CN102576190A - Colored photosensitive resin composition, color filter, and liquid crystal display device - Google Patents

Colored photosensitive resin composition, color filter, and liquid crystal display device Download PDF

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Publication number
CN102576190A
CN102576190A CN2010800432880A CN201080043288A CN102576190A CN 102576190 A CN102576190 A CN 102576190A CN 2010800432880 A CN2010800432880 A CN 2010800432880A CN 201080043288 A CN201080043288 A CN 201080043288A CN 102576190 A CN102576190 A CN 102576190A
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CN
China
Prior art keywords
pattern
color filter
photosensitive composition
exposure
photosensitive resin
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CN2010800432880A
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Chinese (zh)
Inventor
儿玉知启
柏木大助
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Fujifilm Corp
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Fujifilm Corp
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Publication of CN102576190A publication Critical patent/CN102576190A/en
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Classifications

    • 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
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/201—Filters in the form of arrays
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1335—Structural association of cells with optical devices, e.g. polarisers or reflectors
    • G02F1/133509—Filters, e.g. light shielding masks
    • G02F1/133512—Light shielding layers, e.g. black matrix
    • G—PHYSICS
    • 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
    • G02F1/133516—Methods for their manufacture, e.g. printing, electro-deposition or photolithography
    • 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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic 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
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor
    • G03F7/2022—Multi-step exposure, e.g. hybrid; backside exposure; blanket exposure, e.g. for image reversal; edge exposure, e.g. for edge bead removal; corrective exposure
    • 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
    • G02F2202/00—Materials and properties
    • G02F2202/02—Materials and properties organic material
    • G02F2202/022—Materials and properties organic material polymeric
    • G02F2202/023—Materials and properties organic material polymeric curable

Abstract

Disclosed is a colored photosensitive resin composition, which exhibits good patterning properties during development and enables the formation of a fine pattern. Specifically disclosed is a colored photosensitive resin composition, which contains a coloring agent including a black coloring material, an alkali-soluble resin, a polymerizable compound having three or more polymerizable groups, a polymerization initiator or a polymerization initiation system, and a solvent. The colored photosensitive resin composition is characterized in that when a photosensitive resin layer, which contains the colored photosensitive resin composition so as to have an optical concentration of 4.0, is formed on a transparent substrate, and then a first pattern is obtained by exposing and developing the photosensitive resin layer through a mask from a side of the photosensitive resin layer, said side being the reverse side of the transparent substrate-side, under such exposure/development conditions that the line width (W1) of the first pattern to the line width (W2) of the mask, namely W1/W2 is within the range of 0.7-1.5 and a second pattern is obtained by exposing and developing the photosensitive resin layer through a mask from the transparent substrate-side of the photosensitive resin layer under the above-described exposure/development conditions, the ratio of the film thickness (d1) of the second pattern to the film thickness (d2) of the first pattern, namely d1/d2 is not less than 0.3.

Description

Photosensitive composition, color filter and liquid crystal indicator
Technical field
The present invention relates to a kind of photosensitive composition, color filter and liquid crystal indicator.
Background technology
Usually, display device uses color filter on substrates such as glass, red, green, blue scattergram picture being configured to structure rectangular, distinguish its boundary with dark partition walls such as black matrix"s respectively.As such manufacturing method of color filter, at present known have substrates such as using glass as supporter, utilize 1) decoration method, 2) print process, 3) by the coloring phototonus resin liquid method that repeats to form (painted resist method), 4 of coating and the exposure and the development of painted photoresist liquid) image that will on interim supporter, form is needed on the method, 5 on the final or interim supporter successively) only the quantity of color repeat to form dyed layer on the interim supporter through will painted in advance photoresist liquid coating, successively directly with this photosensitive color layer is transferred on the substrate, the method for exposure and development etc. forms multicolor image method (transfer printing mode).In addition, the also known method that the use ink-jet method is arranged.
In these methods, though painted resist method can the positional precision highland be made color filter,, in the coating of photoresist liquid loss many, it is favourable aspect cost, can not to say so.On the other hand, though the loss of ink-jet method photoresist liquid is less and aspect cost, be favourable,, have the problem of locations of pixels low precision.In order to overcome these problems, also proposed to make the color filter autofrettage of rgb pixel with painted resist method formation black matrix" and with ink-jet method.
With above-mentioned relevant, known have contain on the side chain the cinnamic radiation sensitive compositions that contains (methyl) acryloyl group.In view of the above, though the damaged and undercutting (under cut) that does not also produce pattern edge with low exposure, and can remaining not dissolved matter when developing or produce scum silica frost at pattern edge, can form fine pattern (for example with reference to TOHKEMY 2008-181095 communique).
In addition, known have contain the coloring photosensitive combination that acetophenone is a polymerization initiator.In view of the above, though use coloring material,, can form with respect to light is high sensitivity and the black matrix" (for example, with reference to TOHKEMY 2006-276173 communique) high to the adaptation of glass substrate.
Summary of the invention
The problem that solves is wanted in invention
But with regard to the photosensitive composite of putting down in writing in TOHKEMY 2008-181095 communique and the TOHKEMY 2006-276173 communique, it is damaged when black matrix" forms, to produce pixel sometimes.Therefore, need after rgb pixel forms, carry out the defect correction that colour mixture or pixel come off, production efficiency reduces sometimes.
Problem of the present invention is that the pattern when a kind of the development is provided becomes second nature well, can form the photosensitive composition of fine pattern and uses this photosensitive composition and color filter that forms and the liquid crystal indicator with this color filter.
The method that is used to deal with problems
The concrete method that is used to solve above-mentioned problem is described below.
< 1>a kind of photosensitive composition; It comprises colorant, the alkali soluble resin of the colorant that contains black, the polymerizable compound with 3 above polymerizable groups, polymerization initiator or polymerization initiation system and solvent; Wherein, On transparency carrier, become 4.0 mode and form the photo-sensitive resin that contains said photosensitive composition with optical density (OD); From with said photo-sensitive resin and opposing face side opposed of said transparency carrier; Across mask with said photo-sensitive resin make public, development treatment and the live width that forms the 1st pattern is W1, becoming the thickness that obtains said the 1st pattern under the exposure, development conditions of 0.7～1.5 scope with respect to the ratio W1/W2 of the live width W2 of said mask at the live width W1 of the 1st pattern is d2; And from said photo-sensitive resin with opposed side of said transparency carrier; Become at said W1/W2 across mask and said transparency carrier under the exposure, development conditions of 0.7～1.5 scope with said photo-sensitive resin make public, development treatment and the thickness that obtains the 2nd pattern is d1, d1 is more than 0.3 with the ratio of d2.
< 2>like above-mentioned < 1>described photosensitive composition, wherein, the exposure, the said d1/d2 under the development conditions that become 0.8～1.2 scope at said W1/W2 are 0.3～0.7 scope.
< 3>like above-mentioned < 1>or < 2>described photosensitive composition, wherein, said colorant contains carbon black at least.
< 4>like each described photosensitive composition in above-mentioned < 1 >～< 3 >, wherein, said polymerization initiator or polymerization initiation system contain at least a kind of acylphosphine oxide series initiators.
< 5>like each described photosensitive composition in above-mentioned < 1 >～< 4 >, wherein, said polymerizable compound with 3 above polymerizable groups be 3 officials can acrylic monomers and 4 officials can acrylic monomers at least a kind.
< 6>a kind of photosensitive transfer printing material, its photo-sensitive resin that is formed by each described photosensitive composition in above-mentioned < 1 >～< 5>is arranged on the interim supporter and forms.
< 7>a kind of color filter, it has substrate and uses each described photosensitive composition in above-mentioned < 1 >～< 5>and form and be configured in the light shielding part on the said substrate.
< 8>like above-mentioned < 7>described color filter, wherein, said light shielding part is to use above-mentioned < 6>described photosensitive transfer printing material to form.
< 9>like above-mentioned < 7>or < 8>described color filter, wherein, the optical density (OD) of said light shielding part is more than 3.5.
< 10>like each described color filter in above-mentioned < 7 >～< 9 >, wherein, the thickness of said light shielding part is more than 1.5 microns.
< 11>a kind of liquid crystal indicator, it has each described color filter in above-mentioned < 7 >～< 10 >.
According to the present invention, the pattern when a kind of the development can be provided becomes second nature good and can form the photosensitive composition of fine pattern and use this photosensitive composition and color filter that forms and the liquid crystal indicator with this color filter.
Embodiment
< photosensitive composition >
Photosensitive composition of the present invention is the photosensitive composition of colorant, the alkali soluble resin that comprises the colorant that contains black at least, the polymerizable compound with 3 above polymerizable groups, polymerization initiator or polymerization initiation system and solvent.And; It is following photosensitive composition: under the exposure of following regulation, development conditions; To contain the photo-sensitive resin that is configured in the said photosensitive composition on the transparency carrier from said photo-sensitive resin and opposing face side opposed of said transparency carrier, across mask to said photo-sensitive resin make public, development treatment and the thickness that forms the 1st pattern is d2; With from said photo-sensitive resin with opposed side of said transparency carrier, across mask and said transparency carrier to said photo-sensitive resin make public, development treatment and the thickness of the 2nd pattern that obtains is d1, d1 is more than 0.3 with the ratio of d2.
When said ratio d1/d2 less than 0.3 the time, the pattern when developing sometimes becomes second nature insufficient, can not form fine pattern.In addition, when using for example said photosensitive composition to form black matrix" (partition wall), it is damaged to produce pixel sometimes.
The exposure of said regulation, development conditions are exposure, the development conditions of setting as follows; Promptly; On transparency carrier, use said photosensitive composition to become 4.0 mode and form photo-sensitive resin with optical density (OD); From with said photo-sensitive resin and opposing face side opposed of said transparency carrier; Across mask to said photo-sensitive resin make public, development treatment and the live width that forms pattern is W1, the live width W1 of this pattern becomes 0.7～1.5 scope with respect to the ratio W1/W2 of the live width W2 of said mask.
In addition, as the said transparency carrier that uses when the exposure of setting regulation, the development conditions, can use transmitance with respect to the light more than the 350nm is glass, synthetic resin film etc. more than 70%.
In the present invention, said ratio d1/d2 is more than 0.3, is preferably 0.3～0.7, and, becoming under 0.8～1.2 exposure, the development conditions at said ratio W1/W2, ratio d1/d2 more preferably 0.3～0.7.Through said ratio W1/W2 and ratio d1/d2 is described scope, and the pattern when developing thus becomes second nature and further improves, and can form fine pattern, the damaged generation of pixel when more effectively suppressing pattern formation.
Usually; Will the photo-sensitive resin that forms on the transparency carrier from the thickness with the 1st pattern that makes public, develops and obtain across mask with the opposing face side of opposed of transparency carrier be d2 be certain more than exposure and be roughly necessarily, the setting thickness when forming photo-sensitive resin is about equally.On the other hand; From the thickness of the 2nd pattern that the photo-sensitive resin that forms at transparency carrier made public, develops and obtains across mask and transparency carrier with opposed side of transparency carrier is d1; It is big by the change that exposure causes, exposure hour, and d1 is little; When exposure was big, it is big that d1 becomes.Particularly form under the situation of photo-sensitive resin at the high materials of the covering property that becomes 4.0 that kind with optical density (OD); Screening capacity under the emission wavelength zone of exposure light source is also high; Therefore, when under identical exposure, development conditions, handling, d1 and d2 are in a ratio of little value.
On the other hand, the exposure when forming pattern through making is greater than the exposure of regulation, becomes greatly because of exposure for roughly certain value and d1 with d2, and therefore, it is big that the d1/d2 that stipulates among the present invention also becomes.At this moment, not only carry out the curing of thickness direction, and carry out the curing of Width, therefore, under such conditions of exposure, it is big that the live width W1 of pattern becomes.Its result, from photosensitive composite and opposing face side opposed of transparency carrier across mask make public, develop and the ratio W1/W2 of live width W1 after forming pattern, pattern and mask linewidths W2 greater than 1.5, can not obtain desired pattern.
In addition, the live width W1 of pattern is influenced by mask linewidths W2 and exposure not only, and receives the influence of development conditions, through relaxing development conditions, makes W1 become big, in addition, through the intensifying processing condition, W1 is diminished.But, except that the amplitude of adjustment is little, big to the influence damaged, shape of the pattern of the residue of pattern periphery and gained.Therefore, only make development conditions change, realize desired W1/W2 and d1/d2 difficulty.
On the other hand, through the starting material concentration (particularly, for example improving initiator concentration etc.) in the adjustment photosensitive composition, d1/d2 is increased.But, the above-mentioned tendency that likewise exists W1 to increase, in addition, the film during curing after pattern forms shrinks big, is easy to generate substrate contamination.Therefore, only adjust the starting material concentration in the photosensitive composition, realize desired W1/W2 and d1/d2 difficulty.
In the present invention, the ratio W1/W2 of the live width W1 of pattern and mask linewidths W2 is when the scope of regulation, and preferred ratio d1/d2 is greater than the value of regulation.Therefore; Regulation ratio W1/W2 becomes exposure, the development conditions of 0.7～1.5 scope; At this moment; The thickness of the 1st pattern that obtains from developing after mask makes public with the opposing face side of transparent substrate side is d2; After mask exposure, develop and the thickness of the 2nd pattern that obtains is d1 from transparent substrate side, make with respect to the ratio d1/d2 of the thickness d1 of the 2nd pattern of the thickness d2 of the 1st pattern and adjust the composition of photosensitive composition, constitute the photosensitive composition that pattern when developing became second nature well, can form fine pattern thus for the mode of the scope of regulation.
(colorant)
Cured composition for color of the present invention contains at least a kind of colorant.As being used for colorant of the present invention, can preferably use known colorant (organic pigment, inorganic pigment, dyestuff etc.).Particularly, can preferably use the colorant etc. of record in paragraph numbering [0080]～[0088] of pigment, TOHKEMY 2005-17521 communique of record in paragraph numbering [0068]～[0072] of pigment and dyestuff, TOHKEMY 2004-361447 communique of record in paragraph numbering [0038]～[0054] of TOHKEMY 2005-17716 communique.
In the present invention, consider, preferably contain black colorant from the viewpoint of optical density (OD).As black colorant, for example can enumerate that carbon black, titanium are black, oxidation iron, titanium dioxide, graphite etc., wherein, preferred carbon black.
In addition, in the present invention, except that black colorant, can use potpourri of pigment such as red, blue, green etc.
Above-mentioned colorant (preferred pigments, more preferably carbon black) preferably uses as dispersion liquid.This dispersion liquid can be through being pre-mixed the organic solvent of stating after composition that said colorant and pigment dispersing agent obtain is added on (or vehicle) and making it disperse to prepare.Said vehicle is meant the part of the medium that when coating is in liquid condition, makes pigment dispersing, is included as aqueous and forms the composition (bonding agent) of filming with said pigment bonding and it is carried out the composition (organic solvent) of dissolved dilution.
The dispersion machine that uses when making said pigment dispersing; Not special restriction; For example can enumerate towards the storehouse nation make work, " topical reference book of pigment (pigment topical reference book) ", first published, towards the storehouse bookstore, 2000, known dispersion machines such as the kneader of being put down in writing in 438, roller mill, vertical ball mill (attritor), super ball grinding machine, high speed dispersor, homogenizer, puddle mixer.And, the grinding of the machinery through 310 pages of records of the document, it is broken to utilize friction force to carry out micro mist.
Consider the colorant of preferred number average bead diameter 0.001～0.1 μ m of the colorant that uses among the present invention, the further colorant of preferred 0.01～0.08 μ m from the viewpoint of dispersion stabilization.In addition, be meant the diameter of the electron micrograph image of particle being processed bowlder of the same area at this said " particle diameter ", in addition, " number average bead diameter " is meant the particle of majority obtained above-mentioned particle diameter, got its mean value of 100.
Containing ratio as the colorant in the total solid composition of the photosensitive composition among the present invention; Not special restriction is considered from the viewpoint that shortens development time fully, is preferably 15～70 quality %; More preferably 20～60 quality % further are preferably 25～50 quality %.
In addition, said total solid composition is meant the total amount of having removed the involatile composition of solvent from photosensitive composition in this instructions.
(alkali soluble resin)
Photosensitive composition of the present invention preferably contains at least a kind of alkali soluble resin.Thus, alkali-developable is better.
As the alkali soluble resin among the present invention (below, abbreviate " bonding agent " sometimes as), has the polymkeric substance of carboxylic acid group or carboxylate group isopolarity group on preferred main chain or the side chain.As the example, can enumerate: the methacrylic acid copolymer of that kind of being put down in writing in japanese kokai publication sho 59-44615 communique, the special public clear 54-34327 communique of Japan, the special public clear 58-12577 communique of Japan, the special public clear 54-25957 communique of Japan, japanese kokai publication sho 59-53836 communique and the japanese kokai publication sho 59-71048 communique, acrylic copolymer, itaconic acid copolymer, butenoic acid multipolymer, maleic acid, partial esterification maleic acid etc.In addition, also can enumerate the cellulose derivative that has the carboxylic acid group on the side chain, in addition, in addition, also can preferably use have that addition on the polymkeric substance of hydroxyl has cyclic acid anhydride and the material that obtains.
In addition, as special preferred examples, can enumerate the multiple copolymer of (methyl) benzyl acrylate of putting down in writing in No. 4139391 instructions of United States Patent (USP) and (methyl) acrylic acid multipolymer, (methyl) benzyl acrylate and (methyl) acrylic acid and other monomer.These binder polymers with polar group can use separately; Perhaps can form the state use down of composition of polymkeric substance and the usefulness of property with common film; Content with respect to the total solid composition of photosensitive composition is generally 20～50 quality %, is preferably 25～45 quality %.
(polymerizable compound)
Photosensitive composition of the present invention contains at least a kind in the polymerizable compound with 3 above polymerizable groups (below, abbreviate " polymerizable compound " sometimes as).
With regard to said polymerizable compound, so long as have the compound of 3 above polymerizable groups, just can especially restrictedly not use common employed polymerizable compound, be preferably compound with 3～6 polymerizable groups.Wherein, be preferably that to have 3 above ethylenical unsaturated double bonds and boiling point be compound more than 100 ℃ and the monomer or the oligomer that carry out addition polymerization through the irradiation of light under normal pressure.
As such monomer and oligomer, can enumerate: trimethylolethane trimethacrylate acrylic ester, trimethylolpropane tris (methyl) acrylic ester, trimethylolpropane triacrylate, pentaerythrite four (methyl) acrylic ester, pentaerythrite three (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, trimethylolpropane tris (acryloxy propyl group) ether, three (acryloxy ethyl) isocyanates, three (acryloxy ethyl) cyanate, glycerine three (methyl) acrylic ester; Addition has polyfunctional acrylic ester or the multifunctional methacrylates such as material that carries out (methyl) acroleic acid esterification after oxirane or the epoxypropane on polyfunctional alcohols such as trimethylolpropane or glycerine.In addition, the addition of being put down in writing as general formula (1) and (2) in the special public clear 53-11314 communique of Japan on the polyfunctional alcohol has to be carried out compound that (methyl) acroleic acid esterification obtains after oxirane or the epoxypropane and also enumerates as preferred material.
Can also enumerate: the urethane acrylate class of being put down in writing in the special public clear 48-41708 communique of Japan, the special public clear 50-6034 communique of Japan with 3 above polymerizable groups; The polyester acrylate class of being put down in writing in the special public clear 52-30490 communique of special public clear 53-24989 communique of Japan and Japan; Polyfunctional acrylic ester or methacrylates such as epoxy acrylate class as epoxy resin and (methyl) acrylic acid resultant of reaction.
Wherein, preferred trimethylolpropane tris (methyl) acrylic ester, pentaerythrite four (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, three (2-acryloxy ethyl) isocyanates.In addition, " above (methyl) acrylic ester of 3 officials ability " of putting down in writing in the japanese kokai publication hei 11-133600 communique also can be used as preferred material and enumerates.
As said monomer or oligomer, the material of preferred molecular weight 200～1000.In these preferred compounds, preferably contain 3～6 officials can acrylate monomer at least a kind, more preferably contain 3 officials can or 4 officials can acrylate monomer at least a kind.
Particularly; Preferably contain at least a kind that is selected from for example trimethylolpropane tris (methyl) acrylic ester, pentaerythrite four (methyl) acrylic ester and dipentaerythritol six (methyl) acrylic ester, more preferably contain at least a kind that is selected from trimethylolpropane tris (methyl) acrylic ester and pentaerythrite four (methyl) acrylic ester.
These monomers or oligomer can use a kind separately, also can mix and use more than 2 kinds.In addition, can be further and with having the polymerizable compound of 1 polymerizable group and having at least a kind in the polymerizable compound of 2 polymerizable groups.
With respect to the total solid composition of photosensitive composition of the present invention, the content with polymerizable compound of 3 above polymerizable groups is generally 5～80 quality %, is preferably 5～50 quality %, more preferably 10～40 quality %.In the time of in it is said preferred range, control development property more easily.And said content is 5 quality % when above, and the patience to alkaline developer in the exposure portion of composition is better.And then, when it is 80 quality % when following, the increase of the tackiness when suppressing to make photosensitive composition, operability is better.
(polymerization initiator or polymerization initiation system)
Photosensitive composition of the present invention contains at least a kind in polymerization initiator and the polymerization initiation system.As being used for said polymerization initiator of the present invention and polymerization initiation system; Can be in the thermal polymerization initiator system that uses thermal polymerization and the photopolymerization initiator system that uses Photoepolymerizationinitiater initiater any; In the present invention; The viewpoint of the pattern form after solidify is considered the preferred photopolymerization initiator system that uses Photoepolymerizationinitiater initiater that adopts.
The Photoepolymerizationinitiater initiater of this use for the irradiation (being also referred to as exposure) through luminous ray, ultraviolet ray, far ultraviolet, electronics line, X ray israds, can produce the compound of activated source of the polymerization of the above-mentioned polymerizable compound of initiation with 3 above polymerizable groups, can suitably selection from known Photoepolymerizationinitiater initiater or photopolymerization initiator system.Particularly, for example can enumerate: contain compound, acridine based compound, acetophenone based compound, bisglyoxaline based compound, benzoin based compound, benzophenone based compound, α-diketone based compound, multinuclear quinone based compound, xanthone based compound, diazonium based compound, acylphosphine oxide based compound, luxuriant titanium sub-group compound, oxime ester based compound of trihalomethyl etc.
In above-mentioned; Preferably contain at least a kind that is selected from compound, acridine based compound, acetophenone based compound, bisglyoxaline based compound, acylphosphine oxide based compound and the oxime ester based compound that contains trihalomethyl; More preferably contain at least a kind that is selected from the compound that contains trihalomethyl and the acylphosphine oxide based compound, further preferably contain at least a kind that is selected from the acylphosphine oxide based compound.The compound and the acylphosphine oxide based compound that contain trihalomethyl have versatility and aspect cheap, also are being useful.
As compound that contains trihalomethyl and acylphosphine oxide based compound, specifically enumerate the replacement of putting down in writing in the TOHKEMY 2001-117230 communique and have the compound that San halogen Jia oxadiazole compound of putting down in writing in No. 4212976 instructions of trihalomethyl-s-triaizine compounds, United States Patent (USP) of putting down in writing in San halogen Jia oxazole derivatives or the s-pyrrolotriazine derivatives of trihalomethyl, No. 4239850 instructions of United States Patent (USP) etc. contains trihalomethyl; The acylphosphine oxide compound of record in japanese kokai publication sho 55-13794 communique, the japanese kokai publication sho 55-15471 communique etc.As preferred especially compound,, can enumerate 2-trichloromethyl-5-(to the styryl styryl)-1,3 as the compound that contains trihalomethyl; 4-oxadiazole, 2, two (the trichloromethyl)-6-of 4-[4 '-(N, amino-the 3 '-bromophenyl of N-two (ethoxy carbonyl methyl))-s-triazine; As the acylphosphine oxide based compound, can enumerate 2,4; 6-trimethylbenzoyl-diphenyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl)-phenylphosphine oxide etc.
Said polymerization initiator or polymerization initiation system both can use a kind separately, also can be also with more than 2 kinds.As the total containing ratio in the photosensitive composition of said polymerization initiator or polymerization initiation system, 0.1～20 quality % of the total solid composition (quality) of preferred photosensitive composition, preferred especially 0.5～10 quality %.Said total containing ratio is 0.1 quality % when above, and the efficient of the photocuring of composition raises, and can shorten the time shutter.In addition, when it is 20 quality % when following, when developing, can suppress the generation of be full of cracks of the damaged or patterned surfaces of formed picture pattern.
Said polymerization initiator can and be supplied with body with hydrogen.Supply with body as this hydrogen, in that sensitivity is more very considered aspect the change, preferably with undefined mercaptan based compound, amine compound etc." hydrogen supply body " at this is meant the compound that can supply with hydrogen atom to the free radical that produces from said Photoepolymerizationinitiater initiater through exposure.
Said mercaptan based compound is for being parent nucleus with phenyl ring or heterocycle, having the sulfydryl more than 1 that is bonded directly to this parent nucleus, preferred 1～3, further preferred 1～2 compound (below, be called " mercaptan is that hydrogen is supplied with body ").In addition, said amine compound is for being parent nucleus with phenyl ring or heterocycle, having the amino more than 1 that is bonded directly to this parent nucleus, preferred 1～3, further preferred 1～2 compound (below, be called " amine is that hydrogen is supplied with body ").In addition, these hydrogen supply bodies can have sulfydryl and amino simultaneously.
As above-mentioned mercaptan is the concrete example that hydrogen is supplied with body, can enumerate: 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2,5-dimercapto-1,3,4-thiadiazoles etc.Wherein, preferred 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, preferred especially 2-mercaptobenzothiazole.
As above-mentioned amine is the concrete example that hydrogen is supplied with body; Can enumerate: 4; 4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino propiophenone, ethyl-4-dimethylaminobenzoic acid ester, 4-dimethylamino benzoic acid, 4-dimethylamino benzene nitrile etc.Wherein, preferred 4,4 '-two (dimethylamino) benzophenone, 4,4 '-two (diethylamino) benzophenone, preferred especially 4,4 '-two (diethylamino) benzophenone.
Said hydrogen is supplied with body can use a kind or mix and use more than 2 kinds separately.When developing, be difficult for coming off and intensity and sensitivity can consider aspect the raising that also it is that hydrogen is supplied with body and the amine more than a kind is that hydrogen is supplied with body that preferred compositions is used the mercaptan more than a kind from formed image from the permanent support body.
As said mercaptan is that hydrogen is supplied with body and amine is the concrete example that hydrogen is supplied with the combination of body; Can enumerate: 2-mercaptobenzothiazole/4; 4 '-two (dimethylamino) benzophenone, 2-mercaptobenzothiazole/4; 4 '-two (diethylamino) benzophenone, 2-mercaptobenzoxazole/4,4 '-two (dimethylamino) benzophenone, 2-mercaptobenzoxazole/4,4 '-two (diethylamino) benzophenone etc.Preferred 2-mercaptobenzothiazole/4 that are combined as; 4 '-two (diethylamino) benzophenone, 2-mercaptobenzoxazole/4; 4 '-two (diethylamino) benzophenone especially preferably is combined as 2-mercaptobenzothiazole/4,4 '-two (diethylamino) benzophenone.
Combination have said mercaptan be hydrogen supply with body and amine be mercaptan that hydrogen is supplied with the situation of body be hydrogen supply with the mass ratio that body (M) and amine are hydrogen supply body (A) (M: A) common preferred 1: 1～1: 4, more preferably 1: 1～1: 3.
In addition, as the total amount in the photosensitive composition of said hydrogen supply body, 0.1～20 quality % of the total solid composition (quality) of preferred photosensitive composition, preferred especially 0.5～10 quality %.
(solvent)
Photosensitive composition of the present invention contains at least a kind of solvent.As said solvent, can especially restrictedly not use common employed solvent.For example specifically enumerate: ester class, ethers, ketone, aromatic hydrocarbon based etc.
In addition, middle same methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, cyclohexanol, methylisobutylketone, ethyl lactate and the methyl lactate of putting down in writing etc. of Solvent in paragraph numbering [0054] [0055] with the US2005/282073A1 instructions also can preferably use in the present invention.
In these solvents, preferably use 3-ethoxy-propionic acid methyl esters, 3-ethoxyl ethyl propionate, ethyl cellosolve acetate, ethyl lactate, butyl acetate, 3-methoxypropionic acid methyl esters, 2-heptanone, cyclohexanone, diethylene glycol ether acetate alone (ethyl carbitol acetate), diethylene glycol monobutyl ether acetate (BC acetate), 1-Methoxy-2-propyl acetate and methyl ethyl ketone etc. as the solvent among the present invention.These solvents can use a kind separately, perhaps can make up and use more than 2 kinds.
In addition, in the present invention, can use boiling point as required is 180 ℃～250 ℃ organic solvent.As these high boiling solvents; Can enumerate: diethylene glycol monobutyl ether, diethylene glycol ether acetate alone, diethylene glycol monoethyl ether, 3; 5; 5-trimethyl-2-cyclohexene-1-ketone, dipropylene glycol monomethyl ether acetate, PGDA, propylene glycol-n-propyl ether acetate, diethylene glycol diethyl ether, 2-ethylhexyl acetate, 3-methoxyl-3-methyl butyl acetate, gamma-butyrolacton, tripropylene glycol Methylethyl acetate, DPG-n-butyl acetate, propylene glycol phenyl ether acetate, 1,3 butylene glycol diacetate etc.
With respect to the photosensitive composition total amount, the content of the solvent in the photosensitive composition of the present invention, preferred 10～95 quality %, more preferably 15～90 quality % Ga, preferred especially 20～85 quality %.The scope of the content through being set at said solvent, can stably be coated with aspect the photosensitive composite preferred.
Photosensitive composition of the present invention can more contain known adjuvant, for example plastifier, filling agent, stabilization agent, polymerization inhibitor, surfactant, driving fit promoter etc. as required except that above-mentioned colorant, alkali soluble resin, the polymerizable compound with 3 above polymerizable groups, polymerization initiator or polymerization initiation system, solvent.
In addition, said photosensitive composition preferably softens or becomes cohesive, more preferably thermoplasticity under the temperature below at least 150 ℃.Consider from described viewpoint, preferably further contain the good plastifier of compatibility.
As photosensitive composition of the present invention; Preferably comprise carbon black 20～60 quality % as colorant, containing (methyl) more than 3 acrylate-based compound 10～40 quality % and, more preferably comprising be selected from tetramethylol methane tetraacrylate, dipentaerythritol acrylate and the trimethylolpropane triacrylate at least a kind and of carbon black 25～50 quality % as colorant, 10～40 quality % as polymerizable compound as the compound that contains trihalomethyl or acylphosphine oxide based compound 0.5～10 quality % of polymerization initiator as polymerizable compound as the compound that contains trihalomethyl or acylphosphine oxide based compound 0.1～20 quality % of polymerization initiator.
Photosensitive composition of the present invention is preferred for forming the pattern that constitutes color filter.Wherein, be suitable for forming the partition wall (light shielding part, black matrix") that constitutes color filter.
< color filter >
Color filter of the present invention have substrate (below, be sometimes referred to as " permanent support body ") and use said photosensitive composition and form be configured in the light shielding part on the said substrate.In the present invention, with regard to said light shielding part, its optical density (OD) is preferably more than 3.5, more preferably more than 4.0.In addition, with regard to said light shielding part, its thickness is preferably more than the 1.5 μ m, more preferably 1.7～2.5 μ m.Through having described light shielding part, can constitute color filter with good characteristic.
In the present invention, said light shielding part constitutes the for example partition wall of color filter.
(partition wall)
Partition wall with each pixel of color filter in the color filter manufacturing of ink-jet method making rgb pixel preferably uses said photosensitive composition to form.Partition wall is the member that the pixel groups more than 2 is separated, and general most is black, but is not limited to black.
Partition wall preferably through the photo-sensitive resin that will use said photosensitive composition to form under the anoxic atmosphere, make public, developing thereafter forms.
To the not special restriction of the formation method of photo-sensitive resin, can on substrate, be coated with said photosensitive composition and form, the photosensitive transfer printing material of stating after can also using and forming.
As the method for the said photosensitive composition of coating, can especially restrictedly not use common employed coating process.For example, can use apparatus for coating or spin coater to form photo-sensitive resin with gap nozzle.
In addition, be meant under the inert gas under the anoxic atmosphere the when photo-sensitive resin that uses said photosensitive composition to form is carried out photocuring, reduce pressure down and can block under the protective seam of oxygen, these situation are described below in detail.
Said inert gas is meant N 2, H 2, CO 2Etc. rare gas classes such as general gas or He, Ne, Ar.Wherein, consider, preferably utilize N from the problem aspect of security or the easy degree that obtains, cost 2
Be meant the state below the 500hPa, below the preferred 100hPa under the said decompression.
In addition, the said protective seam that can block oxygen for example can be enumerated: the water soluble salt in the water soluble salt of water soluble salt that put down in writing, that contain polyvingl ether/maleic anhydride polymkeric substance, carboxyalkyl cellulose, water-soluble cellulose ether class, carboxyalkyl starch in each communique that japanese kokai publication sho 46-2121 number or Japan are special public clear 56-40824 number, polyvinyl alcohol (PVA), polyvinyl pyrrolidone, various polyacrylamide, various water soluble polyamide, polyacrylic water soluble salt, gelatin, ethylene oxide polymer, the group that is made up of various starch and analog thereof, multipolymer, the maleic ester resin of styrene/maleic acid and make up 2 kinds of these materials with first-class resin bed.
Wherein, the combination of the special pure and mild polyvinyl pyrrolidone of preferably polyethylene.Further the saponification rate of preferably polyethylene alcohol is more than 80%, 1～75 quality % of the content preferred resin layer solid constituent of polyvinyl pyrrolidone, and more preferably 1～50 quality % further is preferably 10～40 quality %.
In addition, as the protective seam that can block oxygen, also can use various films.For example, also can preferably use with PET as the polyesters of representative, with polyamide-based, the ethylene-vinyl acetate copolymer (EVA class) of nylon as representative.These films can stretch as required, and thickness is that 5～300 μ m are fit to, and is preferably 20～150 μ m.
In addition, when using following photosensitive transfer printing material to make partition wall, also can suitably use the layer that can block oxygen on the interim supporter of being arranged on of following record.
The preferred 2000cm of oxygen transmission coefficient of the protective seam of making like this that can block oxygen 3/ (m 2Dayatm) below, 100cm more preferably 3/ (m 2Dayatm) below, most preferably be 50cm 3/ (m 2Dayatm) below.Oxygen permeability is greater than 2000cm 3/ (m 2Dayatm) time, can not block oxygen effectively, therefore, be difficult to control the shape of partition wall sometimes.
(photosensitive transfer printing material)
As easily and with the method for the said partition wall of implemented with low cost; Following method is arranged: the oxygen barrier layer will on interim supporter, be had at least successively and the photosensitive transfer printing material of the layer that is made up of photosensitive composition is needed on the permanent support body, the layer that forms the permanent support body successively, constitutes by photosensitive composition, oxygen barrier layer and the method used.Use under the situation of this material, protected by the oxygen barrier layer, therefore, automatically become under the anoxic atmosphere by the layer that photosensitive composition constitutes.Therefore, has following advantage: need under inert gas or under the decompression, not carry out exposure process, so can directly utilize existing operation.In addition; Also can the photosensitive transfer printing material that on interim supporter, has the layer that is made up of photosensitive composition at least be needed on the permanent support body; The layer, the interim supporter that form the permanent support body successively, constitute by photosensitive composition, and this interim supporter is used as " can block the protective seam of oxygen ".At this moment, above-mentioned oxygen barrier layer need be set, can reduce process number.
Above-mentioned photosensitive transfer printing material can have thermoplastic resin as required.Described thermoplastic resin is alkali-soluble and contains resinous principle at least and constitute.The softening point that this resinous principle is preferably essence is the thermoplastic resin of the alkali-soluble below 80 ℃.Through such thermoplastic resin is set, can after the good adaptation of performance and permanent support body in the partition wall formation method stated.
As softening point is the thermoplastic resin of the alkali-soluble below 80 ℃, can enumerate: saponified, the vinyltoluene of saponified, the styrene of ethene and acrylate copolymer and (methyl) acrylate copolymer and (methyl) acrylate copolymer saponified, gather the saponified etc. of (methyl) acrylate copolymers such as (methyl) acrylic ester, (methyl) butyl acrylate and vinyl acetate etc.
With regard to thermoplastic resin; Can suitably select to use at least a kind in the above-mentioned thermoplastic resin, can also use to be about the thermoplastic resin of the alkaline soluble WS in the organic polymer below 80 ℃ at softening point based on " plastics performance brief guide " (Japan Plastics Industry Federation, all Japan plastics forming industrial combination can be write, the census of manufacturing can be issued, October 25 nineteen sixty-eight distribution).
In addition, be the organic polymer material more than 80 ℃ about softening point, through in this organic polymer material, adding the various plastifier that have compatibility with this polymer substance, also can the softening point of essence be dropped to 80 ℃ with the use of getting off.In addition, in order to regulate the bonding force with interim supporter, also can be in these organic polymer materials,, the softening point of essence adds various polymkeric substance or supercooling material, driving fit modifying agent or surfactant, release agent etc. in being no more than 80 ℃ scope.
As the concrete example of preferred plasticizer, can enumerate: polypropylene glycol, polyglycol, dioctyl phthalate, dibutyl phthalate (DHP), dibutyl phthalate, tricresyl phosphate, phosphate toluene diphenyl ester, phosphoric acid biphenyl diphenyl ester.
As the interim supporter in the above-mentioned photosensitive transfer printing material, can from chemically stable and interim supporter heat-staple and that constitute by flexible material, suitably select.Particularly, sheet material that preferred TEFLON (registered trademark), polyethylene terephthalate, polycarbonate, tygon, polypropylene, polyester etc. are thin or their layered product.As the thickness of said interim supporter, be suitably for 5～300 μ m, be preferably 20～150 μ m.This thickness has crackly tendency during less than 5 μ m when peeling off interim supporter, in addition, under the situation that interim supporter makes public, when surpassing 300 μ m, resolution has the tendency of reduction.In above-mentioned concrete example, preferred especially biaxial stretch-formed polyethylene terephthalate film.
(substrate)
Substrate (permanent support body) as constituting color filter of the present invention can use metallicity supporter, the gluing supporter of metal, glass, pottery, film of synthetic resin etc.Especially preferably be enumerated as good glass of the transparency and dimensional stability or film of synthetic resin.
(partition wall formation method)
Below, the example when using said photosensitive transfer printing material on substrate, to form partition wall describes.
Preparation is provided with oxygen barrier layer, coloring photosensitive combination layer and then on this coloring photosensitive combination layer, is provided with the photosensitive transfer printing material that covers with sheet material on interim supporter.
At first, peel off and remove covering with after the sheet material, the surface of the coloring photosensitive combination layer that will expose is fitted on the permanent support body (substrate), heats, pressurizes and carry out range upon range of (duplexer) through laminating machine etc.With regard to laminating machine, can use the laminating machine of from existing known laminating machine, vacuum laminator etc., suitably selecting, in order further to boost productivity, also can use automatic incised layer press.
Then, between interim supporter and oxygen barrier layer, peel off, remove interim supporter.
Then, above the face of removing after removing interim supporter, under the state that vertically erects desired photomask (for example quartzy exposed mask), suitably set the distance (for example 200 μ m) between exposed mask face and this oxygen barrier layer, and make public.
Then, after the exposure, use predetermined process liquid to carry out development treatment, obtain pattern and form image, continue to wash processing as required, obtain partition wall.
In addition; Use interim supporter as the situation that can block the protective seam of oxygen; State at residual interim supporter (not peeling off); And under the state that vertically erects desired photomask (for example quartzy exposed mask) above this interim supporter, suitably set the distance (for example 200 μ m) between exposed mask face and this interim supporter, and make public.
Then, remove interim supporter, use predetermined process liquid to carry out development treatment, obtain pattern and form image, continue to wash processing as required, obtain partition wall.
As the light source that is used for rayed (exposure), can enumerate: middle pressure～extra-high-pressure mercury vapour lamp, xenon lamp, metal halide lamp etc.Particularly, carry out,, can suitably select (300mJ/cm for example as exposure with the proximity printing machine (for example Hitachi's new and high technology electronic engineering Co., Ltd. system) that for example has extra-high-pressure mercury vapour lamp etc. 2).
In the present invention, preferably use said photosensitive composition to form the photo-sensitive resin of thickness 1.5～2.5 μ m, use proximity printing machine, under the anoxic atmosphere, with 40～300mJ/cm with extra-high-pressure mercury vapour lamp 2Carry out exposure-processed, more preferably form the photo-sensitive resin of thickness 1.7～2.5 μ m, with proximity printing machine, under the anoxic atmosphere, with 50～150mJ/cm with extra-high-pressure mercury vapour lamp 2Carry out exposure-processed.
After the exposure, use predetermined process liquid (developer solution) to carry out development treatment.As the developer solution that is used for development treatment,, also can be further to be added with the developer solution that the organic solvent of miscibility is arranged with glassware for drinking water on a small quantity though can use the dilute aqueous solution of alkaline matter.
In addition, before said development, preferably, make the surface of this coloring photosensitive combination layer wetting equably with spraying pure water such as spray spouts.
As alkaline matter contained in the treating fluid, can enumerate: alkali metal hydroxide (for example NaOH, potassium hydroxide), alkali carbonate class (for example sodium carbonate, sal tartari), alkali metal hydrogencarbonate class (for example soda mint, saleratus), alkali metal silicate salt (for example sodium silicate, potassium silicate), alkali metal silicate class (for example sodium metasilicate, potassium metasilicate), triethanolamine, diethanolamine, monoethanolamine, morpholine, tetra-alkyl ammonium hydroxide class (for example TMAH), tertiary sodium phosphate etc.
Preferred 0.01～30 quality % of the concentration of alkaline matter, pH preferred 8～14.
As said " organic solvent of miscibility being arranged ", for example preferably enumerate: methyl alcohol, ethanol, 2-propyl alcohol, 1-propyl alcohol, butanols, DAA, glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, benzylalcohol, acetone, methyl ethyl ketone, cyclohexanone, 6-caprolactone, gamma-butyrolacton, dimethyl formamide, dimethyl acetamide, hexamethyl phosphoramide, ethyl lactate, methyl lactate, epsilon-caprolactams, N-Methyl pyrrolidone etc. with glassware for drinking water.
With glassware for drinking water preferred 0.1～30 quality % of concentration of the organic solvent of miscibility is arranged in the treating fluid.
And, also can in treating fluid, add known surfactant, as this surfactant concentrations, preferred 0.01～10 quality %.
Said developer solution makes body lotion, and perhaps making spray liquid can use.
When removing the uncured portion of photo-sensitive resin, can be combined in the developer solution method of carrying out wiping etc. with rotating brush or wetting sponge.
In addition, the usually preferred room temperature of the fluid temperature of developer solution is neighbouring to 40 ℃.
With regard to development time, depend on the composition of photo-sensitive resin, the alkalescence or the temperature of developer solution, under the situation of adding organic solvent, depend on its kind and concentration etc., be generally 10 seconds～about 2 minutes.When it was too short, the development of non-sometimes exposure portion was insufficient, and when it was long, the portion of exposure sometimes also was etched.No matter under any situation, the partition wall shape is made all difficulties of suitable shape.
Also can after development treatment, get into washing step.
(back curing process)
In the present invention, preferably as above-mentioned, form after the partition wall, carry out further back cured the fixed in shapeization of partition wall.As method, limit the method that can be listed below not especially with the fixed in shapeization of partition wall.
1) after the development treatment, make public again (below, be sometimes referred to as " post-exposure ").
2) develop after, carrying out heat treated (below, be sometimes referred to as " afterwards curing ") under the lower temperature.
In the present invention, preferably carry out post-exposure and after at least one side of curing, more preferably carry out both successively.
At this, under the situation of carrying out said post-exposure, with regard to its exposure, as long as, then be 500～8000mJ/cm under the atmosphere 2, be preferably 1000～5000mJ/cm 2, be under the situation under the anoxic atmosphere, also can be to make public than its low exposure.In addition, said post-exposure both can be from having carried out with the opposing face side with opposed of said transparency carrier of said photo-sensitive resin, also can also further carry out from the two sides from the carrying out with opposed side of said transparency carrier of said photo-sensitive resin.
In addition, said heat treated is meant the substrate that is formed with partition wall is heated in electric stove, exsiccator etc. or shines infrared lamp.With regard to heating-up temperature, preferably heated 10 minutes～120 minutes down at 120～250 ℃.
Can be through temperature being set at more than 120 ℃ and carry out the curing of partition wall effectively, and give sufficient solvent resistance, alkali resistance.
(water-proofing treatment)
In the present invention, the state that preferably has water proofing property through at least a portion that the partition wall enforcement water-proofing treatment that as above-mentioned, forms is set at this partition wall.Thus, when giving the drop of pigmented fluids composition with ink-jet etc. between to this partition wall thereafter, can suppress that printing ink is crossed this partition wall and with adjacent undesirable conditions such as color colour mixture.
As water-proofing treatment, can enumerate: on partition wall the coating waterproof material method, reset water barrier method, utilize the plasma treatment imparting water repellency method, with water-repellent material mix partition wall method, utilize the method for photocatalyst imparting water repellency etc.
Before or after this water-proofing treatment,, can implement oxygen ashing oleophylics such as (ashing) China ink and handle in order to improve the moistening extendability of the printing ink in the black matrix" peristome on the supporter.
In addition, about the details of water-proofing treatment, can be in the present invention the also item of record in the advantageous applications TOHKEMY 2006-154804 communique etc.
(formation of pixel)
Then, with respect to the recess between the partition wall that forms by above-mentioned developing procedure, give the pigmented fluids that is used to form each pixel of RGB composition.As giving the pigmented fluids method for compositions to the partition wall space, can use known method such as ink-jet method or stripe G ü sser rubbing method, consider preferred ink-jet method from the throughput rate aspect.About ink-jet method, state after carrying out.
Give the pigmented fluids composition to the recess between partition wall and form dyed layer.This dyed layer becomes the yellow (Y) that constitutes color filter, red (R), green (G), blue colored pixels such as (B).
With regard to the formation of dyed layer, can be to as stating, being given the jetted ink that is used to form colored pixels (the for example pattern of pixels of YRGB four looks), formed with the mode that constitutes by a plurality of pixels more than two looks at the recess of the partition wall that forms on substrate encirclement.
About the shape of color filter pattern, not special the qualification can be the general striated as the black matrix" shape, also can be clathrate, can also arrange shape for triangular form.
Said pigmented fluids composition can utilize makes the pigmented fluids composition carry out the method for heat curing or photocuring, after forming transparent development layer on the substrate, give known method such as pigmented fluids method for compositions in advance makes dyed layer.
In the present invention, preferably be provided with and give the pigmented fluids composition to the recess between partition wall and form the heating process of carrying out heat treated (so-called cure processing) after each pixel.That is, the substrate of giving painted fluid composition is heated in electric stove, exsiccator etc. or use the infra-red light irradiation infrared ray.
The temperature and time of heating depends on the composition of pigmented fluids composition and the thickness of formed layer; Generally speaking; Consider from the viewpoint that obtains sufficient solvent resistance, alkali resistance and ultraviolet absorbance, preferably heated about 10 minutes～about 120 minutes down at about 120 ℃～about 250 ℃.
(ink-jet method)
As being used for ink-jet method of the present invention, can adopting spraying continuously charged printing ink and the method for controlling by electric field, using the piezoelectric element method, the whole bag of tricks such as method that printing ink is heated and utilizes its foaming to spray off and on of ink jet off and on.
With regard to the printing ink that uses, no matter be oiliness, water-based, can use.
In addition, colouring matter contained in this printing ink can use with dyestuff, pigment simultaneously, considers from the permanance aspect, more preferably uses pigment.
In addition, composition is used in the ink-jet that also can use the coloring printing ink that is used for the coating method that known color filter makes (colored resin composition, for example be recorded in TOHKEMY 2005-3861 communique [0034]～[0063]) or japanese kokai publication hei 10-195358 communique [0009]～[0026] to put down in writing.
Consider the operation after painted, also can add composition that be cured through heating or that utilize ultraviolet homenergic ray to be cured in the printing ink in the present invention.
As the composition that is cured through heating, can especially restrictedly not use various heat-curing resins.In the present invention, except that heat-curing resin, also can use contain at least bonding agent and 2 officials can or 3 officials can the color filter that contains the epoxy radicals monomer with Thermocurable printing ink as preferred material.
In addition, as the composition that utilizes energy-ray to be cured, can illustration for example in acrylate derivative or methacrylate derivative, be added with the material of photoreaction initiator.Particularly consider thermotolerance, more preferably have the material of a plurality of acryloyl groups, methacryl in the molecule.These acrylate derivatives, methacrylate derivative can preferably be used water miscible material.In addition, even be the material of slightly solubility in water, also can carry out latexization etc. and use.At this moment, can be with the photosensitive composition that contains the colorants of in the item of above-mentioned photosensitive composition, enumerating such as pigment as preferred material.
Color filter among the present invention is preferably the color filter that forms pixel with ink-jetting style, preferably gives the printing ink of RGB three looks and forms the color filter of three looks.
Combination such as this color filter and liquid crystal display cells, electrophoretic display device, electro-luminescent display unit, PLZT is used as display element.
In addition, also can be used for using the purposes of color camera or other color filter.
(overlayer)
After the making of color filter,, overlayer can also be set in order on whole of color filter, to improve patience.Though overlayer can be protected the cured layer of each pixel (for example, R, G, B), makes the surface for smooth simultaneously, considers from the viewpoint that process number increases, and preferably is not provided with.
As forming tectal resin (OC agent), can enumerate acrylic resin composition, composition epoxy resin, polyimide resin composition etc.
Wherein, because the transparency in the visible region is excellent, it is excellent as principal ingredient and adaptation with acrylic resin usually that color filter uses the resinous principle of Photocurable composition in addition, so preferred acrylic resin composition.
As tectal instance, can enumerate overlayer, commercially available article, the JSR society system " オ プ ト マ one SS6699G " put down in writing in the paragraph numbering 0018～0028 of TOHKEMY 2003-287618 communique) as coverture.
[display device]
As display device of the present invention, be meant display device such as liquid crystal indicator, plasma scope display device, EL display device, CRT display device etc.
The definition of display device and the explanation of each display device for example are recorded in " electronic console equipment (the clear husband's work of assistant 々 wood, (strain) census of manufacturing can be issued nineteen ninety) ", " display apparatus (she blows along chapter work, industry books (strain) and puts down into distribution in the first year) " etc.
In the display device of the present invention, preferred especially liquid crystal indicator.About liquid crystal indicator, for example be recorded in " LCD Technology of future generation (Uchida Tatsuo compiles, (strain) census of manufacturing can 1994 distribution) ".
For using the not special restriction of liquid crystal indicator of the present invention, the liquid crystal indicator of the variety of way that can be applied to be put down in writing in for example above-mentioned " LCD Technology of future generation ".
Wherein, the present invention is effective to the liquid crystal indicator of colored TFT mode especially.About the liquid crystal indicator of colored TFT mode, for example be recorded in " colored TFT LCD (upright publication (strain) distribution in 1996 altogether) ".
And the present invention can certainly be applied in the liquid crystal indicator that field angle such as pixel partitioning scheme such as transverse electric field type of drive, MVA such as IPS have carried out amplifying.About these modes, for example be recorded in " the up-to-date trend in EL, PDP, LCD display-technology and market-(Toray research centre investigation department calendar year 2001 distribution) " 43 pages.
Except that color filter, liquid crystal indicator is made up of various members such as electrode base board, polarizing coating, phase retardation film, backlight, dividing plate, field angle guarantee films.In the liquid crystal indicator that color filter of the present invention can be applied to be made up of these known members.About these members, for example be recorded in the market (island Itou Kentaro (strain) CMC 1994 distribution) of " ' 94 LCD periphery materials, chemistry ", " present situation of 2003 liquid crystal relevant markets with prospect (last volume) (good lucky (strain) Kai Meilai of Fuji of table combines and grinds distribution in 2003) " in the future.
[object purposes]
Color filter of the present invention can especially restrictedly not be applied in the purposes such as portable end such as televisor, notebook computer, liquid crystal projection apparatus, game machine, portable phone, digital camera, navigational system.
Japanese publication 2009-224959 number openly it is fully incorporated in this instructions.
With regard to whole documents, patented claim and the technical specification put down in writing in this instructions, each document, patented claim and technical specification be through with reference to being introduced into, with concrete and situation each record with degree ground, through with reference to being introduced in this instructions.
Embodiment
Below, enumerate embodiment the present invention further is described particularly.Below embodiment shown in material, reagent, ratio, equipment, operation etc., only otherwise break away from spirit of the present invention, can suitably change.Therefore, scope of the present invention is not limited to the concrete example shown in following.
Need to prove, in following embodiment, short of specified otherwise, " % " reaches " part " expression " quality % " and reaches " mass parts ", and molecular weight is represented weight-average molecular weight.
< embodiment 1 >
[preparation of photosensitive composition]
(preparation of K pigment dispersing thing 1)
Mode with the composition that becomes following K pigment dispersing thing 1 is mixed carbon black, spreading agent, polymkeric substance and solvent, uses 3 rollers mill and ball mill to obtain K pigment dispersing thing 1.
Black combination K1 (photosensitive composition) obtains through following method; At first, measure K pigment dispersing thing 1, the propylene glycol monomethyl ether acetate (MMPGAc) of the amount of record in the table 1, under 24 ℃ of temperature (± 2 ℃), mix; Stirred 10 minutes with 150RPM; Then, measure methyl ethyl ketone, cyclohexanone, bonding agent 2, phenothiazine, monomer liquid 1, polymerization initiator 1, the surfactant 1 of the amount of record in the table 1, under 25 ℃ of temperature (± 2 ℃), add successively; Under 24 ℃ of temperature (± 2 ℃), stirred 30 minutes with 150RPM.
Need to prove that the amount of record is the umber of quality criteria in the table 1.In addition, each composition is following composition in detail.
(K pigment dispersing thing 1)
Carbon black (goldschmidt chemical corporation system Nipex35): 13.1%
Following spreading agent 1: 0.65%
Polymkeric substance: 6.72%
(random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, molecular weight 3.7 ten thousand)
Propylene glycol monomethyl ether acetate: 79.53%
[changing 1]
Figure BDA0000147800430000221
(bonding agent 2)
Polymkeric substance: 27%
(random copolymers of benzyl methacrylate/methacrylic acid=78/22 mol ratio, molecular weight 3.8 ten thousand)
Propylene glycol monomethyl ether acetate: 73%
(monomer liquid 1)
Tetramethylol methane tetraacrylate: 75%
(NK ESTER A-TMMT, Xin Zhong village chemical industry system)
Methyl ethyl ketone: 25%
(polymerization initiator 1)
2, two (the trichloromethyl)-6-of 4-[4 '-(N, amino-the 3 '-bromophenyl of N-two (ethoxy carbonyl methyl)]-the s-triazine
：100％
(surfactant 1)
Trade name: MEGAFACE F-780F (big Japanese ink system)
Following works 1: 30%
Methyl ethyl ketone: 70%
[changing 2]
Figure BDA0000147800430000231
After alkali-free glass substrate cleaned in the UV cleaning device, use clean-out system to carry out hairbrush and clean, further carry out ultrasonic cleaning with ultrapure water.Substrate 120 ℃ of following thermal treatments 3 minutes, is made the surface state stabilization.With after substrate cooling and the temperature adjustment to 23 ℃, with glass substrate with slit-shaped nozzle with coating machine (FAS Japanese firm system, trade name: MH-1600) be coated with by the above-mentioned black combination K1 that obtains.Then; With dry 30 seconds of the part of solvent, make the flowability forfeiture of coating layer, thereafter with VCD (the chemical industry corporate system is answered in Minton dryer, Tokyo); Remove substrate unwanted coating fluid on every side with EBR (Edge bead removal: the edge photoresist is removed); 120 ℃ of following prebake 3 minutes, obtain black-colored photosensitive resin bed (below, be sometimes referred to as " black photosensitive the layer ") K1 of thickness 2.33 μ m, optical density (OD) 4.0.
With proximity printing machine (new and high technology electronic engineering Co., Ltd. of Hitachi system) with extra-high-pressure mercury vapour lamp; Under the state that vertically erects substrate and mask (quartzy exposed mask) with picture pattern; With the distance setting between exposed mask face and the black photosensitive layer K1 is 200 μ m; Under nitrogen atmosphere, from black photosensitive layer K1 side with exposure 300mJ/cm 2Carry out pattern exposure.
Then; With the spray spout pure water of spraying, make the surface of black photosensitive layer K1 wetting equably after, using KOH is the liquid of developer solution (KOH, contain non-ionic surfactant, trade name: CDK-1, Fujiphoto electronic material (strain) system) 100 times of gained of dilution; Under 23 ℃, developed 80 seconds with flat plate nozzles pressure 0.04MPa spray; Further use the pressure injection ultrapure water of UHV (ultra-high voltage) washer jet, carry out residue and remove, obtain pattern and form image with 9.8MPa.
With regard to regard to the pattern line-width (W1) of mask linewidths 12.0 μ m (W2), the result who measures with small live width determinator (CP-30:Soft works system) is 13.7 μ m.
In addition, the thickness d2 that measures with contact pin type film thickness gauge (P-10:Tencor Instrument system) is 2.33 μ m.
Then, under atmosphere, from with opposed opposing face side of substrate of said black photosensitive layer K1 and with the two sides of opposed the side of substrate of said black photosensitive layer K1 with exposure 2500mJ/cm 2Carry out post-exposure, further carry out under 240 ℃ 50 minutes after cure processing, obtain being formed with the substrate of the partition wall of optical density (OD) 3.9, thickness (d2) 2.0 μ m.
On the other hand; After the above-mentioned black photosensitive layer K1 that likewise forms 2.33 μ m; From substrate-side to be exposed to the mode fixing base of black photosensitive layer K1, in addition, with above-mentioned likewise make public, develop after; The pattern of measuring gained forms the thickness d1 of image, and its result is 0.71 μ m.
Learn W1/W2=1.14, d1/d2=0.305 by above.
[utilizing the preventing hydration of rubbing method to handle]
Add in will be in advance on being formed with that fluorine is arranged is that the soluble photoresist of alkali (Hekist Japanese firm system, positive light anti-etching agent AZP4210) of surfactant (Sumitomo 3M corporate system, Florado FC-430) 0.5% (with respect to the solid constituent of photoresist) is that the mode of 2 μ m uses the slit-shaped nozzle to be coated with thickness, in the warm braw circulation dryer, under 90 ℃, carry out 30 minutes thermal treatment by the substrate of the above-mentioned partition wall that obtains.Then, with 110mJ/cm 2(38mW/cm 2* 2.9 seconds) exposure make public across substrate and partition wall from the back side (not forming the face of partition wall) of the substrate that is formed with partition wall.After dipping shakes 80 seconds in inorganic base developer solution (Hekist Japan society system, AZ400K Developer, 1:4), in pure water, carry out flushing in 30～60 seconds and handle.Then, on partition wall, form the waterproof resin layer.Thus, inside and outside pixel (be separated wall surround recess and partition wall) that surface energy is set is poor.
With regard to the surface energy inside and outside the pixel after the waterproof resin layer forms, pixel outer (on the resin bed) is 10～15dyne/cm, and (on the glass substrate, be separated the recess that wall surrounds) is for about 55dyne/cm in the pixel.
[pixel is used the pigmented fluids preparation of compositions]
In following compositions, at first, pigment, macromolecule dispersing agent and solvent are mixed with the mode that becomes following composition, use 3 rollers mill and ball mill to obtain dispersible pigment dispersion.On one side this dispersible pigment dispersion is fully stirred with high speed dispersor etc., on one side each a small amount of other material that adds, red (R) pixel of preparation is with pigmented fluids composition (below, be sometimes referred to as " pixel is used colored ink compositions ").
< red pixel is with the composition of pigmented fluids composition >
Pigment (C.I. paratonere 254): 5 parts
Macromolecule dispersing agent (AVECIA corporate system Solsperse 24000): 1 part
Bonding agent (GMA-styrol copolymer): 3 parts
First epoxy resin: 2 parts
(phenolic resin varnish type epoxy resin, oiling shell corporate system Epikote 154)
Second epoxy resin: 5 parts
(neopentylglycol diglycidyl ether)
Hardening agent (trimellitic acid): 4 parts
Solvent: 3-ethoxyl ethyl propionate: 80 parts
In addition, replace the C.I. paratonere 254 in the above-mentioned composition, use the C.I. pigment green 36 with amount, in addition, likewise operate with the situation of colored ink compositions with red pixel, green (G) pixel of preparation is used colored ink compositions.
And, replace the C.I. paratonere 254 in the above-mentioned composition, use C.I. pigment blue 15 with amount: 6, in addition, likewise to operate with the situation of colored ink compositions with red pixel, blue (B) pixel of preparation is used colored ink compositions.
Then; Use R, the G of above-mentioned record, the pixel of B to use colored ink compositions; In using the zone of distinguishing by the partition wall of the above-mentioned filter substrate that obtains (by the recess of protuberance encirclement); Use the pen recorder of ink-jetting style to carry out the ejection of ink composite,, make the color filter that the pattern by R, G, B constitutes until becoming desired concentration.Color filter with image after painted cured 60 minutes in 240 ℃ of baking boxs, thus, made black matrix", the equal full solidification of each pixel.
As following, the picture element flaw in the color filter of gained is estimated.Amount to 3 pixels for each 1 pixel and be made as 1 and paint plain 2500 and paint element the RGB of color filter, utilize observation by light microscope to have or not to ooze out, overflow, with the defectives such as colour mixture of adjacent pixels, calculate the defective number of picture elements, estimate according to following metewand.The result is shown in table 1.
～metewand～
A: 0～2 of number of defects
B: 3～5 of numbers of defects
C: 6～10 of numbers of defects
D: 11～25 of numbers of defects
E: number of defects is more than 26
On R pixel, G pixel and B pixel and the black matrix" by the above-mentioned filter substrate that obtains, further form the transparency electrode of ITO (Indium Tin Oxide) through sputter.In addition, prepare glass substrate, forming with implementing pattern with the PVA pattern respectively on the transparency electrode of filter substrate and on the counter substrate as counter substrate.Measure ITO resistance (Mitsubishi Chemical's (strain) system " RORESTA " of this color filter; Measure sheet resistance with four probe method), the result shows the low-down value of 12 Ω/.
Part on the top that is equivalent to the partition wall on the transparency electrode of said ITO is provided with light clapboard, and the alignment films that is made up of polyimide further is set above that.Thereafter, the sealant of the position printing epoxy resin that is equivalent to the black matrix" housing around the mode with the pixel groups of surrounding color filter is arranged at, simultaneously; Drip the PVA pattern and use liquid crystal; After the counter substrate applying, the substrate that will be fitted is heat-treated, and makes sealant cures.Paste the polaroid HLC2-2518 of (strain) SANRITZ system on the two sides of the liquid crystal cells that obtains like this.Then, constitute the backlight of cold-cathode tube, and be configured in side, constituted liquid crystal indicator as the back side of the liquid crystal cells that is provided with said polaroid.The brightness of the liquid crystal indicator of gained is also no problem, and display characteristic is excellent.
To the liquid crystal indicator of gained, use chroma-luminance meter BM-5A (opening up general health corporate system) to measure its brightness (Y), according to following metewand brightness is estimated.
～metewand～
A:875cd/m 2More than
More than the B:850 and less than 875cd/m 2
More than the C:825 and less than 850cd/m 2
More than the D:800 and less than 825cd/m 2
E: less than 800cd/m 2
< embodiment 2 >
[preparation of black-colored photosensitive transfer materials K1]
On the interim supporter of pet film of thickness 75 μ m, use thermoplastic resin that the coating of slit-shaped nozzle is made up of following prescription H1 with coating fluid and make its drying.Then, the middle layer that is made up of following prescription P1 of coating is with coating fluid and make its drying.Further be coated with said black combination K1 and make its drying.Like this; Thermoplastic resin that dry film thickness is 15.1 μ m, middle layer that dry film thickness is 1.6 μ m are set on interim supporter and become 4.0 mode the black photosensitive layer that dry film thickness is 2.2 μ m is set with optical density (OD); At last, crimping diaphragm (thickness 12 μ m polypropylene films).Make the transfer materials that the black photosensitive layer of interim supporter, thermoplastic resin, middle layer (oxygen barrier film) and black (K) becomes one like this, the sample name is set at black-colored photosensitive transfer materials K1.
(thermoplastic resin is used coating fluid: prescription H1)
Methyl alcohol: 11.1 parts
Propylene glycol monomethyl ether acetate: 6.36 parts
Methyl ethyl ketone: 52.4 parts
Methyl methacrylate/acrylic acid-2-ethyl caproite/benzyl methacrylate/methacrylic acid copolymer (copolymerization ratio of components (mol ratio)=55/11.7/4.5/28.8, molecular weight=100,000, Tg70 ℃): 5.83 parts
Styrene/acrylic acid co-polymer (100 ℃ of copolymerization ratio of componentss (mol ratio)=63/37, mean molecular weight=10,000, Tg ≈): 13.6 parts
2, two [4-(methacryloxy polyethoxy) phenyl] propane (Xin Zhong village chemical industry (strain) system) of 2-5: 9.1 parts
Fluorine based polymer: 0.54 part
(C 6F 13CH 2CH 2OCOCH=CH 240 parts and H (OCH (CH 2) CH 2) 7OCOCH=CH 255 parts and H (OCH 2CH 2) 7OCOCH=CH 25 parts multipolymer, mean molecular weight 30,000, methyl ethyl ketone 30% solution, big Japanese ink chemical industry system, trade name: Mega face F780F)
(coating fluid is used in the middle layer: prescription P1)
PVA205: 32.2 parts
(polyvinyl alcohol (PVA), (strain) Kuraray system, saponification degree=88%, the degree of polymerization 550)
Polyvinyl pyrrolidone: 14.9 parts
(ISP, Japanese firm's system, K-30)
Distilled water: 524 parts
Methyl alcohol: 429 parts
The glass cleaner liquid 20 seconds be adjusted into 25 ℃ is sprayed on the limit through spray; Alkali-free glass substrate is cleaned with the rotating brush with nylon hair in the limit; After the pure water spray Cleaning for High Capacity; Spray silane coupling solution (N-β (amino-ethyl) gamma-amino propyl trimethoxy silicane 0.3% WS, trade name: KBM603, SHIN-ETSU HANTOTAI's chemical industry (strain) system) 20 seconds through spray, carry out the pure water spray Cleaning for High Capacity.This substrate was heated 2 minutes down at 100 ℃ with the substrate preheating apparatus.On the silane coupled processing glass substrate of gained, remove coverlay from the black-colored photosensitive transfer materials K1 that makes with above-mentioned method for making; The back is overlapping with the surperficial contacted mode of the surface of the black photosensitive layer that exposes and said silane coupled processing glass substrate removing; Use laminating machine (Co., Ltd. Hitachi's industry system (LamicII type)); At above-mentioned 100 ℃ down on 2 minutes the substrate of heating, under 130 ℃ of rubber rollers temperature, carried out range upon range of with line pressure 100N/cm, transporting velocity 2.2m/ minute.Then, with the interface of thermoplastic resin on peel off the interim supporter of polyethylene terephthalate, remove interim supporter.Peel off after the interim supporter; With proximity printing machine (new and high technology electronic engineering Co., Ltd. of Hitachi system) with extra-high-pressure mercury vapour lamp; Under the state that vertically erects substrate and mask (quartzy exposed mask) with picture pattern; With the distance setting between exposed mask face and this black-colored photosensitive resin composition layer is 200 μ m, with exposure 70mJ/cm 2Carry out pattern exposure.
Then; With triethanolamine is that developer solution (will contain triethanolamine 30%, trade name: T-PD2 (Fuji Photo Film Co., Ltd.'s system) is diluted to 12 times (with mixed of 11 parts of T-PD21 part and pure water) with pure water liquid) sprays with flat plate nozzles pressure 0.1MPa under 30 ℃ and developed 20 seconds, removes thermoplastic resin and middle layer.Then, this above glass substrate injection air and carry out mangle after, sprayed pure water 10 seconds through spray, carry out the pure water spray Cleaning for High Capacity, injection air reduces the liquid holdup on the substrate.
Thereafter; Use is developer solution (trade name: T-CD1 (Fuji Photo Film Co., Ltd.'s system) being diluted to the liquid of 5 times (with 1 part of T-CD1 mixed with 4 parts of pure water) with pure water) with sodium carbonate/bicarbonate; Under 30 ℃, will spray pressure and be set at 0.1MPa, develop 30 seconds, clean with pure water.
Then; Use contains surfactant washing liquid (trade name: T-SD3 (Fuji Photo Film Co., Ltd.'s system) is diluted to 10 times liquid with pure water); Under 33 ℃, sprayed 20 seconds through spray with circular cone type nozzle pressure 0.1MPa; Further utilize the formed pattern image of rotating brush wiping, carry out residue and remove with soft nylon hair.And, with the pressure injection ultrapure water of UHV (ultra-high voltage) washer jet, carry out residue and remove with 9.8MPa, obtain desired black matrix".
With regard to regard to the pattern line-width (W1) of mask linewidths 12.0 μ m (W2), the result who measures with small live width determinator (CP-30:Soft works system) is 13.3 μ m.
In addition, the thickness d2 that measures with contact pin type film thickness gauge (P-10:Tencor Instrument system) is 2.33 μ m.
Then, under atmosphere with exposure 2000mJ/cm 2Carry out post-exposure, further carry out under 240 ℃ 50 minutes after cure processing, obtain being formed with the substrate of the partition wall of optical density (OD) 3.9, thickness 2.0 μ m.
On the other hand; After the above-mentioned black photosensitive layer K1 that likewise forms 2.33 μ m; From substrate-side to be exposed to the mode fixing base of black photosensitive layer K1, in addition, with above-mentioned likewise make public, develop after; The pattern of measuring gained forms the thickness d1 of image, and its result is 0.71 μ m.
[processing of plasma preventing hydration]
Be formed with on the substrate of partition wall, using negative electrode coupling scheme parallel plate-type plasma processing apparatus, under following condition, carrying out the plasma preventing hydration and handle.
Using gases: CF 4Gas, flow: 80sccm, pressure: 40Pa, RF power: 50W, processing time: 30sec
Be formed with the substrate of the partition wall that as above, obtains except that using; Likewise operate with embodiment 1, form after R, G, the B pixel, this color filter was cured in 240 ℃ baking oven 60 minutes with ink-jetting style; Thus, make black matrix", the equal full solidification of each pixel.
The color filter that obtains is like this carried out microscopic examination, the result, the printing ink that constitutes each pixel closely is accommodated in the partition wall gap, do not see ooze out, overflow, with the colour mixture of adjacent pixels and leak and white etc. become the bad of defective, can obtain good color filter.In addition, likewise operate, the picture element flaw of color filter is estimated with embodiment 1.
And, likewise operate with embodiment 1, on R pixel, G pixel and B pixel and black matrix", form the transparency electrode of ITO, the alignment films that light clapboard is set, constitutes by polyimide.Thereafter, the printing and sealing agent also drips liquid crystal, fits with counter substrate and heat-treats, and makes liquid crystal cells, pastes polaroid on the two sides, constitutes backlight, has constituted liquid crystal indicator.The brightness of the liquid crystal indicator of gained is also no problem, and display characteristic is excellent.
In addition, to the liquid crystal indicator of gained, likewise brightness is estimated with embodiment 1.
< embodiment 3～6 >
In embodiment 2, replace black combination K1, prepare black combination K3～K6 respectively with the mode of the composition of record among the embodiment 3～6 that becomes table 1.Use said composition, likewise operate, make black transfer materials K3～K6 respectively, use this black transfer materials, in addition, likewise operate, on substrate, form partition wall, obtain separately W1, d1, d2 simultaneously with embodiment 2 with embodiment 2.
And, use by the above-mentioned substrate that obtains, in addition, likewise make color filter with embodiment 2, continue to make liquid crystal indicator.
The evaluation result of the picture element flaw of the color filter that will likewise estimate with embodiment 1, the brightness of liquid crystal indicator is shown in Table 1 simultaneously.
< embodiment 7,8 >
In embodiment 6, the exposure 70mJ/cm when replacing partition wall to make 2, exposure is set at 40mJ/cm 2, 150mJ/cm 2In addition, likewise operate, on substrate, form partition wall, obtain separately W1, d1, d2 simultaneously with embodiment 6.
And, use by the above-mentioned substrate that obtains, in addition, likewise make color filter with embodiment 6, then make liquid crystal indicator.
The evaluation result of the picture element flaw of the color filter that will likewise estimate with embodiment 1, the brightness of liquid crystal indicator is shown in Table 1 simultaneously.
< embodiment 9～11 >
In embodiment 2, replace black combination K1, prepare black combination K9～K11 respectively with the mode of the composition of record among the embodiment 9～11 that becomes table 1.Use said composition, likewise operate, make black transfer materials K9～K11 respectively, use this black transfer materials, in addition, likewise operate, on substrate, form partition wall, obtain separately W1, d1, d2 simultaneously with embodiment 2 with embodiment 2.
And, use by the above-mentioned substrate that obtains, in addition, likewise make color filter with embodiment 2, then make liquid crystal indicator.
The evaluation result of the picture element flaw of the color filter that will likewise estimate with embodiment 1, the brightness of liquid crystal indicator is shown in Table 1 simultaneously.
In addition, with regard to the R pigment dispersing thing 1 in the table 1, pigment, polymkeric substance and solvent are mixed, use 3 rollers mill and ball mill to obtain R pigment dispersing thing 1 with the mode that becomes following composition.
< composition of R pigment dispersing thing 1 >
Pigment (C.I. paratonere 177): 18%
Polymkeric substance: 12%
(random copolymers of benzyl methacrylate/methacrylic acid=72/28 mol ratio, molecular weight 3.7 ten thousand)
Propylene glycol monomethyl ether acetate: 70%
< comparative example 1 >
The black combination K1 that replaces embodiment 2 prepares black combination K21 with the mode of the composition of record in the comparative example 1 that becomes table 1.Use said composition, likewise make black transfer materials K21 with embodiment 2.
Exposure 70mJ/cm when the partition wall of replacement embodiment 2 is made 2, exposure is set at 150mJ/cm 2, in addition, likewise operate with embodiment 2, on substrate, form partition wall, obtain W1, d1, d2 simultaneously.
And, use by the above-mentioned substrate that obtains, in addition, likewise make color filter with embodiment 2, then make liquid crystal indicator.
The evaluation result of the picture element flaw of the color filter that will likewise estimate with embodiment 1, the brightness of liquid crystal indicator is shown in Table 1 simultaneously.
< comparative example 2 >
Use the black combination K21 in the comparative example 1, the exposure 150mJ/cm the when partition wall of replacement comparative example 1 is made 2, exposure is set at 400mJ/cm 2, in addition, likewise operate with comparative example 1, on substrate, form partition wall, obtain W1, d1, d2 simultaneously.
And, use by the above-mentioned substrate that obtains, in addition, likewise make color filter with embodiment 2, then make liquid crystal indicator.
The evaluation result of the picture element flaw of the color filter that will likewise estimate with embodiment 1, the brightness of liquid crystal indicator is shown in Table 1 simultaneously.
< comparative example 3,4 >
In comparative example 1, replace black combination K21, prepare black combination K23, K24 respectively with the mode of the composition of record in the comparative example 3,4 that becomes table 1.Use said composition, likewise operate, make black transfer materials K23, K24, likewise operate, on substrate, form partition wall, obtain W1, d1, d2 simultaneously with comparative example 1 with comparative example 1.
And, use by the above-mentioned substrate that obtains, in addition, likewise make color filter with embodiment 2, then make liquid crystal indicator.
The evaluation result of the picture element flaw of the color filter that will likewise estimate with embodiment 1, the brightness of liquid crystal indicator is shown in Table 1 simultaneously.
[table 1]
In the table 1, MMPGAc representes propylene glycol monomethyl ether acetate.
Monomer liquid 2 is the propylene glycol monomethyl ether acetate solution (76%) of DPHA (dipentaerythritol acrylate, Japanese chemical drug (strain) system).
Polymerization initiator 2 expression Irgacure 819 (vapour crust Japanese firm system), polymerization initiator 3 expression Irgacure 379 (vapour crust Japanese firm system), polymerization initiator 4 expression Irgacure OXE01 (vapour crust Japanese firm system).
In addition, adjuvant 1 is meant NBCA (10-normal-butyl-2-chloro-acridine ketone, dark fund change into corporate system), and adjuvant 2 is meant EAB-F (photopolymerization causes auxiliary agent, hodogaya chemical industry (strain) system)).
Through as above, using photosensitive composition of the present invention, can positional precision form the pixel that does not have colour mixture etc. well, and make color filter, liquid crystal indicator expeditiously.

Claims (11)

1. photosensitive composition, it comprises colorant, the alkali soluble resin of the colorant that contains black, the polymerizable compound with 3 above polymerizable groups, polymerization initiator or polymerization initiation system and solvent, wherein,
On transparency carrier, become 4.0 mode and form the photo-sensitive resin that contains said photosensitive composition with optical density (OD),
From with said photo-sensitive resin with opposed opposite face side of said transparency carrier; Across mask to said photo-sensitive resin make public, development treatment and the live width at the 1st pattern that forms is W1; And the thickness that becomes said the 1st pattern that obtains under the exposure, development conditions of 0.7～1.5 scope at the live width W1 of the 1st pattern with respect to the ratio W1/W2 of the live width W2 of said mask is d2
From said photo-sensitive resin with opposed side of said transparency carrier; Become at said W1/W2 across mask and said transparency carrier under the exposure, development conditions of 0.7～1.5 scope to said photo-sensitive resin make public, development treatment and the thickness of the 2nd pattern that obtains is d1, d1 is more than 0.3 with the ratio of d2.
2. photosensitive composition as claimed in claim 1, wherein, the exposure, the said d1/d2 under the development conditions that become 0.8～1.2 scope at said W1/W2 are 0.3～0.7 scope.
3. like claim 1 or the described photosensitive composition of claim 2, wherein, said colorant contains carbon black at least.
4. like each described photosensitive composition in claim 1～claim 3, wherein, said polymerization initiator or polymerization initiation system contain at least a kind of acylphosphine oxide series initiators.
5. like each described photosensitive composition in claim 1～claim 4, wherein, said polymerizable compound with 3 above polymerizable groups be 3 officials can acrylic monomers and 4 officials can acrylic monomers at least a kind.
6. photosensitive transfer printing material, its photo-sensitive resin that is formed by each described photosensitive composition in claim 1～claim 5 are arranged on the interim supporter and constitute.
7. color filter, it has substrate and uses each described photosensitive composition in claim 1～claim 5 and form and be configured in the light shielding part on the said substrate.
8. color filter as claimed in claim 7, wherein, said light shielding part is to use the described photosensitive transfer printing material of claim 6 to form.
9. like claim 7 or the described color filter of claim 8, wherein, the optical density (OD) of said light shielding part is more than 3.5.
10. like each described color filter in claim 7～claim 9, wherein, the thickness of said light shielding part is more than the 1.5 μ m.
11. a liquid crystal indicator, it has each described color filter in claim 7～claim 10.
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