyethylene glycol monomethacrylate (32- hydroxyls- 3,6,9,12,15,18,21,24,27,30- ten oxa- dotriacontane -1- base -2- methyl -2- acrylate, 32-hydroxy- 3,6,9,12,15,18,21,24,27,30-decaoxadotriacontan-1-yl-2-methylprop-2-enoate) 600 parts by weight of toluene are put into 174.1 parts by weight, are stirred while putting into 4- (dimethylamino) pyridines (4- (Dimethylamino) pyridine) 0.1 parts by weight, dicyclohexyl-carbodiimide (dicyclohexyl- Carbodiimide) 0.1 parts by weight, 3- mercaptopropionic acids (3-Mercaptopropionic acid) 32.5 parts by weight.
By back flow reaction continue 12 it is small when, in reaction, confirm to confirm that reaction terminates at any time by TLC, so as to be changed 187 parts by weight of compound of formula 3.
[chemical formula 3]
Synthesis example 3
In the three neck round bottom flask comprising cooling tube, blender, to polyalkylene glycol mono methacrylate (19- Hydroxyl -12,15,18- trimethyls -2,4,6,8,11,14,17- seven oxa- nonadecane -1- base 2- methyl -2-2 acrylate, 19- hydroxy-12,15,18-trimethyl-2,4,6,8,11,14,17-heptaoxanonadecan-1-yl2- Methylprop-2-2enoate 600 parts by weight of toluene) are put into 144.7 parts by weight, are stirred while putting into 4- (dimethyl Amino) pyridine (4- (Dimethylamino) pyridine) 0.1 parts by weight, dicyclohexyl-carbodiimide (dicyclohexyl- Carbodiimide) 0.1 parts by weight, 3- mercaptopropionic acids (3-Mercaptopropionic acid) 32.5 parts by weight.
By back flow reaction continue 12 it is small when, in reaction, confirm to confirm that reaction terminates at any time by TLC, so as to be changed 160 parts by weight of compound of formula 4.
[chemical formula 4]
The manufacture of photosensitive composition：Examples 1 to 6 and comparative example 1~7
According to the composition of table 1 below, the photosensitive composition of manufacture embodiment and comparative example.
[table 1]
The manufacture of colour filter：Examples 1 to 6 and comparative example 1~7
The photosensitive composition of embodiment and comparative example is respectively coated to each glass at 2 inches using spin-coating method On glass substrate (#1797, Corning Incorporated's manufacture), it is then placed in heating plate, maintains 3 minutes and formed in 100 DEG C of temperature Film.Afterwards, the light with the pattern that scope of the transmitance 1~100% is made to carry out bench variation is placed on the above-mentioned films Mask will be set to 1000 μm with the interval of experiment photomask and utilize extra-high-pressure mercury vapour lamp (USH-250D, oxtail motor (strain) system Make) under air atmosphere with 40mJ/cm2Light exposure (365nm) irradiation light.By the film of above-mentioned illuminated ultraviolet light in pH Developed 80 seconds using spray development device in 12.5 KOH aqueous development solution.Using distilled water, washing is coated with above-mentioned film Glass plate after, nitrogen blowing and dry, and heated 20 minutes in 220 DEG C of heated oven, manufacture each colour filter.Above-mentioned manufacture Colour filter film thickness be 1.9~2.1 μm.
Experimental example
(1) sensitivity evaluation
It measures required minimum in order to form after development the film for not having figuratum peeling in the manufacturing process of colour filter Light exposure (mJ/cm2) is used as sensitivity.Evaluation criteria is as follows, and shows the result in table 2 below.
<Sensitivity evaluation benchmark>
Zero (outstanding)：30mJ/cm2Below
△ (good)：More than 30mJ/cm2And it is 40mJ/cm2Below
× (bad)：More than 40mJ/cm2
(2) adaptation is evaluated
After the substrate of making is cut in the region of 10 × 10mm with 100 matrix structures, jointing tape, is surveyed on it Determine the number of the matrix to come off when vertically firmly demoulding.Evaluation criteria is as follows, and records the result in table 2 below.
<Adaptation evaluation criteria>
Zero (outstanding)：Less than 5
△ (good)：5 or more and less than 15
× (bad)：15 or more
(3) speckle that develops is evaluated
To glass base be coated on according to the photosensitive composition of embodiment and comparative example manufacture using spin-coating method On plate (#1737, Corning Incorporated's manufacture), it is then placed in heating plate, is maintained 3 minutes in 100 DEG C of temperature and form film. Then, using extra-high-pressure mercury vapour lamp (USH-250D, oxtail motor (strain) manufacture) under air atmosphere with 40mJ/cm2Exposure Measure (365nm) irradiation light.The film of above-mentioned illuminated ultraviolet light is utilized into spray in the KOH aqueous development solution of pH 12.5 Mist developer develops 80 seconds.It is dried thin in nitrogen blowing after washing is covered with the glass substrate of above-mentioned film using distilled water It is added dropwise a small amount of distilled water on film, remains circular and in room temperature 2 minutes, then nitrogen blowing is dried.Then, to above-mentioned base Plate irradiates Na lamps, observes the surface state of film, is visually confirmed whether to generate circular speckle, be commented according to following benchmark Valency, and record the result in table 2 below.
<Develop speckle evaluation criteria>
Zero (outstanding)：Film coated surface does not confirm circular water spots line
△ (good)：Film coated surface is subtle to confirm circular water spots line
× (bad)：Film coated surface substantially confirms circular water spots line
(4) NMP solvent resistances are evaluated
After the substrate of making is cut into 3 × 3cm, impregnated 40 minutes with 80 DEG C of temperature in the nmp solution of 14.6mL.It Afterwards, for solution, absorbance is evaluated using UV-Vis spectrometer (UV-Vis spectrometer), and its result is remembered It is loaded in table 2 below.
Zero (outstanding)：Absorbance is less than 0.5
△ (good)：Absorbance is more than 0.5 and is less than 1.0
× (bad)：More than 1.0
[table 2]
Sensitivity Adaptation Develop speckle NMP solvent resistances
Embodiment 1 ○ △ △ ○
Embodiment 2 ○ ○ ○ ○
Embodiment 3 △ ○ △ △
Embodiment 4 ○ ○ ○ ○
Embodiment 5 △ △ △ △
Embodiment 6 ○ ○ ○ ○
Comparative example 1 × × △ ×
Comparative example 2 × ○ ○ ○
Comparative example 3 × × △ ×
Comparative example 4 × ○ ○ △
Comparative example 5 × × △ ×
Comparative example 6 × △ ○ △
Comparative example 7 × × × ×
With reference to above-mentioned table 2, even if the colour filter manufactured by the photosensitive composition of the present invention is in low light exposure (40mJ/cm2) under also show that the outstanding and good result of sensitivity, closing force, heat resistance and solvent resistance.
On the contrary, by comprising the present invention chemical formula 1 represented by mercaptan system acrylate photopolymerizable compound but its contain Amount is outside the scope of 10~30 parts by weight compared with whole 100 parts by weight of solid constituent in photosensitive composition The colour filter of the photosensitive composition manufacture of comparative example 1~6 shows sensitivity, closing force, development speckle and resistance to More than a project in solvent borne it is undesirable result.
In addition, the comparative example 7 of mercaptan system acrylate photopolymerizable compound by being free of above-mentioned chemical formula 1 color sensation The colour filter of photosensitive resin composition manufacture shows sensitivity, closing force, development speckle and the undesirable result of solvent resistance.
That is, using 1 institute of chemical formula compared with the feline amount present invention in photosensitive composition The content of the mercaptan system acrylate photopolymerizable compound of expression is the coloring phototonus tree of the present invention of 10~30 parts by weight Oil/fat composition can manufacture sensitivity, closing force, development speckle or excellent solvent resistance and colour filter and bag of excellent in reliability Containing its display device.

Claims (4)

1. a kind of photosensitive composition, it includes the mercaptan system acrylate photopolymerization represented by following chemical formula 1 Property compound, compared with whole 100 parts by weight of photosensitive composition solid constituent, the mercaptan system acrylate light The content of polymerizable compound is 10~30 parts by weight,
Chemical formula 1
In the chemical formula 1,
R1 is same or different to each other, and is the linear chain or branch chain alkylene of 2~carbon number of carbon number 40 comprising 1 or more oxygen Base,
R2 be hydrogen or methyl,
N is 1~20 integer.
2. photosensitive composition according to claim 1 is further included selected from by colorant, alkali solubility One or more of group that resin, photopolymerization monomer, Photoepolymerizationinitiater initiater, solvent and additive form.
3. a kind of colour filter, it includes the solidfied materials of the photosensitive composition described in claim 1 or 2.
4. a kind of image display device, it includes the colour filters described in claim 3.
CN201711063207.3A 2016-11-23 2017-11-02 Photosensitive composition, colour filter and image display device Pending CN108089401A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111694216A (en) * 2019-03-12 2020-09-22 东友精细化工有限公司 Blue photosensitive resin composition for organic light emitting diode, color filter comprising same, and image display device

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111694216A (en) * 2019-03-12 2020-09-22 东友精细化工有限公司 Blue photosensitive resin composition for organic light emitting diode, color filter comprising same, and image display device
CN111694216B (en) * 2019-03-12 2023-10-03 东友精细化工有限公司 Blue photosensitive resin composition for organic light emitting diode, color filter comprising same, and image display device

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