CN109782536A - Photosensitive composition, colour filter and image display device - Google Patents
Photosensitive composition, colour filter and image display device Download PDFInfo
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- CN109782536A CN109782536A CN201811312446.2A CN201811312446A CN109782536A CN 109782536 A CN109782536 A CN 109782536A CN 201811312446 A CN201811312446 A CN 201811312446A CN 109782536 A CN109782536 A CN 109782536A
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- Prior art keywords
- photosensitive composition
- mentioned
- pigment
- acid
- colour filter
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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
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
-
- 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
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- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Nonlinear Science (AREA)
- Optics & Photonics (AREA)
- Engineering & Computer Science (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Mathematical Physics (AREA)
- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials For Photolithography (AREA)
- Optical Filters (AREA)
Abstract
The colour filter and image display device that the present invention is provided photosensitive composition, manufactured using the photosensitive composition.Above-mentioned photosensitive composition includes colorant, alkali soluble resins, photopolymerizable compound, Photoepolymerizationinitiater initiater and solvent, the variable quantity of voltage retention (VHR) of the unit after the luminous energy for being exposed to all-wave length region formed using above-mentioned photosensitive composition is≤| 50% |, for the film of above-mentioned photosensitive composition after the luminous energy for being exposed to all-wave length region, volume resistance is 1 × 1014Ω cm or more, 1~10V of voltage, 1~100kHz of wavelength AC field in dielectric loss be 0.01 or less.Even if photosensitive composition of the invention is exposed to the luminous energy in all-wave length region, liquid crystal drive performance will not be impacted, and excellent in reliability.
Description
Technical field
The present invention relates to photosensitive composition, colour filter and image display devices, more specifically, are related to i.e.
Make after being exposed to the luminous energy in all-wave length region, liquid crystal drive performance will not be impacted, and color sensation excellent in reliability
Photosensitive resin composition, the colour filter formed using above-mentioned photosensitive composition and the figure for having above-mentioned colour filter
As display device.
Background technique
Colour filter is widely used in photographing element, liquid crystal display device (LCD) etc., and application range is expanding rapidly.
Especially in color filter application just in widened LCD, colour filter is one of most important component of reproducing colors, is manufactured in LCD
In process, the manufacturing method for proposing large-duty process and product colour filter excellent in reliability is also constantly being studied
[referring to KR published patent the 10-2015-0110348th].
In field of display, photosensitive composition can be in order to form photoresist, insulating film, protective film
It is used etc. diversified photocuring pattern.Specifically, photosensitive composition is carried out by photo-mask process
Selective exposure and imaging is to form desired photocuring pattern, i.e. coloring layer.But it is present in liquid crystal drive in coloring layer
In the case where in electric field, electrical characteristics of the meeting directly by the material of coloring layer are influenced.
Therefore, in liquid crystal drive electric field, even if after being exposed to the luminous energy in all-wave length region, will not be driven to liquid crystal
Dynamic performance impacts, and the requirement of photosensitive composition excellent in reliability is increasing.
Summary of the invention
Project to be solved
Even if, will not be to liquid crystal it is an object of the present invention to provide after the luminous energy that one kind is exposed to all-wave length region
Driveability impacts, and photosensitive composition excellent in reliability.
Another object of the present invention is to provide the colour filters formed using above-mentioned photosensitive composition.
Of the invention and another object is, provides the image display device for having above-mentioned colour filter.
The method to solve the problem
On the one hand, the present invention provides a kind of photosensitive composition, and which contain toner, alkali soluble resins, light
Polymerizable compound, Photoepolymerizationinitiater initiater and solvent, the liquid crystal drive list formed using above-mentioned photosensitive composition
The variable quantity of voltage retention (VHR) of the member after the luminous energy for being exposed to all-wave length region be≤| 50% |, above-mentioned colored photosensitive
Property resin combination film after the luminous energy for being exposed to all-wave length region, volume resistance be 1 × 1014Ω cm or more, in electricity
Pressing the dielectric loss in the AC field of 1~10V, 1~100kHz of wavelength is 0.01 or less.
On the other hand, the present invention provides the colour filter formed using above-mentioned photosensitive composition.
Another aspect, the present invention provide the image display device characterized by having above-mentioned colour filter.
Invention effect
Photosensitive composition of the invention is formed by coloring layer after the luminous energy for irradiating all-wave length not
Liquid crystal drive performance can be impacted, especially can neatly be acted on the electrical characteristics of periphery material, it is reliable so as to provide
The high liquid crystal display device of property.
Specific embodiment
Hereinafter, the present invention is described in more detail.
One embodiment of the present invention is related to a kind of photosensitive composition, and which contain toners (A), alkali solubility
Resin (B), photopolymerizable compound (C), Photoepolymerizationinitiater initiater (D) and solvent (E),
The unit formed using above-mentioned photosensitive composition is in the light for being exposed to all-wave length region
The variable quantity of voltage retention (VHR) after energy be≤| 50% |,
The film of above-mentioned photosensitive composition is after the luminous energy for being exposed to all-wave length region, volume resistance 1
×1014Ω cm, 1~10V of voltage, 1~100kHz of wavelength AC field in dielectric loss be 0.01 or less.
Above-mentioned voltage retention (VHR) means that integrates within the specific time is stored in unit (Cell)
Charge is for the ratio between the charge that is stored on ideal capacitor.This is the scale by the leakage of current of liquid crystal.This hair
In bright, the method for measuring the voltage retention of the unit formed using above-mentioned photosensitive composition is not had
Especially limitation, for example, can be measured by the method illustrated in aftermentioned embodiment.
In one embodiment of the present invention, pass through the liquid crystal drive that above-mentioned photosensitive composition will be utilized to be formed
The variable quantity of voltage retention (VHR) of the unit after the luminous energy for being exposed to all-wave length region is adjusted to≤| 50% |, so as to
Enough provide does not impact liquid crystal drive performance, and photosensitive composition excellent in reliability.
Above-mentioned volume resistance (volume resistance) means the intrinsic resistance of defined substance.Above-mentioned volume
Resistance can be asked by considering the resistance of measurement specimen surface and the thickness of area and measurement sample by following mathematical expressions 1
Out.
[mathematical expression 1]
Volume resistance=A/tRm
In above-mentioned formula, A indicates the contacting section product (cm of electrode2), t indicates that the thickness (cm) of measurement sample, Rm indicate to survey
Determine resistance (Ω).
In the present invention, the method for measuring above-mentioned volume resistance is not particularly limited, such as can pass through aftermentioned embodiment
The method of middle illustration measures.
In one embodiment of the present invention, the film by above-mentioned photosensitive composition is being exposed to all-wave length
After the luminous energy in region, volume resistance is adjusted to 1 × 1014Ω cm or more does not make liquid crystal drive performance so as to provide
At influence, and photosensitive composition excellent in reliability.
Above-mentioned dielectric loss (dielectric loss) means, when applying alternating voltage to dielectric substance, dielectric substance
The interior energy loss being lost by heat.In the present invention, the method for measuring above-mentioned dielectric loss is not particularly limited, such as can be led to
The method that illustrates in aftermentioned embodiment is crossed to measure.
In one embodiment of the present invention, the film by above-mentioned photosensitive composition is being exposed to all-wave length
After the luminous energy in region, by the dielectric loss in the AC field of 1~10V of voltage, 1~100kHz of wavelength be adjusted to 0.01 with
Under, liquid crystal drive performance will not be impacted so as to provide, and photosensitive composition excellent in reliability.
Colorant (A)
In one embodiment of the present invention, above-mentioned colorant includes more than one pigment.
Pigment (a1)
The organic pigment or inorganic pigment used generally in the art can be used in above-mentioned pigment.
Various pigment used in printing ink, jetted ink etc. can be used in above-mentioned organic pigment or inorganic pigment,
Water-soluble azo pigment, insoluble azo colour, phthalocyanine color, quinacridone pigment, isoindolinone face can specifically be enumerated
Material, isoindoline pigment, pigment, pyrene ketone pigment, twoPiperazine pigment, anthraquinone pigment, bi-anthraquinone base pigment, anthracene pyrimidine pigment,
Anthanthrone (anthanthrone) pigment, indanthrone (indanthrone) pigment, flavanthrone pigment, pyranthrone
(pyranthrone) pigment, diketopyrrolo-pyrrole pigment etc..
As above-mentioned inorganic pigment, the metallization such as metal oxide, metal composite oxide or metallic complex salt can be enumerated
Close object；Or carbon black etc..Specifically, iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony can be enumerated as above-mentioned metal
Deng.
In particular, can specifically enumerate colour index (dyeing association, family will (The as above-mentioned organic pigment and inorganic pigment
Society of Dyers and Colourists) publish) in be classified as the compound of pigment, can more specifically enumerate following
The pigment of colour index (C.I.) number, but it is not necessarily limited to this.
C.I. paratonere 7,9,14,41,48:1,48:2,48:3,48:4,81:1,81:2,81:3,97,122,123,
146、149、168、177、178、179、180、184、185、187、192、200、202、208、210、215、216、217、220、
223,224,226,227,228,240,242,246,254,255,264,272 and 279；
C.I. pigment orange 36,43,51,55,59,61,71 and 73；
C.I. pigment yellow 1,2,3,4,5,6,10,12,13,14,15,16,17,18,20,24,31,32,34,35,35:1,
36、36:1、37、37:1、40、42、43、53、55、60、61、62、63、65、73、74、77、81、83、86、93、94、95、97、
98、100、101、104、106、108、109、110、113、114、115、116、117、118、119、120、123、125、126、
127、128、129、137、138、139、144、146、147、148、150、151、152、153、154、155、156、161、162、
164、166、167、168、169、170、171、172、173、174、175、176、177、179、180、181、182、185、187、
188,193,194,199,213 and 214；
C.I. pigment Green 7,10,15,25,36,37,47,58,59,62 and 63；
C.I. pigment blue 15 (15:1,15:2,15:3,15:4,15:6), 16,22,60,64 and 80；
C.I. pigment violet 1,19,23,27,29,30,32,37,40,42 and 50；
C.I. pigment brown 28；
C.I. pigment black 1 and 7 etc..
Above-mentioned pigment (a1) can respectively be used alone or in combination of two or more.
In foregoing illustrative C.I. pigment, preferably it can be used selected from C.I. paratonere 254, C.I. paratonere 177, C.I.
Paratonere 242, C.I. naphthol green 58, C.I. naphthol green 59, C.I. pigment yellow 13 8, C.I. pigment yellow 150, C.I. pigment blue 15:
Pigment in 6 and C.I. pigment Violet 23.
From improve reliability from the aspect of, particularly preferably using one of C.I. naphthol green 58 and C.I. naphthol green 59 with
On pigment.
It is preferable to use the dispersible pigment dispersions that the uniform particle sizes of pigment disperse for above-mentioned pigment.As for keeping the partial size of pigment equal
The example of the method for even dispersion can enumerate the method etc. for carrying out decentralized processing by adding pigment dispersing agent (a2), according to
The above method can obtain the dispersible pigment dispersion of pigment evenly dispersed state in the solution.
Pigment dispersing agent (a2)
Above-mentioned pigment dispersing agent is added in order to which the solution of pigment is solidifying and maintains stability, as the specific of pigment dispersing agent
Example, can enumerate surfactants such as cationic system, anionic system, nonionic system, both sexes system, Polyester, polyamine system etc., they
It can respectively individually or be used in combination of two or more.
Furthermore it is preferred that containing butyl methacrylate (BMA) or n,N-dimethylaminoethyl methacrylate is included
(DMAEMA) acrylic ester dispersing agent (hereinafter referred to as acrylic ester dispersing agent).Disperse as above-mentioned acrylic ester
The commercially available product of agent can enumerate DISPER BYK-2000, DISPER BYK-2001, DISPER BYK-2070 or DISPER
BYK-2150 etc., above-mentioned acrylic ester dispersing agent can respectively individually or be used in combination of two or more.
The face of other resin types other than above-mentioned acrylic ester dispersing agent also can be used in above-mentioned pigment dispersing agent (a2)
Expect dispersing agent.As the pigment dispersing agent of other above-mentioned resin types, the pigment dispersing agent of well known resin type can be enumerated, especially
Be polyurethane, using polyacrylate as the polycarboxylate of representative, 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, hydroxyl polycarboxylic acids ester
And they modification product or there is reacting and being formed for the freely polyester and poly- (low-grade alkylidene imines) of (free) carboxyl
Amide or their salt as oil dispersing agent；(methyl) acrylic-styrene copolymer, (methyl) acrylic acid-(first
Base) acrylate copolymer, styrene-maleic acid copolymer, water solubility is set as polyvinyl alcohol or polyvinylpyrrolidone
Rouge or water-soluble polymeric compounds；Polyester；Modified polyacrylate；Oxireme/propylene oxide addition product；And phosphorus
Acid esters etc..
As the commercially available product of above-mentioned resin-bonded pigment dispersing agent, for cationic system pitch dispersant, such as can be with
Enumerate the trade name of 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；The trade name of Lubrizol (Lu Borun) company:
SOLSPERS-24000,SOLSPERS-32550,NBZ-4204/10；Grind the trade name for the company of refining: HINOACT T- in river
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, common prosperity society: FLORENE DOPA-17HF, FLORENE DOPA-
15BHF, FLORENE DOPA-33, FLORENE DOPA-44 etc..
The pigment dispersing agent of other resin types other than above-mentioned acrylic ester dispersing agent can be respectively individually or by two kinds
Combination of the above uses, and can also be used in combination with acrylic ester dispersing agent.
Relative to 100 parts by weight of solid component of pigment (a1), the content of above-mentioned pigment dispersing agent (a2) can be 5~60
Parts by weight more preferably can be 10~50 parts by weight ranges.If the content of pigment dispersing agent (a2) is more than 60 parts by weight, glue
Degree may increase, and in the case where being lower than 5 parts by weight, the micronized of pigment is difficult, or may cause gelation etc. after dispersion and ask
Topic.
Dyestuff (a3)
In one embodiment of the present invention, under the degree for not damaging electrical characteristics, above-mentioned colorant may include it is a kind of with
On dyestuff.
As long as above-mentioned dyestuff there is dissolubility unlimitedly to use organic solvent.It is preferable to use both have pair
It may insure the dye of the reliabilities such as dissolubility and heat resistance for alkaline developer, solvent resistance again in the dissolubility of organic solvent
Material.
As above-mentioned dyestuff, the acid dyes selected from the acidic-group with sulfonic acid or carboxylic acid etc. can be used, acidity contaminates
Material and the salt of nitrogenous compound, acid dyes sulfonamide body etc. and their derivative in substance in addition to this can also be with
Select the acid dyes and their derivative of azo system, xanthene system, phthalocyanine system.Preferably, above-mentioned dyestuff can enumerate color and refer to
It is classified as the chemical combination of dyestuff in number (dyeing association, family will (The society of Dyers and Colourists) is published)
The well known dyestuff recorded in object or dyeing handbook (Se Ran society).
As the concrete example of above-mentioned dyestuff, for C.I. solvent dye, can enumerate:
C.I. solvent red 8,45,49,89,111,122,125,130,132,146 and 179；
C.I. solvent blue 5,35,36,37,44,45,59,67 and 70；
C.I. solvent purple 8,9,13,14,36,37,47 and 49；
C.I. 4,14,15,16,21,23,24,38,56,62,63,68,79,82,93,94,98,99,151 and of solvent yellow
162；
C.I. solvent orange 2,7,11,15,26,41,45,56 and 62；
C.I. the green dyestuffs such as 1,3,4,5,7,28,29,32,33,34 and 35 of solvent.
C.I. in solvent dye, preferably for the excellent C.I. solvent yellow of the dissolubility of organic solvent 14,16,21,56,
79,93,151；C.I. solvent red 8,49,89,111,122,132,146,179；C.I. solvent orange 41,45,62；C.I. solvent blue
35,36,44,45,70；C.I. solvent violet 13, wherein more preferable C.I. solvent yellow 21,79；C.I. solvent red 8,122,132；
C.I. solvent orange 45,62.
In addition, can be enumerated for C.I. acid dyes:
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、198、206、211、215、216、217、227、228、249、252、257、258、260、261、266、268、270、
274、277、280、281、195、308、312、315、316、339、341、345、346、349、382、383、394、401、412、
417,418,422 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、
212,214,220,221,228,230,232,235,238,240,242,243 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、
267,278,280,285,290,296,315,324:1,335 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.
C.I. in acid dyes, preferably for the C.I. Indian yellow 42 that the solubility of organic solvent is excellent；C.I. acid red
92；C.I. acid blue 80,90；C.I. acid violet 66；C.I. acid green 27.
In addition, can be enumerated for C.I. direct dyes:
C.I. directly red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,
179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246 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,
102,108,109,129,136,138 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、
252,256,257,259,260,268,274,275 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, can be enumerated for C.I. mordant dyes:
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,
38,39,41,43,45,46,48,53,56,63,71,74,85,86,88,90,94 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,
40,41,43,44,48,49,53,61,74,77,83 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 respectively individually or be used in combination of two or more.
Relative to the 100 weight % of all solids ingredient in photosensitive composition of the invention, above-mentioned coloring
The content of agent (A) can be 50 weight % hereinafter, for example can be 5~50 weight %, preferably can be 15~40 weight %.?
In the case that the content of colorant is above range, when colour filter is made, it is abundant to be capable of forming colour saturation, and mechanical strength is abundant
Pattern, moreover, additionally it is possible to provide after the luminous energy for being exposed to all-wave length region liquid crystal drive performance will not be made
At influencing and coloring layer excellent in reliability.
Alkali soluble resins (B)
In one embodiment of the present invention, above-mentioned alkali soluble resins (B) usually has the function of the reaction by light or heat
Property and alkali solubility, as colorant decentralized medium and play a role.It is contained in photosensitive composition of the invention
Alkali soluble resins (B) as long as play a role and as the adhesive for colorant (A) for manufacturing colour filter
The alkali soluble resins that can be dissolved in alkaline-based developer used in development step then can be used.
Alkali soluble resins (B) it can be cited for example that the monomer containing carboxyl and with can with above-mentioned monomer be copolymerized its
The copolymer etc. of his monomer.
As the above-mentioned monomer containing carboxyl, it can be cited for example that unsaturated monocarboxylic, unsaturated dicarboxylic, unsaturation three
Carboxylic acid etc. has unsaturated carboxylic acids such as unsaturated polybasic carboxylic acid of 1 or more carboxyl etc. in the molecule.Wherein, as unsaturated single
Carboxylic acid, it can be cited for example that acrylic acid, methacrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid etc..As unsaturated dicarboxyl
Acid, it can be cited for example that maleic acid, fumaric acid, itaconic acid, citraconic acid, mesaconic acid etc..Unsaturated polybasic carboxylic acid may be acid
Acid anhydride, specifically, maleic anhydride, itaconic anhydride, citraconic anhydride etc. can be enumerated.In addition, unsaturated polybasic carboxylic acid may be
Its single (2- (methyl) acryloxyalkyl) ester, it can be cited for example that mono succinate (2- acryloyl-oxyethyl) ester, amber
Sour single (2- methacryloxyethyl) ester, phthalic acid list (2- acryloyl-oxyethyl) ester, phthalic acid list (2-
Methacryloxyethyl) ester etc..Unsaturated polybasic carboxylic acid can also be the list (methyl) of its two ends dicarboxyl based polyalcohol
Acrylate, it can be cited for example that ω-carboxy-polycaprolactone mono acrylic ester, ω-carboxy-polycaprolactone monomethacrylates
Deng.These monomers for containing carboxyl can respectively individually or be use mixing two or more.
As the other monomers that can be copolymerized with the above-mentioned monomer containing carboxyl, it can be cited for example that styrene, Alpha-Methyl
Styrene, adjacent vinyltoluene, vinyltoluene, to vinyltoluene, p-chlorostyrene, o-methoxystyrene, first
Oxygroup styrene, to methoxy styrene, adjacent vinyl benzyl methyl ether, vinyl benzyl methyl ether, to vinyl benzyl
Methyl ether, adjacent vinylbenzyl glycidyl ether, vinylbenzyl glycidyl ether, to vinylbenzyl glycidyl ether,
The aromatic ethenyl compounds such as indenes；Methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, third
Olefin(e) acid n-propyl, n propyl methacrylate, isopropyl acrylate, isopropyl methacrylate, n-butyl acrylate, methyl-prop
The secondary butyl ester of olefin(e) acid N-butyl, isobutyl acrylate, Isobutyl methacrylate, sec-butyl acrylate, methacrylic acid, acrylic acid
The tert-butyl ester, Tert-butyl Methacrylate, acrylic acid 2- hydroxy methacrylate, 2-hydroxyethyl methacrylate, acrylic acid 2- hydroxyl third
Ester, methacrylic acid 2- hydroxy propyl ester, acrylic acid 3- hydroxy propyl ester, methacrylic acid 3- hydroxy propyl ester, acrylic acid 2- hydroxyl fourth
Ester, methacrylic acid 2- hydroxybutyl, acrylic acid 3- hydroxybutyl, methacrylic acid 3- hydroxybutyl, acrylic acid 4- hydroxyl fourth
Ester, methacrylic acid 4- hydroxybutyl, allyl acrylate, allyl methacrylate, benzyl acrylate, methacrylic acid benzyl
Ester, cyclohexyl acrylate, cyclohexyl methacrylate, phenyl acrylate, phenyl methacrylate, acrylic acid 2- methoxyl group second
Ester, methacrylic acid 2- methoxy acrylate, acrylic acid 2- phenoxy ethyl, methacrylic acid 2- phenoxy ethyl, methoxyl group two
Ethylene glycol acrylate, methoxyl group diethylene glycol methacrylate, methoxy triethylene acrylate, three second two of methoxyl group
Alcohol methacrylate, methoxypropylene glycol acrylate, methoxypropylene glycol methacrylate, methoxyl group dipropylene glycol third
Olefin(e) acid ester, methoxyl group dipropylene glycol methyl acrylate, isobornyl acrylate, isobornyl methacrylate, acrylic acid are double
Cyclopentadiene ester, methacrylic acid dicyclopentadienyl ester, (methyl) adamantyl acrylate, (methyl) acrylic acid norborny
It is ester, acrylic acid 2- hydroxyl -3- phenoxy-propyl, methacrylic acid 2- hydroxyl -3- phenoxy-propyl, glycerol mono-acrylate, sweet
The unsaturated carboxylate types such as oily monomethacrylates；Acrylic acid 2- amino ethyl ester, methacrylic acid 2- amino ethyl ester, acrylic acid
2- dimethylamino ethyl ester, methacrylic acid 2- dimethylamino ethyl ester, acrylic acid 2- amino propyl ester, methacrylic acid 2- amino
Propyl ester, acrylic acid 2- dimethylamino propyl ester, methacrylic acid 2- dimethylamino propyl ester, acrylic acid 3- amino propyl ester, methyl
The unsaturation carboxylic such as acrylic acid 3- amino propyl ester, acrylic acid 3- dimethylamino propyl ester, methacrylic acid 3- dimethylamino propyl ester
Sour aminoalkyl esters；The unsaturated carboxylic acids glycidol esters such as glycidyl acrylate, glycidyl methacrylate；
The generating vinyl carboxylates esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate；Vinyl methyl ether, ethylene
The unsaturated ethers such as benzyl ethyl ether, allyl glycidyl ether；Acrylonitrile, methacrylonitrile, α-chloro-acrylonitrile, ethenylidene two
The vinyl cyanides based compound such as cyanogen；Acrylamide, Methacrylamide, α-chloroacrylamide, N-2- hydroxyethyl acrylamide,
The unsaturated acyls amine such as N-2- hydroxyethyl methacrylamide；Maleimide, benzyl maleimide, N- phenyl Malaysia acyl
The unsaturated acyls imines such as imines, N- N-cyclohexylmaleimide；The aliphatic such as 1,3- butadiene, isoprene, chlorobutadiene
Conjugated diene；And in polystyrene, polymethyl acrylate, polymethyl methacrylate, polyacrylic acid N-butyl, poly- methyl-prop
The end of the polymer molecular chains such as olefin(e) acid N-butyl, polysiloxanes has the polymeric monomer of single acryloyl group or monomethacrylate acyl group
Class etc..These monomers can respectively individually or be use mixing two or more.In particular, as can be with the above-mentioned list containing carboxyl
The other monomers of body copolymerization due to the monomer with norborny skeleton, the monomer with adamantane framework, have rosin skeleton
The large volumes monomer such as monomer there is the tendency for reducing relative permittivity value, therefore preferably.
The acid value of above-mentioned alkali soluble resins is preferably 20~200 (㎎ KOH/g) range.If acid value is above range,
Then the dissolubility in developer solution improves, and non-exposed portion is easy dissolution, and sensitivity increases, and as a result the pattern of exposure portion is stayed in development
Improve membrane left rate (film remaining ratio) down, therefore preferably.Wherein, so-called acid value is as neutralization 1g polymer
The amount (mg) of required potassium hydroxide and the value measured, can usually be titrated to ask by using potassium hydroxide aqueous solution
Out.
Furthermore it is preferred that be following alkali soluble resins: i.e. by gel permeation chromatography (GPC, using tetrahydrofuran as elution it is molten
Agent) measurement polystyrene conversion weight average molecular weight (hreinafter referred to as " weight average molecular weight ") be 3,000~200,000, preferably
For 5,000~100,000 alkali soluble resins.If molecular weight is above range, the hardness with film improves and stays film
Rate is high, the non-exposed portion tendency that dissolubility is excellent in developer solution, resolution ratio improves, therefore preferably.
The molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)] of alkali soluble resins (B) is preferably 1.5~
6.0, more preferably 1.8~4.0.If molecular weight distribution [weight average molecular weight (Mw)/number-average molecular weight (Mn)] is 1.5~6.0,
Then developability is excellent, thus preferably.
Relative to the 100 weight % of all solids ingredient in photosensitive composition, above-mentioned alkali soluble resins (B)
Content typically 5~85 weight %, preferably can be 10~70 weight %.It is upper in the content of alkali soluble resins (B)
In the case where stating range, it is residual that and non-pixel portion abundant with the dissolubility for developer solution is not easy the generation development on substrate
Slag and development when be not susceptible to exposure portion pixel portion film reduce and the good tendency of the spalling of non-pixel portion,
Therefore preferably.
Photopolymerizable compound (C)
In one embodiment of the present invention, above-mentioned photopolymerizable compound (C) is caused by light and aftermentioned photopolymerization
The compound that the effect of agent can polymerize, can enumerate monofunctional monomer, two functional monomers, other polyfunctional monomers etc..
As the concrete example of above-mentioned monofunctional monomer, nonylphenol acrylate phenyl carbitol ester, acrylic acid 2- hydroxyl can be enumerated
Base -3- phenoxy-propyl, acrylic acid 2- ethylhexyl carbitol ester, acrylic acid 2- hydroxy methacrylate, n-vinyl pyrrolidone etc..
As the concrete example of above-mentioned two functional monomer, 1,6- hexylene glycol two (methyl) acrylate, ethylene glycol two (methyl) can be enumerated
Acrylate, neopentyl glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, bisphenol-A bis- (acryloyl-oxies
Base ethyl) ether, 3- methyl pentanediol two (methyl) acrylate etc..As the concrete example of other polyfunctional monomers, can enumerate
Trimethylolpropane tris (methyl) acrylate, pentaerythrite three (methyl) acrylate, pentaerythrite four (methyl) acrylic acid
Ester, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate etc..Wherein, it is preferable to use two officials
Polyfunctional monomer more than energy.
Relative to the 100 weight % of all solids ingredient in photosensitive composition, above-mentioned optical polymerism chemical combination
The content of object (C) typically 5~50 weight % preferably can be 7~45 weight %.In photopolymerizable compound (C)
In the case that content is above range, intensity or flatness with pixel portion become good tendency, therefore preferably.
Photoepolymerizationinitiater initiater (D)
In one embodiment of the present invention, 4- phenoxydichloroacetophenone, uncle 4- is can be used in above-mentioned Photoepolymerizationinitiater initiater
Butyl-dichloroacetophenone, diethoxy acetophenone, 1- (4- isopropyl phenyl) -2- hydroxy-2-methyl propane -1- ketone, 1- hydroxyl
The acetophenones based compounds such as cyclohexyl-phenyl ketone, 2- benzyl -2- dimethylamino -1- (4- morphlinophenyl)-butane -1- ketone；
The benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzil dimethyl ketal system
Close object；Benzophenone, benzil benzoic acid, benzil methyl benzoate, 4- phenyl benzophenone, dihydroxy benaophenonel, propylene
Acylated benzophenone, 4- benzoyl -4'- dimethyl diphenyl sulfide, 3,3', 4,4'- tetra- (tert-butyl hydroperoxide carbonyl) hexichol first
The benzophenone based compounds such as ketone；Thioxanthones, 2-chlorothioxanthone, 2- methyl thioxanthones, isopropyl thioxanthone, 2,4- diisopropyl
The thioxanthones based compounds such as thioxanthones, 2,4- diethyl thioxanthone；The chloro- s-triazine of 2,4,6- tri-, the bis- (trichlorines of 2- phenyl -4,6-
Methyl)-s-triazine, bis- (the trichloromethyl)-s-triazine of 2- (p-methoxyphenyl) -4,6-, 2- (p-methylphenyl) -4,6- bis- (three
Chloromethyl)-s-triazine, bis- (the trichloromethyl)-s-triazine of 2- piperonyl -4,6-, bis- (the trichloromethyl) -6- styryls-of 2,4-
S-triazine, bis- (the trichloromethyl)-s-triazine of 2- (naphthalene -1- base) -4,6-, 2- (4- methoxyl group-naphthalene -1- base) bis- (three chloromethanes of -4,6-
Base)-s-triazine, 2,4- trichloromethyl-(piperonyl) -6- triazine, 2,4- trichloromethyl (4'- methoxyl-styrene) -6- three
The triazine based compounds such as piperazine；1,2- acetyl caproyl, 1- [4- (phenyl) phenyl]-, 2- (o-benzoyl oxime), O- (acetyl group)-
The oximes ester based compounds such as N- (1- phenyl -2- oxygen -2- (4'- methoxy-naphthyl) ethylidene) azanol；Bis- (2,4,6- trimethylbenzenes
Formyl) the phosphines based compound such as phenyl phosphine oxide, 2,4,6- trimethylbenzoyl diphenyl phosphine oxide；9,10- phenanthrenequione, camphorquinone,
The oxime-based compounds such as ethyl hydrazine；Borate-based compound；Carbazole based compound；Imidazole compound；Titanocenes based compound
Deng.These Photoepolymerizationinitiater initiaters can be used one kind or be use mixing two or more.
Relative to the 100 weight % of all solids ingredient in photosensitive composition, above-mentioned Photoepolymerizationinitiater initiater
(D) content can be 0.5~50 weight %, more preferably can be 3~30 weight %.In above-mentioned Photoepolymerizationinitiater initiater (D)
In the case that content is in above range, sufficient photopolymerization can trigger when being exposed in pattern formation process, it will not
The transmitance as caused by unreacted initiator remaining after photopolymerization, which occurs, to be reduced.
Solvent (E)
In one embodiment of the present invention, above-mentioned solvent (E) is suitable as long as photosensitive composition can be made to have
When viscosity, and make remaining ingredient be easy dissolution be just not particularly limited, photosensitive composition field can be used
Used in various organic solvents.
As the concrete example of above-mentioned solvent (E), ethylene glycol single methyl ether, ethylene glycol monomethyl ether, ethylene glycol can be enumerated
The ethylene glycol monoalkyl ethers class such as single propyl ether, ethylene glycol monobutyl ether；Diethylene glycol dimethyl ether, diethylene glycol diethyl ether,
The diethylene glycol dialkyl ethers class such as diethylene glycol dipropyl ether, diethylene glycol dibutyl ether；Methylcellosolve acetate, ethyl are molten
The ethylene glycol alkyl ethers acetate esters such as fine agent acetic acid esters；The propylene-glycol monoalky lethers class such as propylene glycol monomethyl ether；Propylene glycol list first
Base ether acetic acid ester, propylene glycol monoethyl acetic acid esters, propylene glycol monopropyl ether acetic acid esters, methoxybutyl acetic acid esters and methoxyl group
The aklylene glycols alkylether acetates class such as pentaacetic acid ester；Benzene,toluene,xylene, mesitylene etc. are aromatic hydrocarbon；Methyl
The ketones such as ethyl ketone, acetone, methyl amyl ketone, methyl iso-butyl ketone (MIBK), cyclohexanone；Ethyl alcohol, propyl alcohol, butanol, hexanol, cyclohexanol,
The alcohols such as ethylene glycol, glycerol；The esters such as 3- ethoxyl ethyl propionate, 3- methoxy methyl propionate；The ring-type esters such as gamma-butyrolacton
Deng.In above-mentioned solvent (E), from the aspect of coating, drying property, can preferably enumerate boiling point is 100~200 DEG C organic molten
Agent can more preferably enumerate aklylene glycol alkylether acetates class, ketone, 3- ethoxyl ethyl propionate or 3- methoxypropionic acid
The esters such as methyl esters can further preferably enumerate propylene glycol monomethyl ether, propylene glycol monomethyl ether, propylene glycol list ethyl
Ether acetic acid ester, cyclohexanone, 3- ethoxyl ethyl propionate, 3- methoxy methyl propionate etc..
Above-mentioned solvent (E) can respectively individually or be use mixing two or more.
Relative to the whole 100 weight % of photosensitive composition, the content typically 50 of above-mentioned solvent (E)
~90 weight % preferably can be 55~90 weight %.In the case where the content of above-mentioned solvent (E) is above range, utilize
The apparatus for coating such as roll coater, spin coater, slit spin coater, slit coater (sometimes referred to as die coating machine), flush coater into
When row coating, having can make coating become good tendency, therefore preferably.
Additive (F)
The photosensitive composition of one embodiment of the present invention in addition to the above ingredients, can according to need
Further include additive (F).
As above-mentioned additive (F), can be used selected from other high-molecular compounds, curing agent, pigment dispersing agent, silane
It is more than at least one of coupling agent, antioxidant, ultraviolet absorbing agent, anticoagulant etc..
As the concrete example of other above-mentioned high-molecular compounds, the heat such as epoxy resin, maleimide resin can be enumerated
Thermosetting resin, the heat such as polyvinyl alcohol, polyacrylic acid, polyalkylene glycol monoalkyl ether, poly- fluoroalkyl, polyester, polyurethane
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, oxetane compound etc. can be enumerated.
As the concrete example of the epoxide in above-mentioned curing agent, bisphenol A type epoxy resin, A Hydrogenated Bisphenol A can be enumerated
A type epoxy resin, bisphenol f type epoxy resin, A Hydrogenated Bisphenol A F type 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 such epoxy resin
Brominated derivative, the aliphatic other than epoxy resin and its brominated derivative, alicyclic or aromatic epoxy compound, fourth two
Alkene (co) polymer epoxides, isoprene (co) polymer epoxides, (methyl) glycidyl acrylate are (total) poly-
Close object, triglycidyl isocyanurate etc..
As the concrete example of the oxetane compound in above-mentioned curing agent, carbonic ester dioxygen heterocycle fourth can be enumerated
Alkane, dimethylbenzene dioxygen azetidine, adipate ester dioxygen azetidine, terephthalate dioxygen azetidine, hexamethylene two
Carboxylic acid dioxygen azetidine etc..
Above-mentioned curing agent can also be used in combination with curing compound is helped, described to help curing compound that make together with curing agent
The oxetanes scaffolds open polymerization of the epoxy group, oxetane compound of epoxide.It is above-mentioned to help curing compound
Such as have polybasic carboxylic acid class, polybasic carboxylic acid anhydride, acid agent etc..
Above-mentioned polybasic carboxylic acid anhydride can utilize commercially available epoxy curing agent.Tool as above-mentioned epoxy curing agent
Body example can enumerate ADEKA HARDENER EH-700 (trade name, ADEKA industry (strain) manufacture), RIKACID HH (commodity
Name, the manufacture of new Japan Chemical (strain)), MH-700 (trade name, new Japan Chemical (strain) manufacture) etc..
Foregoing illustrative curing agent can be independent or be use mixing two or more.
As above-mentioned pigment dispersing agent, surfactant can be used to improve coating, as above-mentioned surfactant,
It is preferred that silicone based surfactants, fluorine system surfactant, ester system surfactant etc. can be used.
As the concrete example of above-mentioned surfactant, polyoxyethylene alkyl ether class, polyoxyethylene alkylphenyl can be enumerated
Ethers, polyethylene glycol di class, sorbitan fatty ester class, fatty acid modified polyesters, tertiary-amine modified polyurethanes,
Polyethyleneimine amine etc. has the KP (SHIN-ETSU HANTOTAI's chemical industry (strain) manufacture) as trade name, POLYFLOW (altogether as commercially available product
Flourish society chemical (strain) manufacture), EFTOP (manufacture of Tohkem Products company), MEGAFAC (big Japanese ink chemical industry
(strain) manufacture), Fluorad (Sumitomo 3M (strain) manufacture), Asahi guard, Surflon (more than, Asahi Glass glass (strain) make
Make), SOLSPERSE (manufacture of Lubrisol company), EFKA (manufacture of EFKA CHEMICALS company), 821 (aginomoto of PB
(strain) manufacture), Disperbyk serial (manufacture of BYK-chemi company), BM-1000, BM-1100 (manufacture of BM Chemie company)
Deng.
Foregoing illustrative surfactant can respectively individually or be used in combination of two or more.
Above-mentioned silane coupling agent for improving and the adaptation of substrate, can have select free carboxyl group, methylacryloyl,
Reactive substituents in the group of isocyanate group, epoxy group and their combination composition.
As the concrete example of silane coupling agent, trimethoxysilyl benzoic acid, γ-methacryloxypropyl can be enumerated
Propyl trimethoxy silicane, vinyltriacetoxy silane, vinyltrimethoxysilane, γ-isocyanate group propyl three
Ethoxysilane, γ-glycidoxypropyltrimethoxy silane, β-(3,4- epoxycyclohexyl) ethyl trimethoxy silane etc..
Foregoing illustrative silane coupling agent can respectively individually or be used in combination of two or more.
As the concrete example of above-mentioned antioxidant, 2,2'- thiobis (4- methyl-6-tert-butylphenol), 2 can be enumerated,
6- di-tert-butyl-4-methy phenol etc..
As the concrete example of above-mentioned ultraviolet absorbing agent, 2- (3- tert-butyl -2- hydroxy-5-methyl base phenyl)-can be enumerated
5- chlorobenzotriazole, alkoxy benzophenone etc..
As the concrete example of above-mentioned anticoagulant, Sodium Polyacrylate etc. can be enumerated.
The photosensitive composition of one embodiment of the present invention can for example manufacture by the following method.
Firstly, the pigment in above-mentioned colorant (A) is mixed with solvent (E) and makes its dispersion until face using ball mill etc.
The average grain diameter of material reaches 0.2 μm or less degree.At this point, can make as needed pigment dispersing agent, alkali soluble resins (B) one
Partly or entirely or dyestuff is mixed together with solvent (E), is made it dissolve or is dispersed.It is above-mentioned through in mixed dispersion liquid at
Remaining alkali soluble resins (B), Photoepolymerizationinitiater initiater (D), optical polymerism chemical combination are further added for the mode of scheduled concentration
Object (C) and additive (F) and solvent as needed (E), so as to manufacture coloring phototonus resin combination of the invention
Object.
One embodiment of the present invention relates to the use of above-mentioned photosensitive composition and the colour filter that is formed.This
The colour filter of one embodiment of invention is characterized in that, includes that above-mentioned photosensitive composition is coated on substrate
And it is exposed and develops to the coloring layer formed in a predetermined pattern.
Hereinafter, the pattern forming method using photosensitive composition of the invention is described in detail.
The method that pattern is formed using photosensitive composition of the invention can be used in the art
Well known method generally includes application step, step of exposure and removal step.By by coloring phototonus tree of the invention
Oil/fat composition is coated on substrate and carries out photocuring and development and form pattern, so as to be used as colored pixels (coloring
Image) or black matrix.
Specifically, using the method appropriate such as spin coating, slit coating in the glass substrate for not carrying out any coating or
WithThickness be coated on the glass substrate of SiNx (protective film) in the coating of 2.0~3.4 μm of thickness
State photosensitive composition.After coating, irradiation light is to form pattern required for colour filter.After irradiation light, if
Coating layer is handled using alkaline developer, then the non-irradiated part of coating layer can be dissolved, and be formed required for colour filter
Pattern.Such process is repeated according to the quantity of required R, G, B color, it is hereby achieved that having desired figure
The colour filter of case.In addition, the picture pattern obtained by development in above process is carried out again to heat or utilize activity
Radiation exposure etc. makes its solidification, so as to further increase marresistance, solvent resistance etc..
One embodiment of the present invention is related to the image display device for the colour filter for having above-mentioned, can be with as concrete example
It enumerates such as liquid crystal display device, OLED, flexible display, but not limited thereto.
Image display device of the invention is other than having above-mentioned colour filter, also comprising known in the art
It constitutes.
The image display device of one embodiment of the present invention can be further equipped with packet other than above-mentioned colour filter
Containing the red pattern layer containing red quantum dot particle, the green pattern layer containing green quantum dot particles and contain amount of blue
The colour filter of the blue color patterns layer of son point particle.In this case, applied to the sending light of the light source of image display device
It is not particularly limited, from the aspect of more excellent colorrendering quality, the light source for issuing blue light preferably can be used.
The image display device of one embodiment of the present invention can also be further equipped with other than above-mentioned colour filter
Colour filter only comprising the pattern layer of two kinds of colors in red pattern layer, green pattern layer and blue color patterns layer.In such feelings
Under condition, above-mentioned colour filter is further equipped with the transparent pattern layer without containing quantum dot particles.In the pattern for only having two kinds of colors
In the case where layer, the light source for issuing the light for the wavelength that the remaining color for not including is presented can be used.For example, only comprising red
In the case where chromatic graph pattern layer and green pattern layer, the light source for issuing blue light can be used.In this case, red quantum
Point particle issues red light, and green quantum dot particles issue green light, and transparent pattern layer makes blue light be directed through and indigo plant is presented
Color.
Hereinafter, further illustrating the present invention by embodiment, comparative example and experimental example.These embodiments, comparative example and
Experimental example is merely to illustrate the present invention, and the scope of the present invention is not limited, this be to those skilled in the art it is aobvious and
It is clear to.
Manufacture Examples 1 to 6 and manufacture comparative example 1~7: the manufacture of photosensitive composition
Each ingredient is mixed according to the composition of following table 1, manufactures photosensitive composition (unit: weight %)
[table 1]
Colorant (A)
R254:C.I. paratonere 254
R242:C.I. paratonere 242
R177:C.I. paratonere 177
G58:C.I. naphthol green 58
G59:C.I. naphthol green 59
G36:C.I. pigment green 36
Y138:C.I. pigment yellow 13 8
Y150:C.I. pigment yellow 150
B15:6:C.I. pigment blue 15: 6
V23:C.I. pigment Violet 23
Alkali soluble resins (B): SPCY-1L (Showa electrician company)
Photopolymerizable compound (C): A9550 (company, the village Xin Zhong)
Photoepolymerizationinitiater initiater (D): OXE-01 (BASF AG)
Solvent (E): methyl proxitol acetate (PGMEA)
Experimental example 1: the evaluation of physical property of photosensitive composition
It measures above-mentioned manufacture embodiment as follows and manufactures the coloring phototonus resin group that manufactures in comparative example
The physical property of object is closed, and the results are shown in following table 2.
(1) voltage retention
Photosensitive composition is spun on ito glass with 2.0~2.5 μm of film thickness, is utilized after soft baking
High-pressure mercury-vapor lamp forms 100 μm of pattern.Then, developed using KOH aqueous solution, at 230 DEG C by drying firmly, production coloring
Layer.
On above-mentioned coloring layer ito glass, with the vertical PI alignment films 30s of 3000RPM spin coating, after activation procedure,
Ito glass is engaged and makes VA unit (VA Cell).
Using VHR sensing equipment, the voltage retention of above-mentioned coloring layer VA unit is measured, is placed under the xenon lamp of 300W
It after 1000 hours, then is measured, to calculate voltage retention variable quantity after light irradiation.
(2) dielectric loss
In film forming on the photosensitive composition film on ito glass substrate, using vacuum deposition apparatus, withThickness is formedAluminium electrode.
After being placed 1000 hours under the xenon lamp of 300W, existed using LCR measuring instrument (Agilent 4284A LCR Meter)
At select electrode under room temperature any 4, dielectric loss is measured.Choose maximum value.
(3) volume resistance
Photosensitive composition is formed a film with 2.0~3.0 μm on silicon wafer.
After being placed 1000 hours under the xenon lamp of 300W, using volume resistance sensing equipment (MCP-HT450,
MITSUBISHI CHEMICAL) each photosensitive composition film of measurement volume resistance.
[table 2]
| VHR change rate (%) | Volume resistance (Ω cm) | Dielectric loss (tan δ) | |
| It manufactures embodiment 1 (R-1) | 38% | 5.85×10^15 | 0.0052 |
| It manufactures embodiment 2 (R-2) | 35% | 1.62×10^16 | 0.0082 |
| It manufactures comparative example 1 (R-3) | 77% | 2.53×10^15 | 0.0054 |
| It manufactures comparative example 2 (R-4) | 89% | 8.15×10^15 | 0.0121 |
| It manufactures embodiment 3 (G-1) | 40% | 3.54×10^15 | 0.0035 |
| It manufactures embodiment 4 (G-2) | 38% | 1.25×10^15 | 0.0039 |
| It manufactures comparative example 3 (G-3) | 85% | 9.85×10^14 | 0.0042 |
| It manufactures comparative example 4 (G-4) | 73% | 1.21×10^15 | 0.0182 |
| It manufactures comparative example 5 (G-5) | 74% | 3.85×10^13 | 0.0055 |
| It manufactures embodiment 5 (B-1) | 35% | 5.81×10^14 | 0.0048 |
| It manufactures embodiment 6 (B-2) | 48% | 1.28×10^15 | 0.0094 |
| It manufactures comparative example 6 (B-3) | 78% | 2.21×10^15 | 0.0084 |
| It manufactures comparative example 7 (B-4) | 49% | 3.15×10^15 | 0.0162 |
Experimental example 2: the evaluation of physical property of liquid crystal cells
Tool is manufactured as follows using the photosensitive composition manufactured in above-mentioned manufacture embodiment and manufacture comparative example
The liquid crystal cells of the standby colour filter that there is the coloring layer as following Table 3 and table 4 to constitute.
With 2.0~2.5 μm of film thickness spin coating red sensitive resin combination on ito glass, height is utilized after soft baking
Medium pressure mercury lamp forms 100 μm of pattern.Then, developed using KOH aqueous solution, pass through baking work red firmly at 230 DEG C
Chromatograph.Green, blue-colored layer are formed using identical process on red colored layer pattern glass, obtains more kinds of RGB colorings
Layer.
On above-mentioned a variety of coloring layer ito glasses, with the vertical PI alignment films 30s of 3000RPM spin coating, by activation procedure it
Afterwards, ito glass is engaged and makes VA unit.
The physical property of above-mentioned a variety of coloring layer VA units is measured by the following method, and shows the result in following Table 3 and table 4
In.
(1) voltage retention
Using VHR sensing equipment, the voltage retention of above-mentioned a variety of coloring layer VA units is measured, is transferred in the xenon lamp of 300W
It after setting 1000 hours, then is measured, to calculate voltage retention variable quantity after light irradiation.
(2) liquid crystal drive characteristic
After obtaining the voltage-transmittance curve in the portion green (Green) of above-mentioned a variety of coloring layer VA units, 300W's
Light irradiation in 1000 hours is carried out under xenon lamp, voltage-transmittance curve is then similarly obtained, to calculate the exhausted of each integrated value
Liquid crystal drive characteristic is evaluated to variable quantity, and according to following evaluation criteria.
<evaluation criteria>
Zero: voltage-transmittance curve integrated value absolute change amount is before and after light irradiation | 10% | it is following
×: voltage-transmittance curve integrated value absolute change amount is more than before and after light irradiation | and 10% |
[table 3]
[table 4]
As shown in above-mentioned table 3 and table 4, existed by the unit that photosensitive composition of the invention is formed
The variable quantity of voltage retention (VHR) after being exposed to the luminous energy in all-wave length region is≤| 50% |, the film be exposed to it is complete
Volume resistance is 1 × 10 after the luminous energy of wavelength region14Ω cm or more, in the alternating current of 1~10V of voltage, 1~100kHz of wavelength
Even if the dielectric loss in is 0.01 hereinafter, after to be exposed to the luminous energy in all-wave length region, liquid crystal drive performance is also good
And reliability is also excellent.
On the other hand, deviateing comprising any electrical characteristics (voltage retention, volume resistance and/or dielectric loss)
In the case where the comparative example of coloring layer, voltage retention increased tendency astatically, liquid crystal drive are shown after light irradiation
It can be bad.
Specific part of the invention has been described in detail above, for general technical staff of the technical field of the invention
For, it is obvious that such specific technology is preferred embodiment, and the scope of the present invention is not limited to this.As long as
General technical staff of the technical field of the invention can then be based on the above and carry out within the scope of the present invention respectively
Kind application and deformation.
As a result, the actual scope of the present invention by subsidiary claim and and its equivalent determine.
Claims (5)
1. a kind of photosensitive composition, which contain toner, alkali soluble resins, photopolymerizable compound, photopolymerization
Initiator and solvent,
The unit formed using the photosensitive composition is after the luminous energy for being exposed to all-wave length region
Voltage retention VHR variable quantity be≤| 50% |,
For the film of the photosensitive composition after the luminous energy for being exposed to all-wave length region, volume resistance is 1 × 1014
Ω cm or more, 1~10V of voltage, 1~100kHz of wavelength AC field in dielectric loss be 0.01 or less.
2. photosensitive composition according to claim 1, the colorant includes 58 He of C.I. naphthol green
C.I. one or more of naphthol green 59.
3. photosensitive composition according to claim 1, relative in photosensitive composition
100 weight % of all solids ingredient, the content of the colorant are 5~50 weight %.
4. a kind of colour filter is formed using photosensitive composition described in any one of claims 1 to 33.
5. a kind of image display device, which is characterized in that have colour filter as claimed in claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2017-0150549 | 2017-11-13 | ||
| KR1020170150549A KR20190054367A (en) | 2017-11-13 | 2017-11-13 | Colored Photosensitive Resin Composition, Color Filter and Display Device |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109782536A true CN109782536A (en) | 2019-05-21 |
Family
ID=66496351
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811312446.2A Pending CN109782536A (en) | 2017-11-13 | 2018-11-06 | Photosensitive composition, colour filter and image display device |
Country Status (2)
| Country | Link |
|---|---|
| KR (1) | KR20190054367A (en) |
| CN (1) | CN109782536A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101688992A (en) * | 2008-01-07 | 2010-03-31 | 凸版印刷株式会社 | Liquid crystal indicator and liquid crystal indicator color filter |
| CN101738862A (en) * | 2008-11-26 | 2010-06-16 | 凸版印刷株式会社 | Green photosensitive coloured composition and colour filter using same |
| JP2011075642A (en) * | 2009-09-29 | 2011-04-14 | Toppan Printing Co Ltd | Color filter and liquid crystal display device using the same |
| CN102279522A (en) * | 2010-06-08 | 2011-12-14 | 东洋油墨Sc控股株式会社 | Coloring composition for color filter and color filter |
| CN104898373A (en) * | 2014-03-07 | 2015-09-09 | 东友精细化工有限公司 | Colored photosensitive resin composition and color filter using the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR102172686B1 (en) | 2014-03-20 | 2020-11-02 | 동우 화인켐 주식회사 | A color photosensitive resin composition, color filter and display device comprising the same |
-
2017
- 2017-11-13 KR KR1020170150549A patent/KR20190054367A/en not_active Application Discontinuation
-
2018
- 2018-11-06 CN CN201811312446.2A patent/CN109782536A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101688992A (en) * | 2008-01-07 | 2010-03-31 | 凸版印刷株式会社 | Liquid crystal indicator and liquid crystal indicator color filter |
| CN101738862A (en) * | 2008-11-26 | 2010-06-16 | 凸版印刷株式会社 | Green photosensitive coloured composition and colour filter using same |
| JP2011075642A (en) * | 2009-09-29 | 2011-04-14 | Toppan Printing Co Ltd | Color filter and liquid crystal display device using the same |
| CN102279522A (en) * | 2010-06-08 | 2011-12-14 | 东洋油墨Sc控股株式会社 | Coloring composition for color filter and color filter |
| CN104898373A (en) * | 2014-03-07 | 2015-09-09 | 东友精细化工有限公司 | Colored photosensitive resin composition and color filter using the same |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20190054367A (en) | 2019-05-22 |
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