CN101680984B - Curable composition for color filter, method for producing curable composition for color filter, colored curable resin composition, method for forming colored pattern, colored pattern, method for prod - Google Patents
Curable composition for color filter, method for producing curable composition for color filter, colored curable resin composition, method for forming colored pattern, colored pattern, method for prod Download PDFInfo
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- CN101680984B CN101680984B CN2008800184671A CN200880018467A CN101680984B CN 101680984 B CN101680984 B CN 101680984B CN 2008800184671 A CN2008800184671 A CN 2008800184671A CN 200880018467 A CN200880018467 A CN 200880018467A CN 101680984 B CN101680984 B CN 101680984B
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- 0 CCCC(C)C1[C@](C)*C(C2)C2(C)C1C Chemical compound CCCC(C)C1[C@](C)*C(C2)C2(C)C1C 0.000 description 7
- VIIYPNFCLFKWAI-UHFFFAOYSA-N C=CC(C1C(CC(N)=O)C1)=O Chemical compound C=CC(C1C(CC(N)=O)C1)=O VIIYPNFCLFKWAI-UHFFFAOYSA-N 0.000 description 1
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/201—Filters in the form of arrays
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on liquid crystals, e.g. single liquid crystal display cells
- 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
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
- G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/038—Macromolecular compounds which are rendered insoluble or differentially wettable
- G03F7/0388—Macromolecular compounds which are rendered insoluble or differentially wettable with ethylenic or acetylenic bands in the side chains of the photopolymer
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
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- 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
Abstract
Disclosed is a colored curable composition for color filters, which contains (1) at least one alkali-soluble resin selected from (meth)acrylic copolymers having an alicyclic (meth)acryloyl group in a side chain and copolymers having 0.001-0.20 eq/g of a (meth)acryloyl group and an acid value of 10-150, (2) a photopolymerization initiator, (3) a polymerizable monomer or oligomer having a partial structure selected from a urethane, an amide and a urea, and an ethylenically unsaturated double bond, and (4) a coloring agent. Also disclosed is a colored curable resin composition containing (a) a coloring agent, (b) a compound having at least one ethylenically unsaturated double bond, (c) a binder resin containing a (meth)acrylic copolymer having an alicyclic (meth)acryloyl group in a side chain, (d) a photopolymerization initiator, and (e) a compound having at least one ethylenically unsaturated double bond and a partial structure selected from a urethane, an amide and a urea in a molecule.
Description
Technical field
The color filter that the present invention relates to be fit to be produced on the color filter that uses in liquid crystal display cells or the solid-state imager is with solidification compound, color filter and manufacturing approach thereof.
In addition, the present invention relates to manufacturing approach, color filter and the liquid crystal display cells of cured composition for color, colored pattern formation method, colored pattern, color filter.
Background technology
Color filter is a structure member indispensable in LCD or solid-state imager.LCD and CRT are in a ratio of compactness, and aspect of performance be equal more than, therefore,, replacing CRT as TV set image, computer picture, other display device.In addition, in recent years, the trend of the exploitation of LCD is the TV purposes towards the image quality that requires the large-scale and height of picture from the monitor purposes in the past of the smaller area of picture.
In the past, in the manufacturing approach of color filter, the most extensively adopted the pigment dispersing method.In the color filter manufacturing approach of having used the pigment dispersing method, for example, on transparent supporting bodies such as glass substrate, form black matrix; Then; Utilize spin-coating method etc., the cured composition for color of the pigment that has disperseed redness etc. is coated on whole, make public across mask.If after exposure, develop, then obtain red pixel.About blue, green pixel, also utilize identical method to form, form the pixel of three looks thus.
In addition, about color filter, require so far broad abovely color reproduction.In order to improve the color reproduction of color filter, need to improve the colorant content in the dyed layer, carry out high color purityization.In addition, follow the maximization of substrate size, require the raising of the throughput rate of color filter.In order to improve the throughput rate of color filter, also need the acceleration in the exposure process.For this reason, require low exposure to quantize.
Yet; In color filter is made; The increase of the colorant content in the colored Photoresist (color resist) causes the restricted levels of Photoepolymerizationinitiater initiater and photopolymerization monomer shared in the solid state component in solidification compound; Can not get sufficient light sensitivity, the problem that pattern becomes second nature and reduces.In addition, the low exposure in the exposure process also causes the pattern reduction that becomes second nature.The reduction that pattern becomes second nature becomes reasons such as shortcoming or damaged, the rough surface of the pattern in the color filter that obtains, even causes problems such as the demonstration of liquid crystal panel is bad.
In japanese kokai publication hei 11-326624 communique and TOHKEMY 2000-338322 communique; To such problem; Disclose color filter that combined light polymerization initiator, monomer, the resin with polymerism base, epoxy resin etc. form with polymerizable composition, polymerizable composition (yet; Disclosed color filter is big with the polymerizable composition, polymerizable composition especially absorption to ultraviolet region in these documents, in the formation of the low green pixel of exposure light sensitivity, has the become second nature problem of variation of pattern.
LCD (LCD) with the color filter purposes in, for the production of large-scale TV, substrate size is enlarging, and in order to improve the throughput rate under the situation of having used large substrate, expects the curing under low-yield.In addition, in the LCD of TV purposes,, require the more image quality of height with monitor purposes display in comparison in the past.That is, improve contrast and excitation.In order to improve contrast, about the solidification compound that in the making of color filter, uses, the particle size as the colorant (organic pigment etc.) that uses requires more small particle (for example with reference to patent documentation 1).Follow in this, the spreading agent addition that is used for pigment dispersing has the tendency of increase.In addition, in order to improve excitation,, require higher containing ratio as the containing ratio of colorant shared in the solid state component of solidification compound (organic pigment).Thereby, the tendency that the containing ratio of shared Photoepolymerizationinitiater initiater and photopolymerization monomer reduces in the solid state component in the solidification compound.
On the other hand, solid-state imager with the color filter purposes in, also expect low-energy curing.In addition, making progress the filmization of pattern, following in this, the pigment concentration in the composition improves.And then, be in the color filter at pigment, follow the pigment miniaturization, the ratio of the pigment dispersing agent in the composition is in the tendency of increase.Because like this, under the situation of any that LCD is used, solid-state imager is used, also limiting in order to make solidification compound solidify required composition is the content of Photoepolymerizationinitiater initiater and photopolymerization monomer; And colorant concentration uprises, therefore; It is low that so-called light sensitivity also takes place; Can not get sufficient curing, insufficient with the adhesiveness of substrate, the pattern of expectation forms problems such as remarkable difficulty.In japanese kokai publication hei 11-38226 communique,, proposed to import the technology of silane coupling agent, but practical going up expected further to improve in order to improve the substrate adhesiveness as countermeasure to this problem.
On the other hand; In TOHKEMY 2006-28499 communique; Proposed through containing polymerizable compound with specific part-structure and other free-radical polymerised compounds; Thereby can form low viscosity and the property handled superior, the Photocurable resin composition of the formed body that dimensional accuracy is superior.Said composition is fit to stereo modelling, even but present situation is to make it contain pigment isochrome material in a large number, be applicable to the purposes that forms fine pattern, can not realize that sufficient curable, fine pattern become second nature.
In addition, follow the maximization of substrate in recent years, expectation high speed slit coating, in addition; Require yield rate simultaneously, therefore, when expectation contains coloured material with high concentration; Carry out under the situation of high speed slit coating, also can form the tunicle of homogeneous, and the pattern superior cured composition for color that becomes second nature.
Summary of the invention
The present invention considers that said each problem in the past makes, and its problem is to realize following purpose.
That is, the object of the present invention is to provide and containing with high concentration under the situation of colorant, also solidify, have good pattern and become second nature, can form with the color filter of the superior colored pattern of the adhesiveness of supporter and use cured composition for color with ISO.
In addition, another purpose of the present invention be to provide possess the exploring degree and with the color filter of the superior colored pattern of the adhesiveness of supporter, and the manufacturing approach of this color filter.
Another purpose again of the present invention is to provide and can forms the good colored pattern that color filter is used, and has the colored curable resin composition of superior operation adaptability and uses its colored pattern formation method.The color filter of the high-contrast that further purpose of the present invention is to provide the good colored pattern that uses colored curable resin composition of the present invention to form, possess this colored pattern and the liquid crystal display cells that can make the manufacturing approach of this color filter and possess this color filter with high productivity.
According to the present invention, provide as follows.
< 1>a kind of color filter is used cured composition for color, wherein, contains following (1), (2), (3), and each composition of (4):
(1) is selected from side chain and has (methyl) acrylic copolymer of ester ring type (methyl) acryloyl group and have 0.001～0.20eq/g (methyl) acryloyl group and acid number is at least a alkali soluble resin of 10～150 multipolymer;
(2) Photoepolymerizationinitiater initiater;
(3) have and be selected from urethane, acid amides, and the part-structure of urea and the polymerizable monomer or the oligomer of ethene property unsaturated double-bond;
(4) colorant.
< 2>use cured composition for color according to < 1>described color filter, wherein,
It is said that to have 0.001～0.20eq/g (methyl) acryloyl group and acid number be that 10～150 multipolymer is the compound of formula (1-1) expression, the compound of formula (1-2) expression or the compound of formula (1-3) expression,
[changing 1]
At general formula (1-1), (1-2) or (1-3), R representes hydrogen atom or methyl, R
1Phenyl, the aryl of carbon number 6～12 or the aralkyl of carbon number 7～12 of alkyl, the alkyl that is surrounded by carbon number 1～4 or the alkoxy of expression carbon number 1～18.R
2The alkylidene of 1～18 of carbon number of expression, contain carbon number 1～4 alkyl phenyl carbamate or contain the carbamate of the ester ring type base of carbon number 3～18.R
3The expression carbon number is the alkylidene of 2～16 straight or branched; What a～e in a～d in the general formula (1-1), the general formula (1-2), a～e in the general formula (1-3) represented repetitive contains molar ratio (mole %); A～d:b in the general formula (1-1) representes 3～50; C representes 3～40, and d representes 2～60, a+b+c+d=100.A～e:b in general formula (1-2) and the general formula (1-3) representes 0～85, and c representes 3～50, and d representes 3～40, and e representes 2～60, and a+b+c+d+e=100, n are 2～16.
< 3>use cured composition for color according to < 1>or < 2>described color filter, wherein,
Have the part-structure that is selected from said urethane, acid amides urea and the polymerizable monomer or the oligomer of ethene property unsaturated double-bond and have nitrogen heterocyclic ring.
< 4>use cured composition for color according to each described color filter in < 1 >～< 3 >, wherein,
Have the part-structure that is selected from said urethane, acid amides and urea and the polymerizable monomer or the oligomer of ethene property unsaturated double-bond and also have the isocyanuric acid ester skeleton.
< 5>use cured composition for color according to each described color filter in < 1 >～< 4 >, wherein,
Have the part-structure that is selected from said urethane, acid amides and urea and the polymerizable monomer or the oligomer of ethene property unsaturated double-bond and also have oxyalkylene group.
< 6>a kind of color filter wherein, has:
Use the colored pattern that each described color filter forms with cured composition for color in < 1 >～< 5 >.
< 7>a kind of manufacturing approach of color filter wherein, comprising:
Each described color filter is used cured composition for color in coating < 1 >～< 5>on supporter, forms the operation of cured composition for color layer;
The operation that said cured composition for color layer is made public across mask;
Said cured composition for color layer after the exposure is developed, form the operation of colored pattern.
In addition; The inventor etc. are in view of said truth, and the result who has carried out intent research finds to have the adhesive resin and the polymerizable composition, polymerizable composition of specific part-structure through use; Can solve the problem of said second embodiment, thereby accomplish second embodiment.
According to the present invention, provide as follows.
< 8>a kind of colored curable resin composition wherein, comprises:
(a) look material;
(b) has the compound of at least one ethene property unsaturated double-bond;
(c) be included in the adhesive resin that side chain has (methyl) acrylic copolymer of ester ring type (methyl) acryloyl group;
(d) Photoepolymerizationinitiater initiater;
(e) has at least one ethene property unsaturated double-bond and in molecule, have the compound of the part-structure that is selected from urethane, acid amides and urea.
< 9>according to < 8>described colored curable resin composition, it is characterized in that,
Have compound 100 weight portions of at least one ethene property unsaturated double-bond with respect to said (b), to contain the compound that said (e) has at least one ethene property unsaturated double-bond and in molecule, have the part-structure that is selected from urethane, acid amides and urea more than 5 mass parts and less than the amount of 25 mass parts.
< 10>according to < 8>or < 9>described solidification compound, wherein,
The compound that said (e) has at least one ethene property unsaturated double-bond and in molecule, have a part-structure that is selected from urethane, acid amides and urea is the compound with isocyanuric acid ester skeleton.
< 11>according to each described solidification compound in < 8 >～< 10 >, wherein,
The compound that said (e) has at least one ethene property unsaturated double-bond and in molecule, have a part-structure that is selected from urethane, acid amides and urea is compound and the formula with isocyanic acid ester bond
(I) reaction product of the alcoholic compound of expression,
[changing 2]
General formula (I)
In said general formula (I), R
1, R
2Represent hydrogen atom or alkyl, R respectively independently
3The functional group of expression hydrogen atom, alkyl, alkoxy, allyl, aryl, formula (II) expression or the functional group of formula (III) expression,
[changing 3]
General formula (II) general formula (III)
In said general formula (II), n representes 1～10 integer, in addition, in general formula (II) and general formula (III), R
4Expression hydrogen atom or alkyl, in general formula (III), the R of a plurality of existence in molecule
4Can be identical, also can be inequality.
< 12>according to each described solidification compound in < 8 >～< 11 >, it is characterized in that,
Also contain (f-1) alkoxysilane compound containing trialkylsilyl group in molecular structure.
< 13>a kind of colored pattern formation method wherein, comprising:
Utilize the slit coating method, apply the operation of each described colored curable resin composition in < 8 >～< 12 >.
< 14>a kind of colored pattern, wherein,
It utilizes < 13>described colored pattern formation method and forms.
< 15>a kind of manufacturing approach of color filter wherein, has:
Utilize the slit coating method, each described colored curable resin composition in < 8 >～< 12>is coated on substrate surface, form the operation of colored pattern.
< 16>a kind of color filter, wherein,
Utilize < 15>described manufacturing approach to make, and its contrast is more than 5000.
< 17>a kind of liquid crystal display cells, wherein,
Used < 16>described color filter.
Also have, in this manual, expression " acrylic acid " reaches under both sides or arbitrary side's the situation that " methacrylic acid ", " acryloyl group " reach " methacryl ", is recited as " (methyl) acrylic acid ", " (methyl) acryloyl group " respectively.
Can know according to the present invention, can be provided at and contain under the situation of colorant also with high concentration that ISO solidifies, have good pattern and become second nature, can form with the color filter of the superior colored pattern of the adhesiveness of supporter and use solidification compound.
And then the cured composition for color of the application of the invention can provide to possess the exploring degree and with the color filter of the superior colored pattern of the adhesiveness of supporter and can make the manufacturing approach of this color filter with high throughput rate.
Can know, can provide to form color filter to have the colored curable resin composition of superior operation adaptability and use its colored pattern formation method with good colored pattern according to the present invention.
The color filter of the high-contrast that in addition, the superior colored pattern that uses colored curable resin composition of the present invention to form can be provided, possesses this colored pattern and can make the manufacturing approach of this color filter with high throughput rate.
And then, the liquid crystal display cells that has used said color filter can be provided.
Description of drawings
Fig. 1 is illustrated in the thickness evaluation of embodiment the vertical view of the pad that uses in the coating of color solidification resin composition (colored Photoresist (color resist)).
Fig. 2 is the slit die of expression pad that Fig. 1 is installed and the stereographic map of coating state that utilizes the colored Photoresist of slit die.
Embodiment
Below, the color filter that specifies first embodiment is with cured composition for color, color filter and the manufacturing approach thereof of using this cured composition for color to make.
[color filter is used cured composition for color]
The color filter of first embodiment is used cured composition for color, it is characterized in that, contains following (1), (2), (3), and each composition of (4):
(1) be selected from side chain have ester ring type (methyl) acryloyl group (methyl) acrylic copolymer, and have at least a alkali soluble resin that (methyl) acryloyl group and acid number are 10～150 multipolymer with 0.001～0.20eq/g;
(2) Photoepolymerizationinitiater initiater;
(3) have and be selected from urethane, acid amides, and the part-structure of urea and the polymerizable monomer or the oligomer of ethene property unsaturated double-bond;
(4) colorant.
The color filter of first embodiment with cured composition for color (below; Sometimes abbreviate " cured composition for color " as) contain each compositions of above-mentioned (1)～(4); Containing with high concentration under the situation of colorant thus; Also solidify, have good pattern and become second nature, can form the colored pattern superior with the adhesiveness of supporter with ISO.Especially, the cured composition for color of first embodiment also is suitable as with high concentration and contains colorant and be used to form the cured composition for color of the low green pixel of the transmitance of exposure such as I ray light.
Below, each composition of above-mentioned (1)～(4) is described successively.
< (1) composition >
In the cured composition for color of first embodiment; As (1) composition, contain be selected from side chain have ester ring type (methyl) acryloyl group (methyl) acrylic copolymer, and have at least a alkali soluble resin that (methyl) acryloyl group and acid number are 10～150 multipolymer with 0.001～0.20eq/g.
(1-1) has (methyl) acrylic copolymer of ester ring type (methyl) acryloyl group at side chain
(methyl) acrylic copolymer in that side chain has ester ring type (methyl) acryloyl group in first embodiment is that ester ring type (methyl) acryloyl group as polyradical is imported the alkali soluble resin that the side chain of (methyl) acrylic copolymer forms (below, suitably be called " specific alkali soluble resin (1) ").
As the method that ester ring type (methyl) acryloyl group is imported in the resin that comprises acrylic copolymer, for example, can be suitable for the method for record in the special public clear 50-34443 communique of Japan, the special public clear 50-34444 communique of Japan etc.Specifically, have epoxycyclohexyl simultaneously through for example making, carboxyl or a hydroxyl reaction in the compound of ester ring type epoxy radicals such as epoxide ring amyl group and (methyl) acryloyl group etc. and the resin, can obtain having the resin of polyradical at side chain.
Preferred example as the compound that has ester ring type epoxy radicals and (methyl) acryloyl group simultaneously; Can enumerate epoxycyclohexyl methyl (methyl) acrylic ester, epoxy cyclopentyl-methyl (methyl) acrylic ester; (3, the 4-epoxycyclohexyl) methyl (methyl) acrylic ester wherein most preferably.
Importing is (methyl) acrylic copolymer as the resin matrix of (methyl) acryloyl group of polyradical.As can with the monomer of (methyl) acrylic acid copolymer; Can enumerate and make styrene and AMS etc. instead has styrene, (methyl) methyl acrylate, (methyl) acrylic acid ethyl ester, (methyl) acrylic acid propyl diester, (methyl) acrylic acid isopropyl esters, (methyl) butyl acrylate cores, vinyl acetate base ester, vinyl cyanide, (methyl) acrylic amide, glycidyl (methyl) acrylic ester, allyl glycidyl ether, ethylacrylic acid glycidyl esters, crotonyl glycidyl ether, crotonic acid glycidyl ether, (methyl) acryloyl chloride, benzyl (methyl) acrylic ester, hydroxyethyl (methyl) acrylic ester, N hydroxymethyl acrylamide, the N of alkyl in the α position; Enoyl-morpholine, N in N-DMAA, the N-methyl; N-dimethyl aminoethyl (methyl) acrylic ester, N, the multipolymer of monomer copolymerizations such as N-dimethyl aminoethyl acrylic amide.As (methyl) acrylic copolymer, especially preferably (methyl) acrylic acid is reached the multipolymer that instead has the styrene of alkyl to contain as copolymer composition in the α position.
In (methyl) acrylic copolymer as resin matrix, the shared ratio of (methyl) acrylic acid is preferred in molar ratio 0.2～0.8, and more preferably 0.3～0.7.In addition, containing in the multipolymer of above-mentioned copolymer compositions such as styrene is proportional preferred in molar ratio 0.8～0.2, and more preferably 0.7～0.3.
The weight-average molecular weight specific alkali soluble resin (1) that uses in the first embodiment, that measure with GPC is from the viewpoint of film formation property and the stability of composition, preferred 1000～50000.In addition, the preferred content of the acid roots such as carboxyl that contain in (methyl) acrylic copolymer is about 5～200 from concerning the viewpoint of the dissolubility of alkaline developer and light sensitivity by acid number.
In the first embodiment, as the concrete example of specific alkali soluble resin (1), for example can enumerate as follows, but be not limited to this.
[changing 4]
Specific alkali soluble resin (1) can only use a kind of separately, also can share two or more.
(1-2) having (methyl) acryloyl group and acid number with 0.001～0.20eq/g is 10～150 multipolymer
In first embodiment to have (methyl) acryloyl group and acid number with 0.001～0.20eq/g be that 10～150 multipolymer is the wire organic polymer; Be to organic solvent and the soluble alkali soluble resin of weak base aqueous solution (below, suitably be called " specific alkali soluble resin (2) ").
(methyl) acryloyl group in the specific alkali soluble resin (2) is 0.001～0.020eq/g from the viewpoint of curable, preferred 0.001～0.015eq/g, more preferably 0.002～0.010eq/g.
The acid number of specific alkali soluble resin (2) is 10～150, and is preferred 15～120, more preferably 15～100.If acid number is low excessively, then the dissolubility to developer solution is not enough, needs to develop for a long time, maybe can not form pattern.On the contrary, if acid number is too high, then the dissolubility to solvent is not enough, can not prepare coating liquid, or takes place to apply uneven easily.In addition, can not guarantee suitable developing regional.For the acid number that makes specific alkali soluble resin (2) is above-mentioned scope, for example, can enumerate the method that combines acid group (carboxyl, hydroxyl etc.) at the side chain of resin.As acid group, preferred carboxyl or hydroxyl.
Wherein, as specific alkali soluble resin (2), preferably by the compound of formula (1-1) expression, by the compound of general formula (1-2) expression, and by the compound of general formula (1-3) expression.
[changing 5]
In general formula (1-1)～general formula (1-3), R representes hydrogen atom or methyl.In general formula (1-1)～general formula (1-3), the R of a plurality of existence can be identical, also can be different.
In general formula (1-1)～general formula (1-3), a plurality of R of existence can be identical, also can be different.
In general formula (1-1)～general formula (1-3), R
1Be 1～18 (C of carbon number
1～C
18) alkyl, comprise 1～4 (C of carbon number
1～C
4) alkyl or 6～12 (C of phenyl, carbon number of alkoxy
6～C
12) aryl or 7～12 (C of carbon number
7～C
12) aralkyl.
In general formula (1-2) or general formula (1-3), the R of a plurality of existence
1Can be identical, also can be different.
As by R
1The C of expression
1～C
18Alkyl; Can be any of straight chain, branched or ring-type; For example, can enumerate methyl, ethyl, propyl group, butyl, heptyl, hexyl, octyl group, decyl, dodecyl, cetyl, octadecyl, 2-chloroethyl, 2-bromoethyl, 2-cyano ethyl, 2-methoxycarbonyl ethyl, 2-methoxy ethyl, 3-bromopropyl etc.
As R
1The C that contains in the phenyl of expression
1～C
4Alkyl, can enumerate at above-mentioned C
1～C
18The concrete example of alkyl in the alkyl of 1～4 of carbon number of example.In addition, as by R
1The C that contains in the phenyl of expression
1～C
4Alkoxy, preferably can enumerate like methoxyl, ethoxy, propoxyl group, butoxy etc.
As by R
1The C of expression
6～C
12Aryl, for example, can enumerate phenyl, tolyl, naphthyl etc.
As by R
1The C of expression
7～C
12Aralkyl, for example, can enumerate benzyl, phenethyl, 3-phenyl propyl, naphthyl methyl, 2-naphthyl ethyl, benzyl chloride base, bromobenzyl, methyl-benzyl, Ethylbenzyl, methoxy-benzyl, dimethyl benzyl, dimethoxy-benzyl etc.
In general formula (1-1)～general formula (1-3), R
2Be C
1～C
18Alkylidene, comprise C
1～C
4Alkyl phenyl carbamate, comprise C
3～C
18The carbamate of ester ring type base.
As by R
2The C of expression
1～C
18Alkylidene, can enumerate from by said R
1The C of expression
1～C
18Alkyl remove a hydrogen and become the group of divalence.
As by R
2The C that contains in the phenyl carbamate of expression
1～C
4Alkyl, can enumerate by said R
1The C of expression
1～C
18Alkyl concrete example in the alkyl of 1～4 of carbon number.This phenyl carbamate (OCO-NH-C that serves as reasons
6H
4-) expression structure, abovementioned alkyl is the substituting group of phenylene wherein.
As by R
2The C that contains in the carbamate of expression
3～C
18The ester ring type base, can enumerate cyclopentyl, cyclobutyl, cyclohexyl, isophorone base, dicyclohexyl etc.This carbamate is served as reasons, and (NH-COO-) structure of expression, above-mentioned ester ring type base and this structure together form the base of divalence.
R in the general formula (1-3)
3The straight or branched alkylidene that the expression carbon number is 2～16 specifically, can be enumerated from said R
1C
1～C
18Alkyl in the alkyl of 2～16 of carbon numbers remove a hydrogen and become the group of divalence.
What a～e in a～d in the general formula (1-1), the general formula (1-2), a～e in the general formula (1-3) represented repetitive contains molar ratio (mole %).
In general formula (1-1), b representes 3～50, preferably representes 5～40, and c representes 3～40, preferably representes 10～30, and d representes 2～60, preferably representes 5～50, a+b+c+d=100.
In general formula (1-2) and general formula (1-3), b representes 0～85, preferably representes 0～80, and c representes 3～50, preferably representes 5～40, and d representes 3～40, preferably representes 8～30, and e representes 2～60, preferably representes 2～50, a+b+c+d+e=100.N is 2～16, preferred 4～12.
In general formula (1-1)～general formula (1-3), preferred R
1The situation of expression aralkyl, more preferably benzyl is as R
2Preferred substance, can enumerate the alkylidene of 2～16 of carbon numbers, the residue of removing (NCO) of following diisocyanate.Preferably enumerate methyl diphenylene diisocyanate, inferior cresyl vulcabond, eylylene diisocyanate, 2; 4-Stilbene (toluylene) diisocyanate, O-Stilbene diisocyanate, IPDI, dicyclohexyl methyl hydride diisocyanate, more preferably hexamethylene diisocyanate, IPDI, inferior cresyl vulcabond.
As R
3, preferred following structure.
-(CH
2)
n-: n representes 2～10 integer.
As R
3, more preferably following structure.
-(CH
2)
n-: n representes 2～6 integer.
In the first embodiment, as the concrete example of specific alkali soluble resin (2), for example, enumerate as follows, but be not limited to this.
[changing 6]
[changing 7]
Specific alkali soluble resin (2) for example can wait synthetic through the method for record in paragraph numbering [0074]～[0078] of No. 2 communiques of TOHKEMY 2002-2044.
The scope of the weight-average molecular weight preferred 10000～50000 of utilizing GPC mensuration of specific alkali soluble resin (2).
Specific alkali soluble resin (2) can use only a kind of separately, also can share two or more.
In addition,, a side of specific alkali soluble resin (1), specific alkali soluble resin (2) can be only used, also both can be share as the composition in first embodiment (1).
Content as the composition in the cured composition for color of first embodiment (1); From pattern become second nature, with the adhering viewpoint of supporter; Total solid state component with respect to cured composition for color; Preferred 0.5～30.0 quality %, more preferably 1.0～20.0 quality %, and then preferred 5.0～15.0 quality %.
< (2) composition >
Contain Photoepolymerizationinitiater initiater as (2) composition in the cured composition for color of first embodiment.
Photoepolymerizationinitiater initiater in first embodiment is to decompose through light, cause, promote said (1) composition or after state the polymeric compounds of the composition of (3), preferably have the Photoepolymerizationinitiater initiater of absorption in the zone of wavelength 300～500nm.In addition, Photoepolymerizationinitiater initiater can separately or share two or more.
As Photoepolymerizationinitiater initiater; For example; Can enumerate organic halogen compound 、 oxadiazole compound, carbonyls, ketal compound, styrax compound, acridine compound, organic peroxy compound, azo-compound, coumarin compound, triazo-compound, aromatic ring alkene metal derivative compound, six aryl di-imidazolium compoundss, organic boron-oxygen, disulfonic acid compound, oxime ester compound, salt compound, acylphosphanes (oxide) compound; But preferred oxime ester compound in the first embodiment.
The content of (2) Photoepolymerizationinitiater initiater in the hardening composition of first embodiment is about 3～20 quality % by solid component concentration preferably, and then the scope of preferred 5～10 quality %.
< (3) composition >
Conduct (3) composition in the cured composition for color of first embodiment; Contain have be selected from urethane, acid amides, and the polymerizable monomer of the part-structure of urea and ethene property unsaturated double-bond or oligomer (below, suitably be called " specific aggregation property compound ".)。
The viewpoint that specific aggregation compounds in first embodiment becomes second nature from the pattern of solidification compound, the compound that preferably in molecule, urethane bond is had as part-structure.In addition,, preferably have nitrogen heterocyclic ring, more preferably have the compound (cyamelide ester compounds) of isocyanuric acid ester skeleton as specific aggregation property compound.
In addition, from the viewpoint of the development property of solidification compound, specific aggregation property compound preferably except said structure, has oxyalkylene group at molecule, as oxyalkylene group, and optimization ethylene oxide, epoxypropane, especially optimization ethylene oxide base.
Just in the first embodiment; As being suitable as urethane compound (3) composition, that have ethene property unsaturated link base, and the concrete example of cyamelide ester compounds, can preferably enumerating compound and by the reaction product of the alcoholic compound of formula (I) expression with isocyanic acid ester bond.
[changing 8]
General formula (I)
In said general formula (I), R
1, and R
2Represent hydrogen atom or alkyl respectively independently, but as this alkyl, the alkyl of preferred carbon number 1～5.R
1, R
2And then preferably be respectively hydrogen atom or methyl.
R
3Expression hydrogen atom, alkyl, alkoxy, allyl, aryl, by the functional group of formula (II) expression or by the functional group of formula (III) expression.Wherein, the alkyl of preferred hydrogen atom, carbon number 1～5, the alkoxy of carbon number 1～5 or by the functional group of general formula (III) expression, and then preferable methyl or by the functional group of general formula (III) expression.
[changing 9]
General formula (II) general formula (III)
In above-mentioned general formula (II), n representes 1～10 integer, preferred 1～5.In addition, in general formula (II) and general formula (III), R
4Expression hydrogen atom or alkyl, as alkyl, the alkyl of preferred carbon number 1～5.In addition, in general formula (III), the R of a plurality of existence in molecule
4Can be identical, also can be different.As at this preferred R
4, can enumerate hydrogen atom or methyl.
As the concrete example of the alcoholic compound shown in the general formula (I), can be listed below and state compound (example compound (MA-1)～(MA-12)) etc., but be not limited thereto.
[changing 10]
In MA-5～MA-7, the integer of m=1～20
In MA-8～MA-10, R=hydrogen or methyl, the rational number of o, p, q, r, s, t=0～20
[changing 11]
As the urethane compound with ethene property unsaturated link, and cyamelide ester compounds, the alcoholic compound of preferably selecting from said exemplary compounds and following shown in the reaction product of isocyanate compound (exemplary compounds (MU-1)～(MU-27)).
The reaction of isocyanate compound and alcoholic compound is for example undertaken by following condition.
As the addition of isocyanate compound and alcohols, regulate so that the hydroxyl molal quantity of the NCO molal quantity of isocyanate compound and alcoholic compound equates.
As catalysts; Do not limit especially; But preferably use tertiary amines, 1 such as organic zinc (methyl) acrylates, triethylene diamine, triethylamine such as organotin (methyl) acrylates, zinc octoate, zinc naphthenate such as three (2 ethyl hexanoic acid) bismuth, dibutyl tin dilaurate, di-n-butylacetic acid tin, dibutyl tin dichloride, tin octoate, 8-nitrogen two rings [5; 4; 0] undecylene-7 grade has (methyl) acrylic ester of amidine skeleton, with respect to alcohol or isocyanates 100 mass parts, can add with the scope of 0.0001～10 mass parts.
Also have, in this manual, under the both sides of expression acrylic ester, methacrylate or arbitrary side's the situation, be labeled as " (methyl) acrylic ester ".
As reaction conditions, be suitable for-50 ℃～100 ℃ temperature range usually.Under the situation below-50 ℃, the progress of reaction is extremely slow, and under the situation more than 100 ℃, accessory substance increases, and yield reduces, and, possible gelation, not preferred.Utilize solvent as required, dilute.
The solvent that uses all can use except the material of alcohol, carboxylic acid, amine etc. and isocyanate reaction; But from reaction velocity, dissolubility aspect; Preferred acetonitrile, the N of using; Chlorine such as dinethylformamide (DMF), DMAC N,N (DMAc), dimethyl sulfoxide (DMSO) (DMSO), N-N-methyl-2-2-pyrrolidone N-(NMP) isopolarity solvent, chloroform are fragrant family solvents such as solvent, toluene, xylene.In addition, in order to prevent the reaction of residuary water and isocyanates, suitably use dehydrated solvent.
After reaction finishes, after under reduced pressure this reaction solution being concentrated, with silicagel column (eluant: ethyl acetate/n-hexane=1/1) come purifying.Can also be through chromatography, recrystallizationization, deposition is come purifying again.
Preferred (3) composition that obtains first embodiment promptly have the urethane compound of ethene property unsaturated link, and concrete (exemplary compounds (MU-1)～(MU-27)) of the isocyanate compound that uses during the cyamelide ester compounds illustrate as follows.
[changing 12]
[changing 13]
[changing 14]
Secondly, in the first embodiment,, can enumerate the reaction product of amines and isocyanate compound with regard to urea compounds with ethene property unsaturated link as (E) composition.
The reaction of isocyanate compound and amines is for example undertaken by following condition.
The amino molal quantity of adjusting the NCO molal quantity that makes isocyanate compound and amines equates.As catalyzer; Do not limit especially, but preferably use organotin (methyl) acrylates such as three (2 ethyl hexanoic acid) bismuth, dibutyl tin dilaurate, di-n-butylacetic acid tin, dibutyl tin dichloride, tin octoate, organic zincs such as zinc octoate, zinc naphthenate (methyl) acrylates; Tertiary amines such as triethylene diamine, triethylamine; 1,8-diaza-bicyclo [5,4,0] undecylene-7 grade has (methyl) acrylic ester of amidine skeleton; With respect to amine or isocyanates 100 mass parts, with the scope adding of 0.0001～10 mass parts.
In reaction, be suitable for-20 ℃～80 ℃ temperature range usually.Preferably-10 ℃～50 ℃ temperature range, more preferably-5 ℃～30 ℃.
The solvent that uses all can use except the material of alcohol, carboxylic acid, amine etc. and isocyanate reaction; But from reaction velocity, dissolubility aspect; Preferred acetonitrile, the N of using; Chlorine such as dinethylformamide (DMF), DMAC N,N (DMAc), dimethyl sulfoxide (DMSO) (DMSO), N-N-methyl-2-2-pyrrolidone N-(NMP) isopolarity solvent, chloroform are fragrant family solvents such as solvent, toluene, xylene.In addition, in order to prevent the reaction of residuary water and isocyanates, suitably use dehydrated solvent.
After reaction finishes, after under reduced pressure this reaction solution being concentrated, with silicagel column (eluant: ethyl acetate/n-hexane=1/1) come purifying.Can also be through chromatography, recrystallizationization, deposition is come purifying again.
As the concrete example of the urea compounds in first embodiment, can enumerate the reaction product of the concrete example ((MU-28)～(MU-30)) of concrete example (exemplary compounds (A-1)～(A-15)) that following amines is shown and isocyanate compound with ethene property unsaturated link.
[changing 15]
[changing 16]
Then, in the first embodiment,, can enumerate the reaction product that amines and halogen contain compound with regard to amide compound with ethene property unsaturated link as (E) composition.
The reaction that amines and halogen contain compound is for example undertaken by following condition.
In reaction method, molal quantity and the molal quantity of the acid halide group that halogen contains compound of the amino of amines equally added, added catalytic amount to containing the alkali till the compound equivalent with halogen.As the example of alkaline matter, can enumerate triethylamine or pyridine etc.Solvent can be enumerated THF or acetonitrile, dimethyl acetamide etc.The scope that temperature of reaction is preferred-30 ℃～100 ℃, and then preferred-20 ℃～80 ℃.More preferably-20 ℃～50 ℃.After reaction finishes, behind under reduced pressure concentrated this reaction solution, with silicagel column (eluant: ethyl acetate/n-hexane=1/1) come purifying.Can utilize chromatography, recrystallizationization, deposition is come purifying again.
As the concrete example of such amide compound with ethene property unsaturated link, can enumerate the amines that uses in said urea compounds synthetic concrete example (exemplary compounds (A-1)～(A-15)) and following shown in halogen contain the reactive product of compound (following exemplary compounds (C-1)～(C-3)).
[changing 17]
Utilize (3) composition that above-described method obtains preferably in total solid state component of the cured composition for color of first embodiment, to contain, more preferably the scope of 0.3～10.0 quality % with 0.3～15.0 quality %.
< (4) composition >
In the cured composition for color of first embodiment,, contain colorant as (4) composition.
The colorant that contains in the cured composition for color of first embodiment does not limit especially, can be with known various dyestuff or pigment in the past with a kind of or mix two or more uses.As this colorant, from the viewpoint of permanance such as thermotolerance, photostability, preferred pigments.
As the pigment that can in the cured composition for color of first embodiment, use, can use known in the past various inorganic pigments or organic pigment.In addition, no matter inorganic pigment or organic pigment if consider preferred high permeability, then preferably use the thin pigment of trying one's best, if consider to handle property, the preferred 0.01 μ m of the mean grain size of above-mentioned pigment～0.1 μ m, more preferably 0.01 μ m～0.05 μ m.In addition; As above-mentioned inorganic pigment; Metallic compound can be enumerated, specifically, metal oxides such as iron, cobalt, aluminium, cadmium, lead, copper, titanium, magnesium, chromium, zinc, antimony, and the composite oxides of said metal can be enumerated by expression such as metal oxide, metallic complex salt.
As above-mentioned organic pigment, for example, can enumerate
C.I. pigment yellow 11,24,31,53,83,93,99,108,109,110,138,139,147,150,151,154,155,167,180,185,199;
C.I. pigment orange 36,38,43,71;
C.I. pigment red 81,105,122,149,150,155,171,175,176,177,209,220,224,242,254,255,264,270;
C.I. pigment violet 19,23,32,39;
C.I. pigment blue 1,2,15,15:1,15:3,15:6,16,22,60,66;
C.I. pigment Green 7,36,37;
C.I. bistre 25,28;
C.I. pigment black 1,7; Carbon black etc.
In the first embodiment, especially can preferably use the pigment that in the structural formula of pigment, has alkaline N atom.These pigment with alkaline N atom show good dispersiveness in the composition of first embodiment.About its reason, not too fully clear and definite, but infer that the good degree for the affinity of photonasty polymerization composition and pigment has produced influence.
As the pigment that in the application's invention, can preferably use, can enumerate following pigment.But first embodiment is not limited to these.
C.I. pigment yellow 11,24,108,109,110,138,139,150,151,154,167,180,185,
C.I. pigment orange 36,71,
C.I. pigment red 122,150,171,175,177,209,224,242,254,255,264,
C.I. pigment violet 19,23,32,
C.I. pigment blue 15: 1,15:3,15:6,16,22,60,66,
C.I. pigment black 1
These organic pigments can be separately or make up in order to improve excitation use various.The concrete example of combinations thereof illustrates as follows.
For example; As the pigment of redness, can use anthraquione pigmentss, perylene pigment, diketopyrrolopyrrolecocrystals series pigments separately or those at least a and two diazonium be that yellow uitramarine, isoindoline are that yellow uitramarine, Kui phthalein ketone are that yellow uitramarine or perylene are the mixing of red pigment etc.For example, as anthraquione pigmentss, can enumerate C.I. paratonere 177 Zuo is perylene pigment; C.I. paratonere 155, C.I. paratonere 224 can be enumerated,, C.I. paratonere 254 can be enumerated as the diketopyrrolopyrrolecocrystals series pigments; From the color reproduction aspect, preferably with the mixing of C.I. pigment yellow 13 9.In addition, the mass ratio of red pigment and yellow uitramarine is preferred 100: 5～100: 50.Under the situation below 100: 4, be difficult to suppress the light transmission rate of 400nm to 500nm, can not improve excitation sometimes.In addition, under the situation more than 100: 51, predominant wavelength is near the short wavelength, becomes big sometimes from the deviation of NTSC target form and aspect.Especially, as above-mentioned mass ratio, 100: 10～100: 30 scope is best.Also have, under the situation of the combination between the red pigment, can regulate according to colourity.
In addition, as green pigment, can use the halogenated phthalocyanines series pigments separately or be that yellow uitramarine, Kui phthalein ketone are that yellow uitramarine, azomethine are that yellow uitramarine or isoindoline are that yellow uitramarine mixes use itself and two diazonium.For example, as such example, preferred C.I. pigment Green 7,36,37 and the mixing of C.I. pigment yellow 83, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 180 or C.I. pigment yellow 185.Preferred 100: 5～100: 150 of the mass ratio of green pigment and yellow uitramarine.As above-mentioned mass ratio, especially preferred 100: 30～100: 120 scope.
As the pigment of indigo plant, can use phthualocyanine pigment separately, or be that violet pigment mixes use itself Yu dioxazine.For example, preferred C.I. pigment blue 15: 6 with the mixing of C.I. pigment Violet 23.Preferred 100: 0～100: 30 of the mass ratio of blue pigment and violet pigment is more preferably below 100: 10.
In addition, as the pigment that black matrix is used, can use carbon, titanium carbon, iron oxide, titanium dioxide separately or mix use, the combination of preferred carbon and titanium carbon.In addition, preferred 100: 0～100: 60 scope of mass ratio of carbon and titanium carbon.
Under the situation that the composition of first embodiment is used as color filter, from the viewpoint of look inequality or contrast, the preferred 10～100nm of the primary particle size of pigment, more preferably 10～70nm, and then preferred 10～50nm, most preferably 10～40nm.
In addition, under the situation that the composition of first embodiment is used as color filter, from the viewpoint of look inequality or contrast, preferred use is dissolved in the dyestuff in the composition equably.
Can not limit especially as the dyestuff that the colorant that in the cured composition for color of first embodiment, contains uses, can use as color filter in the past and use known dyestuff.For example, can use japanese kokai publication sho 64-90403 communique, japanese kokai publication sho 64-91102 communique, japanese kokai publication hei 1-94301 communique, japanese kokai publication hei 6-11614 communique, Japanese spy and step on disclosed pigment in No. 2592207, No. 4808501 instructions of United States Patent (USP), No. 5667920 instructions of United States Patent (USP), No. 5059500 instructions of United States Patent (USP), japanese kokai publication hei 5-333207 communique, japanese kokai publication hei 6-35183 communique, japanese kokai publication hei 6-51115 communique, japanese kokai publication hei 6-194828 communique, japanese kokai publication hei 8-211599 communique, japanese kokai publication hei 4-249549 communique, japanese kokai publication hei 10-123316 communique, japanese kokai publication hei 11-302283 communique, japanese kokai publication hei 7-286107 communique, TOHKEMY 2001-4823 communique, japanese kokai publication hei 8-15522 communique, japanese kokai publication hei 8-29771 communique, japanese kokai publication hei 8-146215 communique, japanese kokai publication hei 11-343437 communique, japanese kokai publication hei 8-62416 communique, TOHKEMY 2002-14220 communique, TOHKEMY 2002-14221 communique, TOHKEMY 2002-14222 communique, TOHKEMY 2002-14223 communique, japanese kokai publication hei 8-302224 communique, japanese kokai publication hei 8-73758 communique, japanese kokai publication hei 8-179120 communique, japanese kokai publication hei 8-151531 communique etc.
As chemical constitution, can use dyestuffs such as pyrazoles azo system, aniline azo system, triphenyl methane system, anthraquinone system, Anthrapyridone system, benzylidene system, oxygen alcohol (オ キ ソ ノ one Le) are, pyrazolone triazole azo system, pyridone azo system, anthocyanin system, phenothiazines, pyrrolo-pyrazoles azomethine system, xanthene system, phthalocyanine system, chromene system, indigo system.
In addition; After the curing of the pattern exposure of solidification compound and exposure portion; What is called is utilized water or alkali to develop and is removed unexposed portion; Form pattern, for example form under the situation of colored pattern of Photoresist or color filter, from fully removing, can suitably use acid dyes and/or its derivant sometimes based on the light that the develops viewpoint of the bonding agent, dyestuff etc. of irradiating part not.
In addition, can also serviceably use direct dyes, basic-dyeable fibre, mordant dye, acid mordant dyes, azoic dyes, disperse dyes, oil-soluble dyes, food dye and/or these derivant etc.
As long as above-mentioned acid dyes has the acid root of sulfonic acid or carboxylic acid etc.; Just do not limit especially, but consider to organic solvent or developer solution dissolubility, with the salt of alkali compounds form property, absorbance, with composition in he composition necessary performance such as interaction, photostability, thermotolerance whole and select.
Below, enumerate the concrete example of acid dyes, but in the first embodiment, be not limited to these.For example, can enumerate
The purple N of acid alizarine;
Acid black 1,2,24,48;
Blue VRS, 7,9,15,18,23,25,27,29,40,42,45,51,62,70,74,80,83,86,87,90,92,96,103,112,113,120,129,138,147,150,158,171,182,192,210,242,243,256,259,267,278,280,285,290,296,315,324:1,335,340;
Acid chrome violet K;
Acid fuchsin;
Azogeramine; 4; 8; 14; 17; 18; 26; 27; 29; 31; 34; 35; 37; 42; 44; 50; 51; 52; 57; 66; 73; 80; 87; 88; 91; 92; 94; 97; 103; 111; 114; 129; 133; 134; 138; 143; 145; 150; 151; 158; 176; 182; 183; 198; 206; 211; 215; 216; 217; 227; 228; 249; 252; 257; 258; 260; 261; 266; 268; 270; 274; 277; 280; 281; 195; 308; 312; 315; 316; 339; 341; 345; 346; 349; 382; 383; 394; 401; 412; 417; 418; 422; 426;
Acid violet 6B, 7,9,17,19;
Indian yellow 1; 3; 7; 9; 11; 17; 23; 25; 29; 34; 36; 38; 40; 42; 54; 65; 72; 73; 76; 79; 98; 99; 111; 112; 113; 114; 116; 119; 123; 128; 134; 135; 138; 139; 140; 144; 150; 155; 157; 160; 161; 163; 168; 169; 172; 177; 178; 179; 184; 190; 193; 196; 197; 199; 202; 203; 204; 205; 207; 212; 214; 220; 221; 228; 230; 232; 235; 238; 240; 242; 243; 251;
Direct yellow 2,33,34,35,38,39,43,47,50,54,58,68,69,70,71,86,93,94,95,98,102,108,109,129,136,138,141;
Direct orange 34,39,41,46,50,52,56,57,61,64,65,68,70,96,97,106,107;
Direct red 79,82,83,84,91,92,96,97,98,99,105,106,107,172,173,176,177,179,181,182,184,204,207,211,213,218,220,221,222,232,233,234,241,243,246,250;
Direct purple 47,52,54,59,60,65,66,79,80,81,82,84,89,90,93,95,96,103,104;
Direct blue 57; 77; 80; 81; 84; 85; 86; 90; 93; 94; 95; 97; 98; 99; 100; 101; 106; 107; 1 08; 109; 113; 114; 115; 117; 119; 137; 149; 150; 153; 155; 156; 158; 159; 160; 161; 162; 163; 164; 166; 167; 170; 171; 172; 173; 188; 189; 190; 192; 193; 194; 196; 198; 199; 200; 207; 209; 210; 212; 213; 214; 222; 228; 229; 237; 238; 242; 243; 244; 245; 247; 248; 250; 251; 252; 256; 257; 259; 260; 268; 274; 275; 293;
Direct green 25,27,31,32,34,37,63,65,66,67,68,69,72,77,79,82;
Mordant yellow 5,8,10,16,20,26,30,31,33,42,43,45,56,50,61,62,65;
Food yellow 3;
And the derivant of these dyestuffs.
In above-mentioned acid dyes, preferred acidic black 24;
Acid blue 23,25,29,62,80,86,87,92,138,158,182,243,324:1;
Acid orange 8,51,56,74,63;
Acid red 1,4,8,34,37,42,52,57,80,97,114,143,145,151,183,217,249;
Acid violet 7;
Indian yellow 17,25,29,34,42,72,76,99,111,112,114,116,134,155,169,172,184,220,228,230,232,243;
The derivant of these dyestuffs of dye well such as ACID GREEN 25.
In addition, also preferred above-mentioned azo system, xanthene in addition is, the acid dyes of phthalocyanine system, also preferably uses C.I. solvent blue 44,38; C.I. the solvent orange 45; The derivant of acid dyess such as rhodamine B, rhodamine 110 and these dyestuffs.
Wherein, As (D) colorant, be preferably selected from the colorant of triallyl methane series, anthraquinone system, azomethine system, benzylidene system, oxygen alcohol system, anthocyanin system, phenothiazines, pyrrolo-pyrazoles azomethine system, xanthene system, phthalocyanine system, chromene system, indigo system, pyrazoles azo system, aniline azo system, pyrazolone triazole azo system, pyridone azo system, Anthrapyridone system.
As the content of (4) colorant in the cured composition for color of first embodiment, 25～95 quality % in total solid state component of preferred consolidation property composition, more preferably 30～90 quality %, and then preferred 40～80 quality %.
< (5) composition: compound>with ethene property unsaturated double-bond
The cured composition for color of preferred first embodiment also contains the compound that (5) have ethene property unsaturated double-bond except said (1) composition, and (3) the composition.
The compound with ethene property unsaturated double-bond that can use in the first embodiment is the addition polymerization property compound with at least one ethene property unsaturated double-bond, is selected from the compound with at least one preferred plural terminal ethene property unsaturated link.Such compound group is widely known by the people in this industrial field, can these not special qualification ground be used in the first embodiment.These for example have, and monomer, prepolymer are dipolymer, trimer and oligomer or their potpourri and their chemical forms such as multipolymer.
Example as monomer and multipolymer thereof; (for example can enumerate unsaturated carboxylic acid; Acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid etc.) or its ester class, preferably use the ester class of unsaturated carboxylic acid and aliphatic polyol compound.In addition, also be fit to use addition reaction product with the substituent esters of unsaturated carboxylic acids of nucleophilicities such as hydroxyl or amino, sulfydryl and simple function group or many functional group isocyanates's class or epoxies, reach and the dehydration condensation product of simple function group or multi-functional carboxylic acid etc.In addition; Also be fit to have the addition reaction of substituent unsaturated carboxylate types of electrophilicity such as NCO or epoxy radicals and simple function group or multi-functional alcohols, amine, thio-alcohol, and have unsaturated carboxylate type and simple function group or multi-functional alcohols, the amine of cancellation substituents such as halogen radical or tosyloxy, the substituted reactant of thio-alcohol.In addition,, also can use the compound group that is replaced into unsaturated phosphonic acids, styrene, vinyl ether etc., replace above-mentioned unsaturated carboxylic acid as other examples.
In the concrete example of the monomer of the ester of aliphatic polyol compound and unsaturated carboxylic acid; As acrylic ester, glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, trimethylolethane trimethacrylate acrylic ester, hexanediyl ester, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol acrylate, D-sorbite triacrylate, D-sorbite tetraacrylate, D-sorbite five acrylic ester, D-sorbite six acrylic ester etc. are arranged.
As methacrylate, tetramethylene glycol dimethylacrylate, triethylene glycol dimethylacrylate, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, trimethylolethane trimethacrylate methacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethylacrylate, hexanediol dimethacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylic ester, dipentaerythritol dimethylacrylate, dipentaerythritol hexamethyl acrylic ester, D-sorbite trimethyl acrylic ester, D-sorbite tetramethyl acrylic ester, two (p-(3-methacryloxy-2-hydroxyl propoxyl group) phenyl) dimethylmethane, two-(p-(methacryloxy ethoxy) phenyl) dimethylmethane etc. are arranged.
As itaconate, ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1,3-butylene glycol diitaconate, 1,4-butylene glycol diitaconate, tetramethylene glycol diitaconate, pentaerythrite diitaconate, D-sorbite four itaconates etc. are arranged.As crotonates, ethylene glycol bisthioglycolate crotonates, tetramethylene glycol two crotonatess, pentaerythrite two crotonatess, D-sorbite four or two crotonatess etc. are arranged.
As the iso-crotonic acid ester, ethylene glycol bisthioglycolate iso-crotonic acid ester, pentaerythrite two iso-crotonic acid esters, D-sorbite four iso-crotonic acid esters etc. are arranged.As maleate, ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate, D-sorbite four maleates etc. are arranged.
Example as other esters; For example; The aliphatic alcohol that also be fit to use the special public clear 51-47334 of Japan, japanese kokai publication sho 57-196231 record is the ester with aromatic series pastern bone frame of ester class or japanese kokai publication sho 59-5240, japanese kokai publication sho 59-5241, japanese kokai publication hei 2-226149 record, japanese kokai publication hei 1-165613 record contain amino ester etc.And then described ester monomer can also use as potpourri.
And then; Through using the addition polymerization property compounds that in molecule, has amino structure or sulfide based structural of record in japanese kokai publication sho 63-277653 number, japanese kokai publication sho 63-260909 number, japanese kokai publication hei 1-105238 number, can access the very superior optical polymerism composition of film speed.
As other examples, can enumerate the polyester acrylate class put down in writing in japanese kokai publication sho 48-64183 number, special public clear 49-43191 number of Japan, special public clear 52-30490 number each communique of Japan, make epoxy resin and the reaction of (methyl) acrylic acid and multi-functional acrylic ester or methacrylates such as epoxy acrylate class.In addition, can also enumerate Japan special public clear 46-43946 number, Japan special fair 1-40337 number, the specific unsaturated compound of special fair 1-40336 number record of Japan or vinyl phosphonate based compound of japanese kokai publication hei 2-25493 number record etc.In addition, under certain conditions, be fit to use the structure that contains perfluoroalkyl of 61-22048 number record of japanese kokai publication sho.And then, can also use in the publication vol.20 of the bonding association of Japan, No.7,300～308 pages (1984) material of introducing as photo-curable monomer and oligomer.
About these addition polymerization property compounds, its structure, separately use is still share, the details of the method for application of addition etc. can at random set according to the performance design of final composition.For example, select from following viewpoint.
From the aspect of light sensitivity, preferably in the many structures of the unsaturated group content of each molecule, under a large amount of situation, more than preferred two functional groups.In addition; Promptly solidify film strength in order to improve portrait portion; Trifunctional is above to be good; And then through share the material of the different polymerism base of different functional group's numbers (for example acrylic ester, methacrylate, polystyrene compound, vinyl ether based compound), the method for regulating light sensitivity and film strength is also effective.From solidifying the viewpoint of light sensitivity, the preferred compound that contains (methyl) acrylate structural more than 2 that uses more preferably uses and contains the compound more than 3, most preferably uses and contains the compound more than 4.In addition, from solidifying light sensitivity, and the viewpoint of unexposed development property, preferably contain EO modification body.In addition, from solidifying light sensitivity, and the viewpoint of exposure portion intensity, preferably contain urethane bond.
In addition; For with composition in other compositions (for example; The intermiscibility of binder polymer, initiating agent, colorant (pigment, dyestuff etc.), dispersed; The essential factor that the selection of polyaddition compounds attaches most importance to usage to want, for example, use or two or more the share through the low-purity compound sometimes improves intermiscibility.In addition, also sometimes from make substrate or after the purpose that improves of the adhesiveness of the external coating stated etc., can select specific structure.
From above viewpoint; Can bisphenol a diacrylate, bisphenol a diacrylate EO modification body, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, trimethylolethane trimethacrylate acrylic ester, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol five acrylic ester, dipentaerythritol acrylate, D-sorbite triacrylate, D-sorbite tetraacrylate, D-sorbite five acrylic ester, tetramethylol methane tetraacrylate EO modification body, dipentaerythritol acrylate EO modification body etc. be enumerated as preferred material; In addition; As commercially available article, preferred DPHA-40H (Japanese chemical drug corporate system), AH-600, T-600, AI-600 (common prosperity corporate system).
Wherein, More preferably bisphenol a diacrylate EO modification body, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylic ester, dipentaerythritol acrylate, tetramethylol methane tetraacrylate EO modification body, dipentaerythritol acrylate EO modification body etc.; As commercially available article, more preferably DPHA-40H (Japanese chemical drug corporate system), AH-600, T-600, AI-600 (common prosperity corporate system).
In the first embodiment; (1) composition, and content beyond (3) composition, that (5) have a compound of the two keys of ethene property in the solid state component of the cured composition for color of first embodiment, be 0.5～30.0 quality % preferably; More preferably 1.0～20.0 quality %, and then preferred 5.0～15.0 quality %.
< (6) composition: alkali soluble resin >
In the cured composition for color of first embodiment, to first-class purpose,,, use alkali soluble resin also can as binder polymer except (1) the composition from the epithelium characteristic.
As alkali soluble resin, preferably use the wire organic polymer." wire organic polymer " as such can at random use known wire organism.Preferably in order to carry out water development or weak base water development, selecting water or weak base water is the wire organic polymer of solubility or swellability.The wire organic polymer not only forms agent as epithelium and uses, but also uses corresponding to selecting as the purposes of water, weak base water or organic solvent developer.For example, under the situation of using the water dissolvable organic polymer, can carry out water development.As such wire organic polymer; Can enumerate the material that has record in group condensate, for example japanese kokai publication sho 59-44615 number, special public clear 54-34327 number of Japan, special public clear 58-12577 number of Japan, special public clear 54-25957 number of Japan, japanese kokai publication sho 54-92723 number of the carboxylic acid group, japanese kokai publication sho 59-53836 number, japanese kokai publication sho 59-71048 number at side chain, promptly, make monomer homopolymerization with carboxyl or copolymerization and resin, make monomer homopolymerization or copolymerization with acid anhydrides and make hydrolysis of acid anhydrides unit or half esterization or half amideization and resin, with the used for epoxy resin unsaturated monocarboxylic and anhydride modified and epoxy acrylate etc.As monomer with carboxyl, can enumerate acrylic acid, methacrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, 4-carboxyl styrene etc., as monomer, can enumerate maleic anhydride etc. with acid anhydrides.
In addition, the acid cellulose derivant that has carboxylate radical at side chain is arranged equally.In addition, usefully at material with addition cyclic acid anhydride on the condensate of hydroxyl etc.
With alkali soluble resin as under the situation of multipolymer, as the compound of copolymerization, the monomer of can also priority of use enumerating other monomer in addition.As other the example of monomer, can enumerate the compound of following (1)～(13).
(1) 2-hydroxyethylmethacry,ate, 2-hydroxypropyl acrylic ester, 3-hydroxypropyl acrylic ester, 4-hydroxybutyl acrylic ester, 2-hydroxyethyl methacrylate, 2-hydroxy propyl methacrylate, 3-hydroxy propyl methacrylate, 4-hydroxybutyl methacrylate etc. have esters of acrylic acid, and the methyl acrylic ester of aliphatic hydroxyl.
(2) methyl acrylate; The acrylic acid ethyl ester; The acrylic acid propyl diester; Butyl acrylate cores; The acrylic acid isobutyl; Acrylic acid amyl group ester; The acrylic acid hexyl ester; 2-ethylhexyl acrylate; Acrylic acid octyl group ester; The acrylic acid benzyl ester; Acrylic acid-2-chloro-ethyl ester; Glycidyl acrylate; 3; 4-epoxycyclohexyl methacrylate; The vinylacrylic acid ester; 2-phenyl vinyl acrylic ester; 1-propenyl acrylic ester; The allyl acrylic ester; 2-allyloxy ethyl acrylic ester; Alkyl acrylates such as propargyl acrylic ester.
(3) methyl methacrylate; The methacrylic acid ethyl ester; The methacrylic acid propyl diester; The methacrylic acid butyl ester; The methacrylic acid isobutyl; Methacrylic acid amyl group ester; The methacrylic acid hexyl ester; Methacrylic acid 2-ethylhexyl; The methacrylic acid cyclohexyl ester; The methacrylic acid benzyl ester; Methacrylic acid-2-chloro-ethyl ester; Glycidyl methacrylate; 3; 4-epoxycyclohexyl methyl acrylic ester; The vinyl methacrylate; 2-phenyl vinyl methacrylate; 1-propenyl methacrylate; The allyl methyl acrylic ester; 2-allyloxy ethyl methacrylate; Alkylmethacrylates such as propargyl methacrylate.
(4) acrylic amide; Methacrylamide; N hydroxymethyl acrylamide; The N-ethyl acrylamide; N-hexyl methyl acrylic amide; N-cyclohexyl acrylic amide; N-hydroxyethyl acrylic amide; N phenyl acrylamide; N-nitrobenzophenone acrylic amide; N-ethyl-N phenyl acrylamide; The vinyl acrylic amide; The vinyl Methacrylamide; N; N-diallyl acrylic amide; N; N-diallyl Methacrylamide; The allyl acrylic amide; Acrylic amide or Methacrylamides such as allyl methyl acrylic amide.
(5) vinyl ethers such as ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, octyl group vinyl ether, Vinyl phenyl ether.
(6) vinyl esters such as vinylacetate, vinyl chloroacetate ester, vinyl butyrate, benzoic acid vinyl.
(7) phenylethylenes such as styrene, AMS, methyl styrene, 1-chloro-4-methyl-benzene, p-acetoxy-styrene.
(8) vinyl ketones such as methyl vinyl ketone, ethyl vinyl ketone, propyl ethylene base ketone, phenyl vinyl ketone.
(9) olefines such as ethene, propylene, isobutylene, butadiene, isoprene.
(10) N-vinyl pyrrolidone, vinyl cyanide, methacrylonitrile etc.
(11) unsaturated acyl imines such as maleic amide, N-acryloyl group acrylic amide, N-acetyl group Methacrylamide, N-propiono Methacrylamide, N-(p-chlorobenzene acyl group) Methacrylamide.
(12) combined heteroatomic metha crylic monomer in the α position.For example, can enumerate the compound of record in the special 2001-115595 of hope of Japan instructions, No. 598 instructionss of the special 2001-115 of hope of Japan etc.
Wherein, The alkali soluble resin of in side chain has (methyl) acryl resin and TOHKEMY 2000-187322 communique, the TOHKEMY 2002-62698 communique of allyl or vinyl ester group and carboxyl, putting down in writing of in side chain has alkali soluble resin or the TOHKEMY 2001-242612 communique of two keys, putting down in writing that has an amide group at side chain is superior aspect film strength, light sensitivity, development property balanced, thereby is fit to.
In addition; Japan special fair 7-12004 number, Japan special fair 7-120041 number, Japan special fair 7-120042 number, Japan special fair 8-12424 number, japanese kokai publication sho 63-287944 number, japanese kokai publication sho 63-287947 number, japanese kokai publication hei 1-271741 number, Japan be special be willing to flat 10-116232 number etc. in the polyurethane series binder polymer that contains acidic group of record; The side chain of putting down in writing among the TOHKEMY 2002-107918 has the polyurethane series binder polymer of acidic group and two keys; Because intensity is very superior; Therefore consider to have advantage from the adaptive aspect of the low exposure of anti-brush property.
In addition, the ethylidene ether modification polyethenol series binder polymer with acid group of record is superior aspect film strength, development property balanced among Europe patent 993966, Europe patent 1204000, the TOHKEMY 2001-318463 etc., thereby is fit to.
And then, in addition, as water-soluble wire organic polymer, usefully polyvinyl pyrrolidone or polyethylene oxide etc.In addition, in order to improve the intensity of cured film, also usefully pure soluble nylon or 2,2-be two-polyethers of (4-hydroxy phenyl)-propane and chloropropylene oxide etc.
As the weight-average molecular weight of the alkali soluble resin that can use in the first embodiment, preferred more than 5000, more preferably 10,000～300,000 scope is preferred more than 1000 about number-average molecular weight, more preferably 2000～250,000 scope.Polydispersity (weight-average molecular weight/number-average molecular weight) is preferred more than 1, and then preferred 1.1～10 scope.
These polymkeric substance can be atactic polymers, block polymer, graft polymer etc.
(1) as the addition of the alkali soluble resin beyond the composition, the scope of 5～20 quality % in total solid state component of the cured composition for color of preferred first embodiment, more preferably 5～12 quality %.
< (7) spreading agent >
In the cured composition for color of first embodiment, contain under the situation of pigment, from improving the viewpoint of this dispersing of pigments property, preferred (7) spreading agent that adds as colorant.
As the spreading agent that can use in the first embodiment (pigment dispersing agent); Macromolecule dispersing agent (for example, daiamid gathers (methyl) acrylic ester, (methyl) acrylic acid series copolymer, naphthalene sulfonic acids formalin condensation product with its salt, poly carboxylic acid and its salt, HMW unsaturated acid ester, modified polyurethane, modified poly ester, modification) be can enumerate, polyxyethylated phosphate, polyoxyethylene alkyl amine, alkanolamine, pigment derivative etc. reached.Macromolecule dispersing agent is according to its structure, and then is categorized as straight chain shape macromolecule, terminal-modified type macromolecule, graft type macromolecule, block type polymer.
The macromolecule dispersing agent performance is adsorbed in the surface of pigment, prevents the effect of condensing again.Therefore, can the terminal-modified type macromolecule, graft type macromolecule, the block type polymer that have to the anchor site of surface of pigments be enumerated as preferred construction.On the other hand, pigment derivative has: through to the surface of pigments modification, promote the effect of the sorption of macromolecule dispersing agent.
As the concrete example of the pigment dispersing agent that can use in the first embodiment, can enumerate BYK Chemie corporate system " Disperbyk-101 (daiamid phosphate), 107 (carboxylates), 110 (copolymer that comprises acid group), 130 (polyamide), 161,162,163,164,165,166,170 (high-molecular copolymers) ", " BYK-P104, P105 (HMW unsaturated polyester carboxylic acid), EFKA corporate system " EFKA4047,4050,4010,4165 (polyurethane series), EFKA4330,4340 (block copolymer), 4400,4402 (modified polyacrylates), 5010 (polyesteramides), 5765 (HMW polycarboxylate), 6220 (fatty acid polyesters), 6745 (phthalocyanine derivates), 6750 (AZOpigments derivative) ", monosodium glutamate fine techniques corporate system " this handkerchief of Archie PB821, PB822 ", common prosperity company chemistry corporate system " Fu Lulong TG-710 (urethane oligomers) ", " gathering Off ロ one No.50E, No.300 (acrylic acid series copolymer) ", nanmu originally change into soap corporate system " this handkerchief silk 5000 (phthalocyanine derivates), 22000 (AZOpigments derivative) of Oulu, 13240 (polyesteramines), 3000,17000,270 00 (portion has the macromolecule of function portion endways), 24000,28000,32000,38500 (graft type macromolecules) ", daylight chemicals person system " Nikkor T106 (polyoxyethylene sorbitan monoleate), MYS-IEX (polyoxyl 40 stearate) " etc. in corporate system " Di Sipalong KS-860,873SN, 874, #2150 (aliphatic polyvalent carboxylic acid), #7004 (polyether ester), DA-703-50, DA-705, DA-725 ", KAO. Corp. SA's system " Di Moer RN, N (the heavy condensation product of naphthalene sulfonic acids formalin), MS, C, SN-B (the heavy condensation product of aromatic sulphonic acid formalin) ", " He Mona gill L-18 (polymeric polycarboxylic acid) ", " Chinese mugwort Viktor Markin 920,930,935,985 (polyoxyethylene nonylplenyl ether) ", " A Xitamin 86 (stearyl amine acetic acid esters) ", the conduct.
These spreading agents can use separately, also can two or morely use.In the first embodiment, especially preferred compositions is used pigment derivative and macromolecule dispersing agent.
As the content of the spreading agent in first embodiment, be 1～80 quality % preferably with respect to pigment, more preferably 5～70 quality %, and then preferred 10～60 quality %.
Specifically, using under the situation of macromolecule dispersing agent, as its use amount, preferably is the scope of 5～100 quality %, the more preferably scope of 10～80 quality % with respect to pigment.In addition, using under the situation of pigment derivative, as its use amount, preferably is the scope of 1～30 quality % with respect to pigment, the more preferably scope of 3～20 quality %, the scope of especially preferred 5～15 quality %.
In the first embodiment; Under the situation of use as the pigment of colorant and spreading agent; From solidifying the viewpoint of light sensitivity, colour saturation; The summation of the content of preferred colorant and spreading agent is more than the 30 quality % below the 90 quality %, more preferably below the above 85 quality % of 40 quality %, and then below the above 80 quality % of preferred 50 quality % with respect to the total solid state component that constitutes cured composition for color.
The cured composition for color of first embodiment also can further contain adjuvant.Below, preferred additives etc. is described.
< alkoxysilane compound containing trialkylsilyl group in molecular structure >
The cured composition for color of first embodiment is from the adhering viewpoint of raising with substrate, and preferred alkoxysilane compound containing trialkylsilyl group in molecular structure wherein preferably share silane coupling agent.
In the silane coupling agent as can with the preferred alkoxysilyl of the chemically combined water-disintegrable base of inorganic material; With organic resin combine preferred (methyl) acryloyl group of base, phenyl, sulfydryl, epoxy silane, wherein more preferably (methyl) acryloyl group propyl trimethoxy silicane.
As the addition under the situation of using silane coupling agent, the scope of 0.2～3.0 quality % in total solid state component of the cured composition for color of preferred first embodiment, more preferably 0.5～1.0 quality %.
<being total to sensitizer >
The cured composition for color of preferred first embodiment contains common sensitizer according to expectation.In the first embodiment, altogether sensitizer has: further improve sensitizing coloring matter or polymerization initiator to the light sensitivity of active radioactive ray or the polymerization that suppresses the polymerizable compound that oxygen causes effect such as encumber.
Example as so common sensitizer; Can enumerate the compound of people such as amine, for example M.R.Sander outstanding " polymer science magazine " the 10th volume 3173 pages of (1972), the special public clear 44-20189 communiques of Japan, japanese kokai publication sho 51-82102 communique, japanese kokai publication sho 52-134692 communique, japanese kokai publication sho 59-138205 communique, japanese kokai publication sho 60-84305 communique, japanese kokai publication sho 62-18537 communique, japanese kokai publication sho 64-33104 communique, No. 33825 records of research announcement etc.; Specifically, can enumerate triethanolamine, p-dimethylamino benzoic acid ethyl ester, p-formoxyl xylidin, p-methyl sulfo-xylidin etc.
Other example as sensitizer altogether; Can enumerate mercaptan and thioether class, for example; Japanese kokai publication sho 53-702 communique, the special public clear 55-500806 communique of Japan, the mercaptan compound of japanese kokai publication hei 5-142772 communique record, the disulfide compound of japanese kokai publication sho 56-75643 communique etc., specifically, can enumerate 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-sulfydryl-4 (3H)-quinazoline, β-mercaptonaphthalene etc.
In addition; As other example of sensitizer altogether, can enumerate the hydrogen donor that the special public clear 55-34414 communique of organometallics (example, tributyl tin acetic acid esters etc.), Japan of amino-acid compound (example, N-phenylglycine ester etc.), the special public clear 48-42965 communique record of Japan puts down in writing, the sulphur compound (example, trithiane etc.) that japanese kokai publication hei 6-308727 communique is put down in writing etc.
The viewpoint that makes progress of the curing rate that the content of these common sensitizers causes from the equilibrium of aggregation growth speed and chain transfer; Preferably the quality with respect to total solid state component of solidification compound is the scope of 0.1～30 quality %; The more preferably scope of 1～25 quality %, and then the scope of preferred 0.5～20 quality %.
< polymerization inhibitor >
In the first embodiment, in order to stop the useless thermal polymerization of the compound of the ethene property unsaturated double-bond with possibility polymerization in the manufacturing of solidification compound or in preserving, expectation is added a spot of thermal polymerization and is prevented agent.
As using thermal polymerization to prevent agent in the first embodiment, can enumerate quinhydrones, p-metoxyphenol, two-t-butyl-p-cresols, 1,2,3,-thrihydroxy-benzene, t-butyl catechol, benzo quinone, 4,4 '-thiobis (3-methyl-6-t-butylphenol), 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-t-butylphenol), the N-nitroso-phenyl hydramine first cerium salt etc.
The addition that preferred thermal polymerization prevents agent is about 0.01 quality %～about 5 quality % with respect to the quality of total compsn.In addition, as required,, add the advanced higher fatty acid derivative of behenic acid or behenamide and so on etc., in the process of the drying after the coating, in the set of surfaces of photographic layer, also can for the polymerization that anti-block causes.About 0.5 quality % of the preferred total compsn of addition of advanced higher fatty acid derivative～about 10 quality %.
< other adjuvant >
And then, in the first embodiment,, add known adjuvants such as inorganic filler or plastifier and also can in order to improve the rerum natura of cured film.
As plastifier; For example; Dioctyl phthalate (dop), two dodecyl phthalate ester, triethylene glycol dicaprylate, dimethyl glycol phthalate ester, trimethylphenyl phosphonate ester, dioctyl adipate, dibutyl sebacate, triacetyl glycerine etc. are arranged; Used under the situation of bond, can add below the 10 quality % with respect to the total quality of compound with ethene property unsaturated double-bond and binder polymer.
< solvent >
The cured composition for color of first embodiment also is dissolvable in water various organic solvents and supplies in use when when the manufacturing of color filter, being coated on supporter.
As organic solvent, acetone, methyl ethyl ketone, cyclohexane, acetic acid ethyl ester, ethene dichloride, tetrahydrofuran, toluene, glycol monomethyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol dimethyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether, pentanedione, cyclohexanone, DAA, monoethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, glycol monomethyl isopropyl ether, ethylene glycol monobutyl ether acetic acid esters, 3-methoxypropanol, methoxymethoxy ethanol, diethylene glycol monomethyl ether, TC, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol list ethylether acetic acid esters, 3-methoxy propyl yl acetate, N, dinethylformamide, dimethyl sulfoxide (DMSO), gamma-butyrolacton, lactic acid methyl ester, lactic acid ethyl ester etc. are arranged in this use.
These solvents can separately or mix and use.The concentration of the solid state component in the preferred organic solvent is 2～60 quality %.
The color filter of first embodiment solidifies with ISO with cured composition for color, and has good pattern system generation, and is superior with the adhesiveness of supporter.
[color filter and manufacturing approach thereof]
Secondly, the color filter and the manufacturing approach thereof of first embodiment are described.
The color filter of first embodiment is characterized in that, has the colored pattern that the color filter that uses first embodiment forms with cured composition for color.
Below, about the color filter of first embodiment, detail through its manufacturing approach (manufacturing approach of the color filter of first embodiment).
The manufacturing approach of the color filter of first embodiment; It is characterized in that; Comprise: on supporter; The color filter that applies first embodiment is used cured composition for color, the operation of formation cured composition for color layer (below, suitably abbreviate " the cured composition for color layer forms operation " as); With said cured composition for color layer across the operation of mask exposure (below, suitably abbreviate " exposure process " as); Said cured composition for color layer after the exposure is developed, the operation of formation colored pattern (below, suitably abbreviate " developing procedure " as.)。
Below, each operation in the manufacturing approach of first embodiment is described.
< the cured composition for color layer forms operation >
Form in the operation at the cured composition for color layer, on supporter, apply the cured composition for color of first embodiment, form the cured composition for color layer.
As the supporter that can in this operation, use; For example; Can enumerate soda-lime glass, Pa Likesi (registered trademark) glass, the quartz glass that uses in the liquid crystal display cells etc. and make them adhere to the supporter of nesa coating, or the photo-electric conversion element substrate that uses in the imaging apparatus etc. for example silicon substrate etc. or auxilliary property burning film semiconductor (CMOS) etc. mutually.These substrate is formed with the black streaking of isolating each picture element sometimes.
In addition, on these supporters, as required, for top the layer adhesion improvement, the diffusion preventing of material or the planarization of substrate surface, undercoat is set also can.
As the coating method of the cured composition for color of first embodiment on supporter, can be suitable for slit coating, ink-jet method, spin coating, stream and mould various coating methods such as coating, roller coat, stencil printing.
As the coating thickness of solidification compound, preferred 0.1～10 μ m, more preferably 0.2～5 μ m, and then preferred 0.2～3 μ m.
With regard to the drying (prebake) of the cured composition for color layer that on substrate, applies, can utilize in hot plate, the baking box etc., under 50 ℃～140 ℃ temperature, carried out with 10～300 seconds.
< exposure process >
In exposure process, will form the cured composition for color layer that forms in the operation at said cured composition for color layer and make public across the mask of mask pattern with regulation.
Exposure in this operation is preferably carried out through the irradiation of radioactive ray, wherein, preferably uses ultraviolet rays such as g ray, i ray, especially preferably uses high-pressure sodium lamp.
Preferred 5～the 1500mJ/cm of exposure
2, more preferably 10～1000mJ/cm
2, 10～500mJ/cm most preferably
2
< developing procedure >
Behind exposure process, then carry out the alkali development treatment, make thus in the exposure process light not illuminated portion be eluted in the aqueous alkali.
As developer solution, expectation does not cause the organic base developer solution of damage to the loop of substrate etc.
As development temperature, be generally 20 ℃～30 ℃, development time is 20～90 seconds.
As the alkaline agent that in developer solution, uses; For example; Can enumerate ammoniacal liquor, ethylamine, diethylamide, dimethylethanolamine, TMAH, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1,8-diaza-bicyclo-[5,4,0]-organic basic compounds such as 7-undecylene; As developer solution, it is 0.001～10 quality % that preferred use pure water is diluted to concentration with these alkaline agents, preferably becomes the alkaline aqueous solution of 0.01～1 quality %.Also have, use under the situation of the developer solution that comprises such alkaline aqueous solution, after development, clean (spray) usually with pure water.
Also have; In the manufacturing approach of first embodiment; After having carried out above-mentioned cured composition for color layer formation operation, exposure process, reaching developing procedure, as required, also can comprise colored pattern utilization heating that forms and/or the curing process that makes public and solidify.
As in this heat treated of carrying out (afterwards curing),, carry out 100 ℃～240 ℃ heat curing usually and handle for being used to make the heat treated after the development that completion of cure carries out.At substrate is under the situation of glass substrate or silicon substrate, in the said temperature scope preferred 200 ℃～240 ℃.
After this, cure in the processing,,, utilize heating arrangements such as hot plate or baking oven (heated air circulation type dryer), high frequency heating machine, carry out with continous way or batch type like above-mentioned condition for the coated film after developing.
The cured composition for color layer of counting the above explanation of degree through the form and aspect of expecting repeatedly forms operation, exposure process, reaches developing procedure (and then curing process as required), makes the color filter of the form and aspect that comprise expectation.
The color filter of first embodiment uses the cured composition for color of first embodiment; Therefore; The colored pattern that forms shows and the high adhesiveness of supporter substrate that the anti-development property of cured compositions is superior, so the exposure light sensitivity is superior; The good adhesion of exposure portion and substrate, and can form the pattern of the high-resolution of the section shape of giving expectation.Thereby, can be fit to be used in solid-state imagers such as liquid crystal display cells or CCD, especially, be fit to surpass among CCD element or the CMOS etc. of high-resolution of 1,000,000 pixels.The color filter that the color filter of first embodiment for example can be used as at the light accepting part of each pixel that constitutes CCD and be used for disposing between the lenticule of optically focused.
Below, specify second embodiment.
< colored curable resin composition >
The colored curable resin composition of second embodiment; It is characterized in that; Comprise: (a) compound, (c) with at least one ethene property unsaturated double-bond of look material, (b) is included in adhesive resin that side chain has (methyl) acrylic copolymer of ester ring type (methyl) acryloyl group, (d) Photoepolymerizationinitiater initiater, and (e) has at least one ethene property unsaturated double-bond, in molecule, has to be selected from urethane, acid amides, and the compound of the part-structure of urea.
Except said necessary composition, can also add other any compositions in the said colored curable resin composition.
Preferred 2～50 quality % of concentration of shared total solid state component in the said colored curable resin composition, in total colored curable resin composition, and then preferred 10～30 quality %, the scope of especially preferred 15～25 quality %.
Below, specify the constituent of this colored curable resin composition etc.
< (e) have at least one ethene property unsaturated double-bond, in molecule, have the compound that is selected from urethane, acid amides, reaches the part-structure of urea >
As (e) in second embodiment have at least one ethene property unsaturated double-bond (below; Suitably be called the polymerism base); In molecule, has the compound that is selected from urethane, acid amides, reaches the part-structure of urea; Can be for being selected from the compound that in molecule, has polymerism base and urethane bond, the compound that in molecule, has polymerism base and amide group, and in molecule, having any of compound of polymerism base and urea bond; But the viewpoint from pattern becomes second nature wherein preferably has polymerism base and urethane bond in molecule as part-structure.In this manual, this compound suitably is called (e) specific aggregation property compound or (e) composition.
Be somebody's turn to do (e) specific aggregation property compound preferably has the nitrogen atom heterocycle in its structure compound, and then preferably have the compound of cyamelide ester bond.
In addition, if consider the influence that (e) composition is given the rerum natura of the solidification compound of second embodiment, then for example; Viewpoint from development property; Preferably except said structure, in molecule, has oxyalkylene group, as oxyalkylene group; Optimization ethylene oxide, epoxypropane, especially optimization ethylene oxide base.
(e) composition has ethene property unsaturated double-bond base in molecule, therefore, together contribution is played in the curable raising of composition with other polymerizable compounds.
Also have; As the urethane compound that in second embodiment, be fit to use, and the concrete example of cyamelide ester compounds, can preferably enumerate compound and by the reaction product of the alcoholic compound of formula (I) expression with isocyanic acid ester bond with ethene property unsaturated link as (e) composition.
[changing 18]
General formula (I)
In said general formula (I), R
1, R
2Represent hydrogen atom or methyl respectively independently.
R
3Expression hydrogen atom, methyl, by the functional group of formula (II) expression or by the functional group of formula (III) expression, wherein preferably by the functional group of general formula (III) expression.
[changing 19]
General formula (II) general formula (III)
In above-mentioned general formula (II), n representes 1～10 integer.In addition, in general formula (II) and the general formula (III), R
4Expression hydrogen atom or methyl, in general formula (III), the R of a plurality of existence in molecule
4Can be identical, also can be inequality.As at this preferred R
4, can enumerate hydrogen atom or methyl.
As alcoholic compound, can enumerate following illustrative compound (MA-1)～(MA-4), (MA-11), (MA-12) or compound (MA-5)～(MA-10) etc., but be not limited to this by said general formula (I) expression.
(alcohols: exemplary compounds (MA-1)～(MA-12))
[changing 20]
In MA-5～MA-7, the integer of m=1～20
In MA-8～MA-10, R=hydrogen or methyl
The rational number of O, p, q, r, st=0～20
[changing 21]
As (e) composition, the reaction product of the alcohols that is preferably selected from said exemplary compounds and the compound that is selected from the isocyanates based compound (MU-1)～(MU-27) shown in following.
Having the compound of isocyanic acid ester bond and the reaction of alcoholic compound for example carries out through following condition.
As the addition of isocyanate compound and alcoholic compound, the hydroxyl molal quantity of regulating the NCO molal quantity that makes isocyanate compound and alcoholic compound equates.
As catalysts; Do not limit especially; But preferably use organotin (methyl) acrylates such as three (2 ethyl hexanoic acid) bismuth, dibutyl tin dilaurate, di-n-butylacetic acid tin, dibutyl tin dichloride, tin octoate; Organic zinc such as zinc octoate, zinc naphthenate (methyl) acrylates, tertiary amines such as triethylene diamine, triethylamine, 1,8-nitrogen two ring [5,4,0] undecylenes-7 etc. have (methyl) acrylic ester of amidine skeleton; Can add with the scope of 0.0001～10 weight portion with respect to mercaptan or isocyanates 100 weight portions.
Also have, in this instructions, under the both sides of expression acrylic ester, methacrylate or arbitrary side's the situation, be labeled as " (methyl) acrylic ester " sometimes.
As reaction conditions, be suitable for-50 ℃～100 ℃ temperature range usually.Under the situation below-50 ℃, the progress of reaction is extremely slow, and under the situation more than 100 ℃, accessory substance increases, and yield reduces, and, possible gelation, thus not preferred.As required, utilize solvent to dilute.The solvent that uses all can use except the material of alcohol, carboxylic acid, amine etc. and isocyanate reaction; But from reaction velocity, dissolubility aspect, preferably using chlorine such as acetonitrile, N, dinethylformamide (DMF), N, N-dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO), N-N-methyl-2-2-pyrrolidone N-(NMP) isopolarity solvent, chloroform is fragrant family solvents such as solvent, toluene, xylene.In addition, in order to prevent the reaction of residuary water and isocyanates, suitably use dehydrated solvent.
After reaction finishes, after under reduced pressure this reaction solution being concentrated, with silicagel column (eluant: ethyl acetate/n-hexane=1/1) come purifying.Can also be through chromatography, recrystallizationization, deposition is come purifying again.
Can generate urethane compound as preferred (e) composition of second embodiment with ethene property unsaturated link, and the concrete compound of the isocyanates of cyamelide ester compounds illustrate as follows.
(isocyanates: exemplary compounds (MU-1)～(MU-27))
[changing 22]
[changing 23]
[changing 24]
In addition; As can also be in second embodiment except above-mentioned isocyanates based compound suitably used isocyanates based compound; As concrete example; For example, can enumerate the polyisocyanate compounds of putting down in writing in the special public clear 48-41708 communique of Japan that in a molecule, has 2 above NCOs.
In addition, the isocyanates based compound in the urethane compound class with oxirane pastern bone frame that special public clear 58-49860 number of the urethane acrylate class of record or Japan, Japanese spy public clear 56-17654 number, special public clear 62-39417 number of Japan, Japan spy put down in writing for public clear 62-39418 number in japanese kokai publication sho 51-37193 number, Japanese special fair 2-32293 number, Japanese special fair 2-16765 number also is fit to.
As concrete reaction product; Can also preferably enumerate three (acryloxy ethyl) isocyanuric acid ester; In addition; Commercially available article, preferred urethane oligomers UAS-10, UAB-140 (adret state basic policy slurry corporate system), DPHA-40H (Japanese chemical drug corporate system), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600 (common prosperity corporate system), more preferably UA-306H, UA-306T, UA-306I (common prosperity corporate system).
As other preferred routine urea compounds that promptly have ethene property unsaturated link of (e) composition in second embodiment, can enumerate the reaction product of compound with amines and urethane bond.
Having the compound of isocyanic acid ester bond and the reaction of amines for example carries out through following condition.
(addition)
So that the mode that the urea base molal quantity of the NCO molal quantity of isocyanate compound and urea compounds equates is regulated.As catalyzer; Do not limit especially; But preferably use organotin (methyl) acrylates such as three (2 ethyl hexanoic acid) bismuth, dibutyl tin dilaurate, di-n-butylacetic acid tin, dibutyl tin dichloride, tin octoate; Organic zinc such as zinc octoate, zinc naphthenate (methyl) acrylates, tertiary amines such as triethylene diamine, triethylamine, 1,8-diaza-bicyclo [5,4,0] undecylene-7 etc. has (methyl) acrylic ester of amidine skeleton; With respect to mercaptan or isocyanates 100 weight portions, with the scope adding of 0.0001～10 weight portion.
(catalyzer, solvent, temperature of reaction)
Usually be suitable for-20 ℃～80 ℃ temperature range.Preferably-10 ℃～50 ℃ temperature range, and then preferred-5 ℃～30 ℃.The solvent that uses all can use except the material of alcohol, carboxylic acid, amine etc. and isocyanate reaction; But from reaction velocity, dissolubility aspect, preferably using chlorine such as acetonitrile, N, dinethylformamide (D M F), N, N-dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO) (DMSO), N-N-methyl-2-2-pyrrolidone N-(N MP) isopolarity solvent, chloroform is fragrant family solvents such as solvent, toluene, xylene.In addition, in order to prevent the reaction of residuary water and isocyanates, suitably use dehydrated solvent.
After reaction finishes, after under reduced pressure this reaction solution being concentrated, with silicagel column (eluant: ethyl acetate/n-hexane=1/1) come purifying.Can also be through chromatography, recrystallizationization, deposition is come purifying again.
As the amines of the raw material that becomes such urea compounds, have the concrete example of the compound of urethane bond, the compound (MU-28)～(MU-30) that can enumerate amines (A-1)～(A-15) and urethane bond is contained as part-structure.
[changing 25]
L, m, n are respectively 0～20 integer independently
[changing 26]
Promptly have the concrete example of the amide compound of ethene property unsaturated link as other preferred exemplary of (e) composition in second embodiment, can enumerate the reaction product of amines and halogen contained compound.
In reaction method, the amino molal quantity and the molal quantity of acid halide group equally added, add catalytic amount and arrived the alkali with etheride equivalent.As the example of alkaline matter, can enumerate triethylamine or pyridine etc.Solvent can be enumerated THF or acetonitrile, dimethyl acetamide etc.The scope that temperature of reaction is preferred-30 ℃～100 ℃, and then preferred-20 ℃～80 ℃.More preferably-20 ℃～50 ℃.After reaction finishes, behind under reduced pressure concentrated this reaction solution, with silicagel column (eluant: ethyl acetate/n-hexane=1/1) come purifying.Can also utilize chromatography, recrystallizationization, deposition is come purifying again.
As the example of such amide compound, can preferably enumerate the synthetic middle amines (A-1)～(A-15) that uses of said urea compounds and the reaction product of halogen contained compound with ethene property unsaturated link.The halogen contained compound (exemplary compounds (C-1)～(C-3)) that in this is synthetic, uses illustrates as follows.
[changing 27]
In addition; As the concrete example of the monomer of the acid amides of aliphatics multivalence amines and unsaturated carboxylic acid, have di-2-ethylhexylphosphine oxide-acrylic amide, di-2-ethylhexylphosphine oxide-Methacrylamide, 1,6-hexa-methylene two-acrylic amide, 1,6-hexa-methylene be two-Methacrylamide, diethylenetriamine three acrylic amides, xylylene bisacrylamide, the two Methacrylamides of xylylene etc.Preferred acid amides as other is the example of monomer, and the acid amides that can enumerate the cyclohexylene structure of the special public clear 54-21726 record of Japan is a monomer.
(e) composition that obtains so preferably contains with 0.3～5.0 quality % in total solid state component of the solidification compound of second embodiment, and then the scope of preferred 0.5～2.0 quality %.
In addition, (e) composition preferably with respect to after (b) ethene property unsaturated double-bond compound 100 mass parts of stating, containing more than 2 mass parts and less than the amount of 25 mass parts, and then preferred 5 mass parts are above and less than 10 mass parts.
(c) adhesive resin
As the adhesive resin in second embodiment, be included in side chain as polyradical have ester ring type (methyl) acryloyl group (methyl) acrylic copolymer (below, also abbreviate " adhesive resin " as.)。
As the synthetic schemes that said polyradical is imported resin, know the method that record in the special public clear 50-34443 communique of Japan, the special public clear 50-34444 communique of Japan etc. is arranged.
Specifically, through making carboxyl or the hydroxyl in the resin and for example having the reactions such as compound of ester ring type epoxy radicals such as epoxycyclohexyl, epoxide ring amyl group and (methyl) acryloyl group simultaneously, can access the resin that has polyradical at side chain.
As the preference of above-claimed cpd, can enumerate epoxycyclohexyl methyl (methyl) acrylic ester, epoxy cyclopentyl-methyl (methyl) acrylic ester, wherein most preferably (3,4-epoxycyclohexyl) methyl (methyl) acrylic ester.
In second embodiment; Side chain through to adhesive resin imports the ester ring type base; Can form especially that adhesiveness with substrate is superior, resistance to chemical reagents is high, can make and apply planar good Photocurable resin composition, especially be suitable as and make color filter and use.
The resin matrix that has imported as (methyl) acryloyl group of polyradical is (methyl) acrylic copolymer; As with the monomer of (methyl) acrylic acid copolymer, can enumerate and make styrene and AMS etc. instead has the multipolymer of the monomer copolymerization such as styrene, (methyl) methyl acrylate, (methyl) acrylic acid ethyl ester, (methyl) acrylic acid propyl diester, (methyl) acrylic acid isopropyl esters, (methyl) butyl acrylate cores, vinyl acetate base ester, vinyl cyanide, (methyl) acrylic amide, glycidyl (methyl) acrylic ester, allyl glycidyl ether, ethylacrylic acid glycidyl esters, crotonyl glycidyl ether, crotonic acid glycidyl ether, chlorine (methyl) acrylic acid, benzyl (methyl) acrylic ester, hydroxyethyl (methyl) acrylic ester, N hydroxymethyl acrylamide, N, N-DMAA, N-methacryl morpholine, N, N-dimethyl aminoethyl (methyl) acrylic ester, N, N-dimethyl aminoethyl acrylic amide of alkyl in the α position.Especially, preferably (methyl) acrylic acid is reached the multipolymer that instead has the styrene of alkyl to contain as copolymer composition in the α position.
Having imported as the shared ratio of (methyl) acrylic acid in (methyl) acrylic copolymer of (methyl) acryloyl group of said polyradical preferably is 0.2～0.8 in molar ratio, more preferably 0.3～0.7.In addition, containing in the multipolymer of above-mentioned copolymer compositions such as styrene is proportional preferred 0.8～0.2, and more preferably 0.7～0.3.
The GPC that utilizes of the adhesive resin that in second embodiment, uses promptly said (methyl) acrylic copolymer measures weight-average molecular weight preferred 1000～50000.
If weight-average molecular weight is below 1000, then be difficult to obtain filming of homogeneous, in addition,, then become unstable if surpass 50000, the tendency of gelation is arranged.
The colored curable resin composition of second embodiment can use said adhesive resin separately, also can share two or more.
The content of (c) adhesive resin in the colored curable resin composition of second embodiment is 10～90 quality % corresponding to the ratio (concentration) of total solid-state amount preferably, more preferably 20～80 quality %, and then preferred 30～75 quality %.
Be made as 10～90 quality % through content, form easily and apply planar good coated film the adhesive resin in the said colored curable resin composition, preferred on this point.
In second embodiment, in composition, except above-mentioned resinous principle,, can in the scope of the effect of not sacrificing second embodiment, add other resins for the improvement of development property, rerum natura improvement (mechanics rerum natura, adhesiveness etc.) etc.
Can together share benzyl (methyl) acrylic ester/(methyl) acrylic copolymer or benzyl (methyl) acrylic ester/(methyl) acrylic acid/and the multiple copolymer thermoplastic resins such as (mol ratio of benzyl (methyl) acrylic ester and sour composition are 5/5～9/1) of other monomers with above-mentioned resin.
The compound of ethene property unsaturated group < (b) have >
The colored curable resin composition of second embodiment contains: the compound (following, suitably be called polymerizable compound) that (b) has ethene property unsaturated group.
The polymerizable compound that can in second embodiment, use is the addition polymerization property compound with at least one ethene property unsaturated double-bond, is selected to have the compound that at least one preferably has terminal ethene property unsaturated link more than at least two.Such compound group is widely known by the people at this industrial field, in second embodiment, can it be used unqualifiedly.It for example has monomer, prepolymer, is dipolymer, trimer and oligomer or their potpourri and their chemical forms such as multipolymer.
As the example of monomer and multipolymer thereof, can enumerate unsaturated carboxylic acid (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, iso-crotonic acid, maleic acid etc.) or its ester class, the ester of preferred unsaturated carboxylic acid and aliphatic polyol compound.In addition, also be fit to use addition reaction with the substituent esters of unsaturated carboxylic acids of nucleophilicities such as hydroxyl, sulfydryl and simple function group or multifunction group epoxy class, reach and the dehydration condensation thing of simple function group or multi-functional carboxylic acid etc.In addition, also be fit to have the addition reaction of substituent esters of unsaturated carboxylic acids of electrophilicity such as epoxy radicals and simple function group or multi-functional alcohols, thio-alcohol and have halogen radical or the substituted reactant of the saturated carboxylic acid ester of cancellation substituent such as tolysulfonyl oxygen base and simple function group or multi-functional alcohols, thio-alcohol.In addition,, replace above-mentioned unsaturated carboxylic acid, also can use the compound group that is replaced into unsaturated phosphonic acids, styrene, vinyl ether etc. as other examples.
Concrete example with regard to the monomer of the ester of aliphatic polyol compound and unsaturated carboxylic acid; As acrylic ester, glycol diacrylate, triethylene glycol diacrylate, 1,3-butanediol diacrylate, tetramethylene glycol diacrylate, propylene glycol diacrylate, neopentylglycol diacrylate, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, trimethylolethane trimethacrylate acrylic ester, hexanediyl ester, 1,4-cyclohexanediol diacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol acrylate, D-sorbite triacrylate, D-sorbite tetraacrylate, D-sorbite five acrylic ester, D-sorbite six acrylic ester, three (acryloxy ethyl) isocyanuric acid ester, polyester acrylic ester oligomer, cyamelide EO modification triacrylate are arranged.
As methacrylate, tetramethylene glycol dimethylacrylate, triethylene glycol dimethylacrylate, neopentylglycol dimethacrylate, trimethylol-propane trimethacrylate, trimethylolethane trimethacrylate methacrylate, ethylene glycol dimethacrylate, 1,3-butanediol dimethylacrylate, hexanediol dimethacrylate, dimethyl pentaerythritol acrylate, pentaerythritol acrylate trimethyl, pentaerythrite tetramethyl acrylic ester, dipentaerythritol dimethylacrylate, dipentaerythritol hexamethyl acrylic ester, D-sorbite trimethyl acrylic ester, D-sorbite tetramethyl acrylic ester, two (p-(3-methacryloxy-2-hydroxyl propoxyl group) phenyl) dimethylmethane, two-(p-(methacryloxy ethoxy) phenyl) dimethylmethane etc. are arranged.
As itaconate, ethylene glycol bisthioglycolate itaconate, propylene glycol diitaconate, 1,3-butylene glycol diitaconate, 1,4-butylene glycol diitaconate, tetramethylene glycol diitaconate, pentaerythrite diitaconate, D-sorbite four itaconates etc. are arranged.As crotonates, ethylene glycol bisthioglycolate crotonates, tetramethylene glycol two crotonatess, pentaerythrite two crotonatess, D-sorbite four or two crotonatess etc. are arranged.As the iso-crotonic acid ester, ethylene glycol bisthioglycolate iso-crotonic acid ester, pentaerythrite two iso-crotonic acid esters, D-sorbite four iso-crotonic acid esters etc. are arranged.As maleate, ethylene glycol bisthioglycolate maleate, triethylene glycol dimaleate, pentaerythrite dimaleate, D-sorbite four maleates etc. are arranged.
Example as other esters; For example, also be fit to use the aliphatic alcohol of the special public clear 51-47334 of Japan, japanese kokai publication sho 57-196231 record be ester class or japanese kokai publication sho 59-5240, japanese kokai publication sho 59-5241, japanese kokai publication hei 2-226149 record the material with aromatic series pastern bone frame, japanese kokai publication hei 1-165613 record have an amino material etc.And then said ester monomer can also use as potpourri.
As other examples, can enumerate the polyester acrylate class of putting down in writing in japanese kokai publication sho 48-64183 number, special public clear 49-43191 number of Japan, special public clear 52-30490 number each communique of Japan, multi-functional acrylic ester or the methacrylates such as epoxy acrylate class that makes epoxy resin and the reaction of (methyl) acrylic acid.In addition, can also enumerate Japan special public clear 46-43946 number, Japan special fair 1-40337 number, the specific unsaturated compound of special fair 1-40336 number record of Japan or vinyl phosphonate based compound of japanese kokai publication hei 2-25493 number record etc.In addition, under certain conditions, be fit to use the structure that contains perfluoroalkyl of 61-22048 number record of japanese kokai publication sho.And then can also use in the Japanese bonding publication vol.20 of association, No.7,300～308 pages (1984) material of introducing as photo-curable monomer and oligomer.
About these addition polymerization property compounds, its structure, separately use is still share, the details of method of application such as addition can at random set according to the performance design of final composition.For example, select from following viewpoint.
From the aspect of light sensitivity, preferably in the many structures of the unsaturated group content of each molecule, under a large amount of situation, more than preferred two functional groups.In addition; Promptly solidify film strength in order to improve colored pattern portion; Trifunctional is above to be good; And then through share the material of the different polymerism base of different functional group's numbers (for example acrylic ester, methacrylate, polystyrene compound, vinyl ether based compound), two sides' of adjusting light sensitivity and film strength method is also effective.From solidifying the viewpoint of light sensitivity, the preferred compound that contains (methyl) acrylate structural more than 2 that uses more preferably uses and contains the compound more than 3, most preferably uses and contains the compound more than 4.In addition, from solidifying light sensitivity, and the viewpoint of unexposed development property, preferably contain EO modification body.
In addition; For with the colored curable resin composition of second embodiment in other compositions (for example; (a) look material, (d) Photoepolymerizationinitiater initiater or (c) the special adhesive resin that share according to expectation or as the alkali soluble resin of other any compositions) intermiscibility, dispersed; The essential factor that the selection of polyaddition compounds attaches most importance to usage to want for example, can improve intermiscibility through the use or two or more the share of low-purity compound sometimes.In addition, when colored curable resin composition being applicable to substrate etc., also, select specific structure sometimes from the adhering purpose that improves with substrate etc.
From above viewpoint, can bisphenol a diacrylate, bisphenol a diacrylate EO modification body, trimethylolpropane triacrylate, trimethylolpropane tris (acryloxy propyl group) ether, trimethylolethane trimethacrylate acrylic ester, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol tetraacrylate, dipentaerythritol five acrylic ester, dipentaerythritol acrylate, D-sorbite triacrylate, D-sorbite tetraacrylate, D-sorbite five acrylic ester, D-sorbite six acrylic ester, tetramethylol methane tetraacrylate EO modification body, dipentaerythritol acrylate EO modification body etc. be enumerated as preferred material.
Wherein, more preferably bisphenol a diacrylate EO modification body, pentaerythritol triacrylate, tetramethylol methane tetraacrylate, dipentaerythritol five acrylic ester, dipentaerythritol acrylate, tetramethylol methane tetraacrylate EO modification body, dipentaerythritol acrylate EO modification body etc.
In second embodiment, (b) polymerizable compound except independent use is a kind of, can also make up use two or more.
As the content of (b) polymerizable compound in the colored curable resin composition of second embodiment, preferably the total solid state component with respect to said composition is 1～90 quality %, more preferably 5～80 quality %, and then preferred 10～70 quality %.If the content of polymerizable compound then can be cured reaction fully in said scope.
Especially, the colored curable resin composition of second embodiment is used under the situation that the colored pattern of color filter forms preferred 5～50 quality % in the scope of said content, more preferably 7～40 quality %, and then preferred 10～35 quality %.
< (a) look material >
(a) the look material is meant: the material that the colored curable resin composition of second embodiment is painted.As the look material, can use and dye pigment, but from aspects such as thermotolerance, photostability, preferred pigments.
As pigment, can use versicolor pigment such as blue pigment, viridine green, red pigment, yellow uitramarine, violet pigment, orange pigment, brown pigments, black pigment.In addition; As its structure; Except azo system, anthraquinone system, phthalocyanine system, quinacridone, benzene imidazolone system, isoindoline are the organic pigments such as the 、 dioxazine is, indanthrene Xi 、 perylene system, diketopyrrolopyrrolecocrystals system, Kui phthalein ketone system, can also utilize various inorganic pigments.
Below, the concrete example of the pigment that can use illustrates with the pigment numbering.Also has " C.I. " expression colour index (C.I.) of below enumerating.
As red pigment, can enumerate C.I. paratonere 1,2,3,4,5,6,7,8,9,12,14,15,16,17,21,22,23,31,32,37,38,41,47,48,48:1,48:2,48:3,48:4,49,49:1,49:2,50:1,52:1,52:2,53,53:1,53:2,53:3,57,57:1,57:2,58:4,60,63,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276.
Wherein, preferred C.I. pigment red 4 8:1,122,168,177,202,206,207,209,224,242,254, and then preferably enumerate C.I. paratonere 177,209,224,254.
As blue pigment, can enumerate C.I. pigment blue 1,1:2,9,14,15,15:1,15:2,15:3,15:4,15:6,16,17,19,25,27,28,29,33,35,36,56,56:1,60,61,61:1,62,63,66,67,68,71,72,73,74,75,76,78,79.
Wherein, preferred C.I. pigment blue 15,15:1,15:2,15:3,15:4,15:6, and then can preferably enumerate the C.I. pigment blue 15: 3,15:6.
As viridine green, can enumerate C.I. naphthol green 1,2,4,7,8,10,13,14,15,17,18,19,26,36,45,48,50,51,54,55.
Wherein, can preferably enumerate C.I. pigment Green 7,36.
As yellow uitramarine, can enumerate C.I. pigment yellow 1,1:1,2,3,4,5,6,9,10,12,13,14,16,17,24,31,32,34,35,35:1,36,36:1,37,37:1,40,41,42,43,48,53,55,61,62,62:1,63,65,73,74,75,81,83,87,93,94,95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139,142,147,148,150,151,153,154,155,157,158,159,160,161,162,163,164,165,166,167,168,169,170,172,173,174,175,176,180,181,182,183,184,185,188,189,190,191,191:1,192,193,194,195,196,197,198,199,200,202,203,204,205,206,207,208.
Wherein, preferred C.I. pigment yellow, 117,129,138,139,150,154,155,180,185, and then can preferably enumerate C.I. pigment yellow 13 8,139,150,180,185.
As orange pigment, can enumerate C.I. pigment orange 1,2,5,13,16,17,19,20,21,22,23,24,34,36,38,39,43,46,48,49,61,62,64,65,67,68,69,70,71,72,73,74,75,77,78,79.
Wherein, can preferably enumerate C.I. pigment orange 38,71.
As violet pigment, can enumerate C.I. pigment violet 1,1:1,2,2:2,3,3:1,3:3,5,5:1,14,15,16,19,23,25,27,29,31,32,37,39,42,44,47,49,50.
Wherein, preferred C.I. pigment violet 19,23, and then can preferably enumerate the C.I. pigment Violet 23.
In addition, the colored curable resin composition of second embodiment is under the situation of black matrix with colored curable resin composition of color filter, as the look material, can use the look material of black.Black look material can be independent for black look material, maybe can be the black look material based on the mixing of red, green, blue etc.In addition, these look materials can suitably be selected from inorganic or organic pigment, dyestuff.Under the situation of inorganic, organic pigment, below mean grain size 1 μ m, preferably use to disperse below the 0.5 μ m.
As the look material that can mix use in order to prepare black look material; Can enumerate that the yellow O (41000) of Victoria blue (42595), Chinese scholartree, grand (CATHILON) lucidin of card magnetic (alkalescence 13), rhodamine 6G CP (45160), rhodamine B (45170), Safranine O K 70:100 (50240), Airy Ao Gulaxin (エ リ オ グ ラ ウ シ Application) X (42080), yellow (21090), neat Nore difficult to understand (ジ オ ノ one Le) the yellow GRO (21090) of N0.120/ thunder Nore difficult to understand, Heinrich Himmler (シ system ラ one) firm yellow 8GF (21105), benzidine yellow 4T-564D (21095), Heinrich Himmler are firmly red 4015 (12355), 6), Qi Aonagen (ジ オ ノ one ゲ Application) red GD (paratonere 168), the thunder green 2YS of Nore difficult to understand (pigment green 36) wait (also have, the numeral that above-mentioned () is interior is meant colour index (C.I.)) the thunder red 7B4401 of Nore (15850) difficult to understand, firm root (ゲ Application) blue TGR-L (74160), the blue SM (26150) of thunder Nore difficult to understand, the blue ES of thunder Nore difficult to understand (pigment blue 15:.
In addition; If about so other the pigment that can mix use; Show with the C.I. numbering, then for example can enumerate C.I. yellow uitramarine 20,24,86,93,109,1 10,117,125,137,138,147,148,153,154,166, C.I. orange pigment 36,43,51,55,59,61, C.I. red pigment 9,97,122,123,149,168,177,180,192,215,216,217,220,223,224,226,227,228,240, C.I. violet pigment 19,23,29,30,37,40,50, C.I. blue pigment 15,15:1,15:4,22,60,64, C.I. viridine green 7, C.I. brown pigments 23,25,26 etc.
In addition, as the black look material that can use separately, can enumerate metallics such as carbon black, acetylene black, dim, bone black, graphite, iron oxide black, nigrosine, cyanine black (cyanine black), titanium are black, silver or have the particle etc. of metal.
As constituting these metals is the example of the preferred metal of particulate, can enumerate to be selected from copper, silver, gold, platinum, palladium, nickel, tin, brill, rhodium, iridium, iron, calcium, ruthenium, osmium, manganese, molybdenum, tungsten, niobium, tantalum, bismuth, antimony, and these alloy at least a.And then preferred metal is be selected from copper, silver, gold, platinum, palladium, tin, calcium and these alloy at least a; Especially preferred metal is be selected from copper, silver, gold, platinum, tin and these alloy at least a, goes back the compound of other elements beyond preferred and the metal.
As the compound of metal and other elements, can enumerate the oxide, sulfide, sulfate, carbonate of metal etc., as the metallic compound particle, suitable is these particles.Wherein, from the easness of tone or particulate formation, the particle of preferred sulfide.
In addition, also can and with metal, its alloy and metallic compound, can be for two or more.Wherein, especially the screening effect of silver or its alloy and their sulfide is high, thereby preferred.As the example of alloy, can silver-colored ashbury metal be enumerated as preference.
In these black look materials, carbon black, titanium are black, the screening effect of the alloy of silver, silver-colored tin etc. and these sulfide is high, thereby preferably.As the example of carbon black, can enumerate the carbon black shown in following.
Mitsubishi Chemical Ind's system: MA7; MA8; MA11; MA100; MA100R; MA220; MA230; MA600; #5; #10; #20; #25; #30; #32; #33; #40; #44; #45; #47; #50; #52; #55; #650; #750; #850; #950; #960; #970; #980; #990; #1000; #2200; #2300; #2350; #2400; #2600; #3050; #3150; #3250; #3600; #3750; #3950; #4000; #4010; OIL7B; OIL9B; OIL11B; OIL30B; OIL31
Enlightening Gus's corporate system: PrintexS; Printex3OP; PrintexSO; Pril:itex30OP; Printex40; Printex 45; Printex 55; Printex GO; Printex 75; Printex SO; Printex 85; Printex 9O; Printex A; Printex L; Printex G; Printex P; Printex U; Printexv; Printex G; Deceive 550 especially; SpecialBlack 350; Special Black 250; Deceive 100 especially; Deceive 6 especially; Deceive 5 especially; Deceive 4 especially; Color is deceived FW1; Color is deceived FW2; Color is deceived FW2V; Color is black; FW18; Color is deceived FW200; Color is deceived S160; Color is deceived S170
Special corporate system: the Monarch120 of gilbert; Monarch 280; Monarch 4; 60; Monarch 800; Monarch 880; Monarch 900;: Monarch 1000; Monarch1100; Monarch 1300; Monarch 1400; Monarch 4630; REGAL 99; REGAL 99R; REGAL415; REGAL415R; REGAL250; REGAL250R; REGAL 330; REGAL 400R; REGAL 55R0; REGAL 660R; Black PEARlS 480; PEARLS 130; VULCAN XC72R; ELFTEX-8
Ke Longbi rock carbon corporate system: RAVEN 11; RAVEN14; RAVEN15; RAVEN 16; RAVEN 22R AVEN 30; RAVEN 35; RAVEN 40; RAVEN 410; RAVEN 420; RAVEN 450; RAVEN 500; RAVEN 780; RAVEN 850; RAVEN 890H; RAVEN 1000; RAVEN 1020; RAVEN 1040; RAVEN 1060U; RAVEN 1080U; RAVEN 1170; RAVEN 1190U; RAVEN 1250; RAV EN1500; RAVEN2000; RAVEN2500U; RAVHN 3500; RAVEN 5000; RAVEN 5250; RAVENS750; RAVEN 7000
In addition, titanium is black can enumerate following material.
As the black work system method of titanium, the method (japanese kokai publication sho 49-5432 communique) that the amalgam of titania and Titanium is heated and makes its reduction under reducing atmosphere is arranged; The method (japanese kokai publication sho 57-205322 communique) that the ultra rme titanium dioxide that the pyrohydrolysis of tetrachloromethane is obtained reduces in containing the reducing atmosphere of hydrogen; Method (japanese kokai publication sho 60-65069 communique, japanese kokai publication sho 61-201610 communique) with titania or titanium hydroxide high temperature reduction in the presence of ammonia; Make vfanadium compound be attached to titania or titanium hydroxide, and in the presence of ammonia the method (japanese kokai publication sho 61-201610 communique) etc. of high temperature reduction, but be not limited to these.
As the example of the black commercially available article of titanium, can enumerate the black 10S of Mitsubishi's malleable iron Leah system titanium, 12S, 13R, 13M, 13M-C etc.
As the example of other black pigments, can the benzene mixed amido black, iron oxide black pigment, and the organic pigment of red, green, blue three looks, as black pigment.
In addition, as pigment, can also use barium sulphate, lead sulfate, titanium dioxide, yellow lead, colcother, chromium oxide etc.
Above-mentioned various pigment can also share multiple.For example, for the adjusting of colourity,, can share viridine green and yellow uitramarine, or share blue pigment and violet pigment as pigment.
Also have average 1 the preferred 10nm～100nm of particle diameter, the more preferably 10nm～50nm of these pigment.
As stated, from aspects such as thermotolerance, photostability, as the look material, preferred pigments, but also can use dyestuff.
With regard to can be used as the dyestuff that the look material uses, can enumerate azo based dye, anthraquinone based dye, phthalocyanine based dye, quinone imines based dye, quinoline based dye, nitro based dye, carbonyl based dye, methine based dye etc.
As the azo based dye; For example, can enumerate that C.I. acid yellow 11, C.I. acid orange 7, C.I. acid red 37, C.I. acid red 18 0, C.I. acid blue 29, C.I. are directly red 28, C.I. is directly red 83, C.I. is directly yellow 12, nonactive red 17, the C.I. reactive red 120 of nonactive yellow 2, the C.I. of C.I. direct orange 26, C.I. direct green 28, C.I. direct green 59, C.I., C.I. reactive black 5, C.I. disperse orange 5, C.I. disperse red 58, C.I. disperse blue 16
5, C.I. alkali blue 41, C.I. Basic Red 18, C.I. mordant rouge 7, C.I. mordant yellow 5, C.I. mordant dyeing black 7.
As the anthraquinone based dye, for example, can enumerate C.I. vat blue 4, C.I. Acid Blue 40, C.I. ACID GREEN 25, C.I. active blue 19, C.I. reactive blue 49, C.I. disperse red 60, C.I. Disperse Blue-56, C.I. disperse blue 60 etc.
In addition, as the phthalocyanine based dye, for example, can enumerate C.I. vat blue 5 etc.; As the quinone imines based dye, for example, can enumerate C.I. alkali blue 3, C.I. alkali blue 9 etc.; As the quinoline based dye, for example, can the C.I. solvent yellow 33, C.I. quinoline yellow, C.I, dispersion yellow 64 etc.; As the nitro based dye, for example, can enumerate C.I. Indian yellow 1, C.I. acid orange 3, C.I. Disperse Yellow 42 etc.
(a) content of look material is 3 with respect to the total solid-state amount of colored curable resin composition preferably
Below the above 70 quality % of 0 quality %, more preferably below the above 60 quality % of 38 quality %, and then below the above 60 quality % of preferred 42 quality %.
Also have, " total solid-state amount " is that all compositions except solvent composition promptly comprise (a) look material, (c) special adhesive resin, (d) Photoepolymerizationinitiater initiater, (e) specific aggregation property compound, and (f) other the one-tenth meaning of grading in second embodiment.
(d) Photoepolymerizationinitiater initiater
The colored curable resin composition of second embodiment comprises: have direct absorbing light, or by light sensitizing, cause decomposition reaction or dehydrogenation reaction, produce the Photoepolymerizationinitiater initiater of the function of polymerization activity free radical.Photoepolymerizationinitiater initiater preferably has the Photoepolymerizationinitiater initiater of absorption in the zone of wavelength 300～500nm.In addition, can separately or share two or more.
When utilizing colored curable resin composition to form the optical polymerism layer of black; Begin to draw a portrait exposure from the optical polymerism layer across pattern mask; Therefore; Photoepolymerizationinitiater initiater is meant the compound of ultraviolet light～luminous ray performance light sensitivity, when the portrait exposure, preferably uses the exposure light source that matches with it.
In addition, in each red, green, blue optical polymerism layer, utilize exposure or additive method across pattern mask of all kinds; Between said black matrix pattern; Form red, green, blue phase homoatomic portrait pattern, therefore, with the identical ground of situation of black matrix; As Photoepolymerizationinitiater initiater is the compound to ultraviolet light～luminous ray performance light sensitivity, wherein preferably to below the 450nm, the compound of the performance of the wavelength below 400nm spectral sensitivity especially.
As Photoepolymerizationinitiater initiater; For example, can enumerate the oxime ester series initiators put down in writing in free radical activity agent such as N-aryl-alpha-amido-acids, N-aryl-alpha-amido-Barbiturates, N-aryl-alpha-amido-esters of gallic acid, alpha-amido-alkyl phenones based compound, the TOHKEMY 2000-80068 communiques such as six aryl di-imdazole derivatives, halogenated methyl-s-pyrrolotriazine derivatives, N-phenyl-glycocoll of the aromatic ring alkene metal derivative compound that comprises two luxuriant titaniums (チ タ ノ セ Application) compound put down in writing in japanese kokai publication sho 59-152396 number, japanese kokai publication sho 61-151197 number each communique or the record of japanese kokai publication hei 10-39503 communique etc.
As Photoepolymerizationinitiater initiater; For example, can enumerate organic halogen compound 、 oxadiazole compound, carbonyls, ketal compound, styrax compound, acridine compound, organic peroxy compound, azo-compound, coumarin compound, triazo-compound, aromatic ring alkene metal derivative compound, six aryl di-imidazolium compoundss, organic boron-oxygen, disulfonic acid compound, oxime ester compound, salt compound, acylphosphanes (oxide) compound.
As organic halogen compound; Specifically; Can enumerate if woods etc., " Bull Chem.Soc Japan " 42,2924 (1969), No. 3905815 instructions of United States Patent (USP), special public clear 46-4605 number of Japan, japanese kokai publication sho 48-36281 number, japanese kokai publication sho 55-32070 number, japanese kokai publication sho 60-239736 number, japanese kokai publication sho 61-169835 number, japanese kokai publication sho 61-169837 number, japanese kokai publication sho 62-58241 number, japanese kokai publication sho 62-212401 number, japanese kokai publication sho 63-70243 number, japanese kokai publication sho 63-298339 number, M.P.Hutt " heterocyclic chemistry journal 1 (No3), (1970) " compound put down in writing in the chapter, especially can enumerate trihalomethyl group Qu Dai De oxazole compound, s-triaizine compounds.
The concrete example of the Photoepolymerizationinitiater initiater that can in second embodiment, use is listed below.
Halogenated methylation pyrrolotriazine derivatives such as 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-methoxyl naphthyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-ethoxy naphthyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-ethoxy carbonyl naphthyl)-4, two (the trichloromethyl)-s-triazines of 6-.
As the s-triaizine compounds, what be more suitable for is, the s-pyrrolotriazine derivatives that at least one is single, two or three halogen substituent methyls combine with the s-triazine ring, specifically; For example, can enumerate 2,4,6-three (monochloro methyl)-s-triazine, 2; 4,6-three (dichloromethyl)-s-triazine, 2,4,6-three (trichloromethyl)-s-triazine, 2-methyl-4; Two (the trichloromethyl)-s-triazines of 6-, 2-n-propyl group-4, two (the trichloromethyl)-s-triazines of 6-, 2-(α, α, β-three chloroethyl)-4; Two (the trichloromethyl)-s-triazines of 6-, 2-phenyl-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-methoxyphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(3, the 4-epoxy-phenyl)-4; Two (the trichloromethyl)-s-triazines of 6-, 2-(p-chlorphenyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(1-(p-methoxyphenyl)-2,4-butadienyl)-4; Two (the trichloromethyl)-s-triazines of 6-, 2-styryl-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-methoxyl-styrene)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(p-i-propoxyl group styryl)-4; Two (the trichloromethyl)-s-triazines of 6-, 2-(p-tolyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-(4-methoxyl naphthyl)-4, two (the trichloromethyl)-s-triazines of 6-, 2-phenyl sulfo--4; Two (the trichloromethyl)-s-triazines of 6-, 2-dibenzylsulfide generation-4, two (the trichloromethyl)-s-triazines of 6-, 4-(o-bromo-p-N, N-(di ethoxy carbonyl is amino)-phenyl)-2,6-two (trichloromethyl)-s-triazine, 2; 4,6-three (two bromomethyls)-s-triazine, 2,4; 6-three (trisbromomethyl)-s-triazine, 2-methyl-4, two (the trisbromomethyl)-s-triazines of 6-, 2-methoxyl-4, two (the trisbromomethyl)-s-triazines of 6-etc.
2-trichloromethyl-5-(2 '-benzofuranyl)-1,3,4-oxadiazole, 2-trichloromethyl-5-(β-(2-benzofuranyl) vinyl)-1; 3; 4-oxadiazole, 2-trichloromethyl-5-(β-(2 '-(6 "-benzofuranyl) vinyl))-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-1; 3, halogenated methyl oxadiazole derivants such as 4-oxadiazole.
Zuo Wei oxadiazole compound can be enumerated 2-trichloromethyl-5-styryl-1,3; 4-oxadiazole, 2-trichloromethyl-5-(cyano styrene base)-1,3,4-oxadiazole, 2-trichloromethyl-5-(naphthalene-1-yl)-1; 3; 4-oxadiazole, 2-trichloromethyl-5-(4-styryl) styryl-1,3,4-oxadiazole etc.
2-(2 '-chlorphenyl)-4; 5-diphenyl-imidazole dipolymer, 2-(2 '-chlorphenyl)-4; Two (3 '-methoxyphenyl) imidazole dimers of 5-, 2-(2 '-fluorophenyl)-4; 5-diphenyl-imidazole dipolymer, 2-(2 '-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer, (4 '-methoxyphenyl)-4, imdazole derivatives such as 5-diphenyl-imidazole dipolymer.
Styrax alkyl ethers such as styrax methyl ether, styrax phenyl ether, benzoin isobutyl butyl ether, benzoin isobutyl propyl group ether.
Anthraquinone derivatives such as 2-methylanthraquinone, 2-EAQ, 2-t-butyl anthraquinone, 1-chloroanthraquinone.
Benzophenone derivates such as benzophenone, Michler's keton, 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2-chlorobenzophenone, 4-bromine benzophenone, 2-carboxyl benzophenone.
2; 2-dimethoxy-2-phenyl acetophenone, 2; 2-diethoxy acetophenone, 1-hydroxycyclohexylphenylketone, alpha-hydroxy-2-aminomethyl phenyl acetone, 1-hydroxyl-1-Methylethyl (p-isopropyl phenyl) ketone, 1-hydroxyl-1-(p-dodecylphenyl) ketone, 2-methyl-(4 '-(methyl sulfo-) phenyl)-2-morpholino-1-acetone, 1; 1,1-trichloromethyl-acetophenone derivs such as (p-butyl phenyl) ketone.
Thioxanthones, 2-ethyl thioxanthones, 2-isopropyl thioxanthone, 2-clopenthixal ketone, 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2, thioxanthone derivates such as 4-diisopropyl thioxanthones.
Benzoic acid ester derivants such as p-dimethylamino benzoic acid ethyl ester, p-diethylamino benzoic acid ethyl ester.
Acridine derivatives such as 9-phenylacridine, 9-(p-methoxyphenyl) acridine.
9, azophenlyene derivants such as 10-dimethylbiphenyl azophenlyene.
Benzanthrone anthracyclinone derivatives such as (benzanthrone).
Dicyclopentadienyl-Ti-dichloride, the two phenyl of dicyclopentadienyl-Ti-, dicyclopentadienyl-Ti-two-2,3,4; 5,6-pentafluorophenyl group-1-base, dicyclopentadienyl-Ti-two-2,3; 5,6-tetrafluoro phenyl-1-base, dicyclopentadienyl-T i-two-2,4; 6-trifluorophenyl-1-base, dicyclopentadienyl-Ti-2,6-difluorophenyl-1-base, dicyclopentadienyl-Ti-2,4-difluorophenyl-1-base, dimethyl cyclopentadienyl group-Ti-two 2; 3,4,5; 6-pentafluorophenyl group-1-base, dimethyl cyclopentadienyl group-Ti-are two-2,6-difluorophenyl-1-base, dicyclopentadienyl-Ti-2,6-two fluoro-3-(pyrroles-1-yl)-phenyl-two luxuriant titanium derivatives such as 1-base.
2-methyl isophthalic acid [4-(methyl-sulfo-) phenyl]-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1; 2-benzyl-2-dimethyl-amino-1-(4-morpholino phenyl-) butanone-ketone, 4-dimethyl aminoethyl benzoate, 4-dimethylamino isopentyl benzoate, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino propiophenone, 2-ethylhexyl-1; 4-dimethylamino benzoate, 2, alpha-aminoalkyl benzophenone based compounds such as two (the 4-diethylamino benzal) cyclohexanone of 5-, 7-diethylamino-3-(4-diethylamino benzoyl group) cumarin, 4-(diethylamino) chalcone.
1,2-octadione-1-[4-(phenyl sulfo-) phenyl]-2-(O-benzoyl group oxime), ethyl ketone-1-[9-ethyl-6-(2-methylbenzene acyl group)-9H-carbazole-3-yl]-1-oxime ester based compounds such as (O-acetyl group oximes).
As carbonyls; Can enumerate benzophenone derivates such as benzophenone, Michler's keton, 2 methyl benzophenone, 3-methyldiphenyl ketone, 4-methyldiphenyl ketone, 2-chlorobenzophenone, 4-bromine benzophenone, 2-carboxyl benzophenone; 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy acetophenone, 1-hydroxycyclohexylphenylketone, alpha-hydroxy-2-aminomethyl phenyl acetone, 1-hydroxyl-1-Methylethyl-(p-isopropyl phenyl) ketone, 1-hydroxyl-1-(p-dodecylphenyl) ketone, 2-methyl isophthalic acid-(4 '-(methyl sulfo-) phenyl)-2-morpholino-1-acetone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1; 2; 4; 6 trimethylbenzene acyl group-diphenyl-phosphine oxides, 1; 1; 1-trichloromethyl-(p-butyl phenyl) ketone, 2-benzyl-2-dimethylamino-acetophenone derivs such as 4-morpholino bromobenzene ketone, thioxanthones, 2-ethyl thioxanthones, 2-isopropyl thioxanthone, 2-clopenthixal ketone, 2,4-dimethyl thioxanthones, 2; 4-diethyl thioxanthone, 2, benzoic acid ester derivants such as thioxanthone derivates such as 4-diisopropyl thioxanthones, p-dimethylamino benzoic acid ethyl ester, p-diethylamino benzoic acid ethyl ester etc.
As ketal compound, can enumerate benzyl dimethyl ketal, benzyl-'beta '-methoxy ethyl diethyldithiocarbamate acetal etc.
As the styrax compound, can enumerate m-benzoin isobutyl propyl group ether, benzoin isobutyl butyl ether, styrax methyl ether, methyl o-benzoyl group benzoate etc.
As the acridine compound, can enumerate 9-phenylacridine, 1, two (9-acridinyl) heptane of 7-etc.
As the organic peroxy compound, for example, can enumerate trimethyl hexanone peroxide, acetyl acetone peroxide, 1; Two (tert-butyl peroxide)-3,3 of 1-, 5-trimethyl-cyclohexane, 1; Two (tert-butyl peroxide) cyclohexanes, 2 of 1-, two (tert-butyl peroxide) butane of 2-, tert butyl hydroperoxide, cumenyl hydroperoxides, diisopropyl benzene hydroperoxides, 2,5-dimethylhexane-2; 5-dihydro-peroxidase, 1,1,3; 3-tetramethyl butyl hydroperoxides, tert-butyl group cumyl peroxide, dicumyl peroxide, 2,5-dimethyl-2,5-two (tert-butyl peroxide) hexane, succinic acid peroxide, benzoyl peroxide, 2; 4-dichloro-benzenes acyl peroxide, diisopropyl peroxy two carbonic esters, two-2-ethylhexyl peroxy, two carbonic esters, two-2-ethoxyethyl group peroxy, two carbonic esters, dimethoxy isopropyl peroxy carbonic ester, two (3-methyl-3-methoxyl butyl) peroxy two carbonic esters, peroxide tert-butyl acetate, tert-butyl peroxide neopentyl ester, tert-butyl peroxide new decanoate ester, tert-butyl peroxide caprylate, tert-butyl peroxide laurate, tertiary carbon acid esters, 3; 3 ', 4,4 '-four-(tert-butyl peroxide carbonyl) benzophenone, 3; 3 '; 4,4 '-four-(peroxidating uncle hexyl carbonyl) benzophenone, 3,3 '; 4,4 '-four-(p-isopropyl cumyl peroxy carbonyl) benzophenone, carbonyl two (tert-butyl peroxide dihydro two phthalate esters), carbonyl two (peroxidating uncle hexyl dihydro two phthalate esters) etc.
As azo-compound, for example, can enumerate azo-compound of putting down in writing in the japanese kokai publication hei 8-108621 communique etc.
As coumarin compound; For example, can enumerate 3-methyl-5-amino-((s-triazine-2-yl) amino)-3-phenyl cumarin, 3-chloro-5-diethylamino-((s-triazine-2-yl) amino)-3-phenyl cumarin, 3-butyl-5-dimethylamino-((s-triazine-2-yl) amino)-3-phenyl cumarin etc.
As triazo-compound; Can enumerate the organic azide of putting down in writing in No. 2848328 instructions of United States Patent (USP), No. 2852379 instructions of United States Patent (USP) and No. 2940853 instructions of United States Patent (USP), 2, two (4-phenylazide the methylene)-4-ethyl cyclohexanones (BAC-E) of 6-etc.
As aromatic ring alkene metal derivative compound, can enumerate various two cyclopentadiene titanium compounds of japanese kokai publication sho 59-152396 communique, japanese kokai publication sho 61-151197 communique, japanese kokai publication sho 63-41484 communique, japanese kokai publication hei 2-249 communique, japanese kokai publication hei 2-4705 communique, the record of japanese kokai publication hei 5-83588 communique, for example, dicyclopentadienyl-Ti-is two-phenyl, dicyclopentadienyl-Ti-two-2; 6-difluorophenyl-1-base, dicyclopentadienyl-Ti-are two-2,4-two-fluorophenyl-1-base, dicyclopentadienyl-Ti-two-2,4; 6-trifluorophenyl-1-base, dicyclopentadienyl-Ti-two-2,3,5; 6-tetrafluoro phenyl-1-base, dicyclopentadienyl-Ti-two-2,3,4; 5,6-pentafluorophenyl group-1-base, dimethyl cyclopentadienyl group-Ti-are two-2,6-difluorophenyl-1-base, dimethyl cyclopentadienyl group-Ti-two-2; 4,6-trifluorophenyl-1-base, dimethyl cyclopentadienyl group-Ti-two-2,3; 5; 6-tetrafluoro phenyl-1-base, two-methyl cyclopentadienyl-Ti-two-2,3,4; 5, the iron-aromatic hydrocarbons coordination compound of 6-pentafluorophenyl group-1-base, japanese kokai publication hei 1-304453 communique, the record of japanese kokai publication hei 1-152109 communique etc.
As six aryl di-imidazolium compoundss, for example, can enumerate all cpds of putting down in writing in each instructions of the special fair 6-29285 communique of Japan, No. the 3479185th, United States Patent (USP), No. the 4311783rd, United States Patent (USP), No. the 4622286th, United States Patent (USP) etc., specifically 2,2 '-two (o-chlorphenyl)-4,4 '; 5,5 '-tetraphenyl di-imidazoles, 2,2 '-two (o-bromophenyl)) 4,4 ', 5,5 '-tetraphenyl di-imidazoles, 2; 2 '-two (o, p-dichlorophenyls)-4,4 ', 5,5 '-tetraphenyl di-imidazoles, 2,2 '-two (o-chlorphenyl)-4; 4 ', 5,5 '-four (m-methoxyphenyl) di-imidazoles, 2,2 '-two (o, o '-dichlorophenyl)-4; 4 ', 5,5 '-tetraphenyl di-imidazoles, 2,2 '-two (o-nitrobenzophenone)-4,4 '; 5,5 '-tetraphenyl di-imidazoles, 2,2 '-two (o-aminomethyl phenyl)-4,4 ', 5; 5 '-tetraphenyl di-imidazoles, 2,2 '-two (o-trifluorophenyl)-4,4 ', 5,5 '-tetraphenyl di-imidazoles etc.
As the organic boronic salt compound; For example; Can be with the special organic borate of being willing to 2000-310808 number etc. that each communique and Kunz, Martin " red technology (Rad Tech) ' 98. programs (Proceeding) 19-22 in April, 1998, Chicago " put down in writing in waiting of No. 4, japanese kokai publication sho 62-14304, japanese kokai publication sho 62-150242 number, japanese kokai publication hei 9-188685 number, japanese kokai publication hei 9-188686 number, japanese kokai publication hei 9-188710 number, TOHKEMY 2000-131837, TOHKEMY 2002-107916, No. the 2764769th, Jap.P., Japan; Organic boron sulfonium coordination compound of putting down in writing in japanese kokai publication hei 6-157623 communique, japanese kokai publication hei 6-175564 communique, the japanese kokai publication hei 6-175561 communique or organic boron oxygen base sulfonium coordination compound; Organic boron iodine coordination compound of putting down in writing in japanese kokai publication hei 6-175554 communique, the japanese kokai publication hei 6-175553 communique; The You Ji Peng Phosphonium coordination compound of putting down in writing in the japanese kokai publication hei 9-188710 communique, organic boron transition metal complex compound of japanese kokai publication hei 6-348011 communique, japanese kokai publication hei 7-128785 communique, japanese kokai publication hei 7-140589 communique, japanese kokai publication hei 7-306527 communique, japanese kokai publication hei 7-292014 communique etc. etc. is enumerated as concrete example.
As two sulphones, can enumerate the compound of records such as japanese kokai publication sho 61-166544 communique, the special 2001-132318 of hope of Japan instructions etc.
As oxime ester compound, can enumerate J.C.S.Perkin II (1979) 1653-1660), compound, the spy of J.C.S.Perkin II (1979) 156-162, photopolymer Science and Technology magazine (1995) 202-232, the record of TOHKEMY 2000-66385 communique open the compound etc. of 2000-80068 communique, the record of Japan special table 2004-534797 communique.As concrete example, the IRGACUREOXE-01 of Ciba corporate system that suitable is, OXE-02 etc.
As salt compound; For example, can enumerate the salt compounded of iodine put down in writing in each communique of each instructions, japanese kokai publication hei 2-150848 number, japanese kokai publication hei 2-296514 number of record De phosphonium salt, No. the 104143rd, Europe patent, No. the 3 39049, United States Patent (USP), No. the 410201st, United States Patent (USP) in each instructions of No. the 4069055th, ammonium salt, United States Patent (USP), No. 4069056, United States Patent (USP) of record in No. 4069055 instructionss of overlapping salt, United States Patent (USP), japanese kokai publication hei 4-365049 number etc. of record among S.I.Schlesinger, Photogr.Sci.Eng., 18,387 (1974), T.S.Bal etc., the Polymer, 21,423 (1980) etc.
Can be adapted at the salt compounded of iodine that second embodiment uses and be diaryl group iodized salt,, preferably replaced more than two by electron donability bases such as alkyl, alkoxy, aryloxy group from stable aspect.In addition, as other the form of preferred sulfonium salt, a substituting group of preferred triarylsulfonium salt has cumarin, anthraquinone (ア Application ト ア キ ノ Application) structure, more than 300nm, has the salt compounded of iodine of absorption etc.
As the sulfonium salt that can be adapted at using in second embodiment; The sulfonium salt of putting down in writing in can enumerate the Europe patent No. 370693, each instructions of No. 390214, Europe patent, No. 233567, Europe patent, No. 297443, Europe patent, No. 297442, Europe patent, No. the 4933377th, United States Patent (USP), No. 161811, United States Patent (USP), No. 410201, United States Patent (USP), No. 339049, United States Patent (USP), No. 4760013, United States Patent (USP), No. 4734444, United States Patent (USP), No. 2833827, United States Patent (USP), No. the 2904626th, Deutsche Bundespatent, No. 3604580, Deutsche Bundespatent, No. 3604581, Deutsche Bundespatent; From the light sensitivity aspect of stability, preferably replaced by the electron attractivity base.As the electron attractivity base, preferred Hamann paricular value is greater than 0.As preferred electron attractivity base, can enumerate halogen atom, carboxylic acid etc.
In addition, as other preferred sulfonium salts, a substituting group can enumerating triarylsulfonium salt has cumarin, anthraquinone ring, more than 300nm, has the sulfonium salt of absorption.As other preferred sulfonium salts, can enumerate triarylsulfonium salt and have allyloxy, the aryl thio group is the substituent sulfonium salt that more than 300nm, has absorption.
In addition; As salt compound, can enumerate selenium salt, C.S.Wen etc., Teh, Proc.Conf.Rad.Curing Asia, the p478 Tokyo of record among J.V.Crivello etc., Macromolecules, 10 (6), 1307 (1977), J.V.Crivello etc., J.Polymer Sci., the Polymer Chem.Ed., 17,1047 (1979), the salt such as arsenic salt of record in November (1988) etc.
As acylphosphanes (oxide) compound, can enumerate IRGACURE819, DAROCURE 4265, DAROCURE TPO of Ciba corporate system etc.
As (d) Photoepolymerizationinitiater initiater that in second embodiment, uses; Viewpoint from the exposure light sensitivity is preferably selected from the compound that is made up of group trihalomethyl group triazine based compound, benzyl dimethyl ketal compound, alpha-hydroxyacetone compounds, alpha-amido ketonic compound, acylphosphanes based compound, phosphine oxide based compound, aromatic ring alkene metal derivative compound, oxime compound, triallyl imidazole dimer, based compound, benzothiazole based compound, benzophenone based compound, acetophenone based compound and derivant, cyclopentadiene-benzene-iron complex compound and salt thereof, halogen for first oxadiazole compound, 3-aryl substituted cumarin compound.
And then; Preferred trihalomethyl group triazine based compound, alpha-amido ketonic compound, acylphosphanes based compound, phosphine oxide based compound, oxime compound, triallyl imidazole dimer, based compound, benzophenone based compound, acetophenone based compound most preferably are selected from least a compound of the group that is made up of trihalomethyl group triazine based compound, alpha-amido ketonic compound, oxime compound, triallyl imidazole dimer, benzophenone based compound.
As concrete Photoepolymerizationinitiater initiater set member; For example; Except the dialkyl benzene ethyl ketone system of record in the 16th～26 page of " Off ア イ Application ケ ミ カ Le (fine chemicals) " (, March 1 day number, vol.20, N0.4 in 1991), styrax, thioxanthone derivates etc., can also enumerate record in japanese kokai publication sho 58-403023 communique, the special public clear 45-37377 communique of Japan etc. the middle combinations of putting down in writing such as six aryl di-imidazoles system, S-trihalomethyl group triazine system, japanese kokai publication hei 4-221958 communique, japanese kokai publication hei 4-219756 communiques two luxuriant titaniums and xanthene pigment, have amino or urethane groups can addition polymerization contain ethene property unsaturated double-bond compound be etc.
(d) Photoepolymerizationinitiater initiater can use a kind ofly separately, also can share two or more.
The content of Photoepolymerizationinitiater initiater is 0.1～50 quality % with respect to the total solid-state amount of colored curable resin composition preferably, more preferably 0.5～30 quality %, especially preferred 1～20 quality %.In this scope, obtain good light sensitivity and pattern and become second nature.
< (f) other compositions >
In the colored curable resin composition of second embodiment, except the necessary composition of the composition of (a) composition～(e), can under the situation of the effect of not sacrificing second embodiment,, share various compositions according to purpose.
(f-1) alkoxysilane compound containing trialkylsilyl group in molecular structure
The viewpoint that the colored curable resin composition of second embodiment makes progress from the adhesiveness with substrate, and then preferred alkoxysilane compound containing trialkylsilyl group in molecular structure are wherein preferably share silane coupling agent.
In the silane coupling agent as can with the chemically combined water-disintegrable base of inorganic material; Preferred alkoxysilyl; With organic resin combine preferred (methyl) acryloyl group of base, phenyl, sulfydryl, epoxy silane, wherein more preferably (methyl) acryloyl group propyl trimethoxy silicane.
Using the addition under the situation of silane coupling agent, is the scope of 0.2～3.0 quality % in total solid state component of the solidification compound of second embodiment preferably, more preferably 0.5～1.0 quality %.
Below, other preferred additives etc. are described.
(f-2) surfactant
The colored curable resin composition of second embodiment can use various surfactants from the purpose of improving screening characteristics.Can use the various surfactants of nonionic system, kation system, negative ion system, amphoteric surfactant; But wherein preferred nonionic is a surfactant; As preferred nonionic is that surfactant is polymkeric substance and the oligomer that comprises more than one polyethers (the for example multipolymer of polyglycol, polypropylene glycol and ethylene glycol and propylene glycol) segment; In addition, the fluorine that preferably has a perfluoroalkyl is a surfactant.
As anionic surfactant; For example, can enumerate Ai Maer 10 salt such as alkyl sulfate such as grade that colored king's strain formula can corporate system is that alkylnaphthalene sulfonates such as this NB-L of Marie-Jos that surfactant, flower king strain formula can corporate systems are the W004, W005, W017 of special macromolecular surfactants such as He Mona gill L-18 that surfactant, flower king strain formula can corporate systems, L-100, abundant merchant's corporate system etc.
Wherein, preferred special macromolecular surfactant, and then preferred special polyocarboxy acid type macromolecular surfactant.
As cationic surfactant; For example, can enumerate A Xitamin 24 alkylamine salts such as grade that colored king's strain formula can corporate system is that quaternary ammonium salts such as the quick 24P of bandit's tower that surfactant, flower king strain formula can corporate systems, 86W are surfactant, the gloomy phthalocyanine derivates of the EFKA-745 of industry corporate system down; The W001 that gathers Hu Lu No.75, No.90, No.95 etc. (methyl) acrylic acid series (being total to) condensate, abundant merchant's corporate system of oil chemistry industrial group of common prosperity company system etc.
Wherein, preferred quaternary ammonium salt is a surfactant, and then preferred stearyl leptodactyline is a surfactant.
As non-ionic surfactant; For example, preferred polyoxygenated ethylene alcohols, polyoxygenated trimethylene glycol class, polyoxyethylene alkyl ether class, polyoxyethylene alkylaryl ether class, polyxyethylated ester class, polyoxypropylene alkyl ether, polyoxypropylene alkylaryl ethers, polyoxypropylene alkyl esters, sorbitan alkyl esters, monoglyceride alkyl esters etc.
Specifically, polyoxyalkylene glycol classes such as polyoxygenated ethylidene glycol, polyoxygenated trimethylene glycol are arranged; Polyoxyalkylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxypropylene stearyl ether, polyoxyethylene oleoyl ether; Polyoxyethylene aryl ethers such as NONIN HS 240, polystyrene-basedization of polyoxyethylene ether, polyoxyethylene tribenzyl phenyl ether, polystyrene-basedization of polyoxyethylene-propylene ether, polyoxyethylene nonylplenyl ether; Non-ionic surfactants such as polyoxyalkylene dialkyls such as polyoxyethylene dilaurate, polyoxyethylene distearate, sorbitan fatty acid esters, polyoxyalkylene sorbitan fatty acid esters class.
The concrete example of non-ionic surfactant for example has segmented copolymer (the tergitol MIMFOAM of alliance's carbide company of propylene two pure and mild ethylene glycols; The Pluronic L10 of BASF AG; L31; L43; L61; L62; L64; 1107; P103; And 10R5; 17R2; 25R2; Taide Le Nike 304; 701; 704; 901; 904; 150R1 etc.) or ethoxylation or propenoxylated the acrylate oligomer ((Exton of Sartomer company; PA) polyethoxylated (20) trimethylolpropane triacrylate; Polyglycol (600) diacrylate; Gather propoxylation materialization (6) trimethylolpropane triacrylate; SR415; SR610; SR501 etc.); And polyethoxylated alkylphenol and polyethoxylated fatty alcohol (Tuo Li of alliance's carbide company gulps down X-100; Tuo Li gulps down X-102; Tuo Li gulps down X-165; Tuo Li gulps down X-305; Tuo Li gulps down X-405; Tuo Li gulps down X-705; Tuo Li gulps down X-45; Tuo Li gulps down X-114; Tuo Li gulps down CF-10; Tuo Li gulps down CA and the holder profit gulps down DF-12 etc.).
In addition, have A Dikele Knicks series, A Dike Nore series, Taide Le Nike series (above ADEKA strain system), Chinese mugwort Viktor Markin series, lining watt Dorr series (above colored king (strain) system), like that Lei Minuoer series, Nuo Nipuer are serial, Ao Kuta pul series, the good pul series of many morals, Niu Puer serial (above Sanyo changes into (strain) system), clap Buddhist nun's appearance difficult to understand serial (above this grease of bamboo (strain) system), Nissan nonionic serial (above Japanese grease (strain) system) etc.Can suitably use these commercially available article.
Preferred HLB value is 8～20, and then preferred 10～17.
As fluorine is the concrete example of surfactant, and the manicure that can enumerate big Japanese ink chemical industry (strain) system cuts down the Florey moral (registered trademark) serial (FC 430 etc.) of gram (registered trademark) series (manicure cut down gram F 172, manicure cut down gram F 173, manicure cut down gram F 176, manicure and cut down gram F 177, manicure and cut down gram F 183, manicure and cut down gram 470, manicure and cut down that gram F 475, manicure cut down gram F 780, manicure cuts down gram F 781 etc.), 3M corporate system etc.
In addition, as the silicone-based surfactant, for example, can enumerate the SH 8400 of eastern beautiful silicone strain formula meeting corporate system, the KP 341 of SHIN-ETSU HANTOTAI's chemical industry strain formula meeting corporate system etc.
As surfactant; Having used fluorine is under the situation of surfactant; The use level of surfactant is more than the 0.01 quality % below the 1.00 quality %, more preferably below the above 3.0 quality % of 0.1 quality % with respect to the total solid-state amount of colored curable resin composition preferably.If the use level of surfactant is above-mentioned scope, then wetting state and levelability improve.
Having used fluorine is under the situation of the surfactant beyond the surfactant, and its use level is more than the 0.001 quality % below the 1.0 quality %, more preferably below the above 0.5 quality % of 0.01 quality % with respect to the total solid-state amount of colored curable resin composition preferably.
(f-3) spreading agent (dispersion resin)
As spreading agent; As macromolecule dispersing agent; For example, can use the multipolymer, acid amides based compound, urethane based compound, lactams based compound, barbiturates based compound etc. of acrylic acid and styrene, acrylic ester and methacrylic acid, acrylic acid and methacrylate, styrene and maleic acid etc. or the resin type spreading agent (being Bick chemicals corporate system Di Sipa Bick 130, Di Sipa Bick 161, Di Sipa Bick 182, Di Sipa Bick 170, Ai Fujia corporate system Ai Fujia 46, Ai Fujia 47 etc.) of polyamide-based compound or polyurethane series compound and so on by commercially available article.
Wherein, preferably have the spreading agent of nitrogen-containing functional group, and then preferably acrylic acid series spreading agent, urethane are spreading agent, graft copolymer spreading agent.
As the acrylic acid series spreading agent, be preferably included in side chain have the A block of quaternary ammonium salt base and do not have quaternary ammonium salt base the B block, A-B segmented copolymer and/or B-A-B segmented copolymer.
The A block that constitutes the segmented copolymer of acrylic acid series spreading agent is a quaternary ammonium salt base, preferably has by-N
+R
1aR
2aR
3aY
-(wherein, R
1a, R
2a, and R
3aRepresent hydrogen atom or can substituted ring-type or the alkyl of chain respectively independently.Or R
1a, R
2a, and R
3aIn mutually combine more than two, form ring texture and also can.Y
-Be expressed as negative ion.) expression quaternary ammonium salt base.This quaternary ammonium salt base can directly combine with main chain, also can combine with main chain through the concatenating group of divalence.
-N
+R
1aR
2aR
3aIn, as R
1a, R
2a, R
3aIn mutually combine more than two and the ring texture that forms, for example can enumerate the nitrogen heterocyclic ring monocycle of 5～7 yuan of rings or the condensed ring that they form with two condensations.This nitrogen heterocyclic ring does not preferably have aromaticity, under the situation of saturated rings more preferably.Specifically, can enumerate following substances.
[changing 28]
In above-mentioned formula, R representes R
1a～R
3aIn any base.
These ring texturees and then have substituting group and also can.As-N
+R
1aR
2aR
3aIn R
1a～R
3a, more preferably can have the alkyl of substituent carbon number 1～3, maybe can have substituent phenyl, maybe can have substituent benzyl.
As the A block, especially preferably contain the material of the part-structure of formula (9) expression.
[changing 29]
General formula (9)
In above-mentioned general formula (9), R
1a, R
2a, R
3aRepresent hydrogen atom or can substituted ring-type or chain alkyl respectively independently.Perhaps, R
1a, R
2a, and R
3aIn the formation ring texture that also can mutually combine more than two.R
4aExpression hydrogen atom or methyl.X representes the concatenating group of divalence, and Y-representes counter anion.
In above-mentioned general formula (9), as the concatenating group X of divalence, for example can enumerate carbon number 1～10 alkylidene, arlydene ,-CONH-R
5a-,-COO-R
6a-(wherein, R
5aAnd R
6aExpression is combination, the alkylidene of carbon number 1～10 or the ether (R of carbon number 1～10 directly
7a-O-R
8a-: R
7aAnd R
8aBe alkylidene independently respectively).) etc., preferred-COO-R
6a-.
In addition, as the Y of counter anion
-, can enumerate Cl
-, Br
-, I
-, ClO
4 -, BF
4 -, CH
3COO
-, PF
6 -Deng.
The part-structure that contains specific quaternary ammonium salt base like above-mentioned general formula (9) can contain two or more in an A block.Under the sort of situation, the two or more part-structures that contains quaternary ammonium salt base can contain with any form of random copolymerization or block copolymerization in this A block.In addition, the part-structure that does not contain this quaternary ammonium salt base also can be contained in the A block, as the example of this part-structure, and the part-structure of stating after can enumerating that derives from (methyl) acrylic ester monomer etc.
Preferred 0～50 quality % of the content of part-structure in the A block that does not contain said quaternary ammonium salt base, more preferably 0～20 quality %, the said part-structure that does not contain quaternary ammonium salt base most preferably is not contained in the A block.
On the other hand, as the B block of the segmented copolymer that constitutes spreading agent, for example, can enumerate styrenic monomers such as making styrene, AMS; (methyl) methyl acrylate; (methyl) acrylic acid ethyl ester; (methyl) acrylic acid propyl diester; (methyl) acrylic acid isopropyl esters; (methyl) butyl acrylate cores; (methyl) acrylic acid octyl group ester; (methyl) acrylic acid-2-ethyl hexyl ester; Glycidyl (methyl) acrylic ester; Benzyl (methyl) acrylic ester; Hydroxyethyl (methyl) acrylic ester; The ethylacrylic acid glycidyl esters; N; (methyl) acrylic ester monomers such as N-dimethyl aminoethyl (methyl) acrylic ester; (methyl) acrylates such as chlorine (methyl) acrylic acid are monomer; (methyl) acrylamide monomers such as (methyl) acrylic amide, N hydroxymethyl acrylamide, N, N-dimethyl-acrylic amide, N, N-dimethyl aminoethyl acrylic amide; The vinyl acetate base; Vinyl cyanide; Acyl group (ア ジ Le) glycidyl ether, crotonic acid glycidyl ether; The polymer architecture of comonomer copolymerization such as N-methacryl morpholine.
The part-structure that derives from (methyl) acrylic ester monomer of especially preferred formula (10) expression of B block.
[changing 30]
General formula (10)
In above-mentioned general formula (10), R
9aExpression hydrogen atom or methyl.R
10aExpression can have substituent ring-type or chain-like alkyl, can have substituent allyl, maybe can have substituent aralkyl.
The part-structure of above-mentioned deriving from (methyl) acrylic ester monomer can contain two or more in a B block.Certainly, this B block also can and then contain the part-structure beyond these.When the two or more part-structures from monomer existed in not containing the B block of quaternary ammonium salt base, the each several part structure can any form with random copolymerization or block copolymerization contain in this B block.
In the B block, contain under the situation of the part-structure beyond the part-structure of above-mentioned deriving from (methyl) acrylic ester monomer; Be somebody's turn to do preferred 0～50 quality % of the content in the B block of the part-structure beyond (methyl) acrylic ester monomer; More preferably 0～20 quality %, but the part-structure beyond said (methyl) acrylic ester monomer most preferably is not contained in the B block.
The acrylic acid series spreading agent that in second embodiment, uses is A-B block or the B-A-B block copolymerization type macromolecular compound that comprises this A block and B block, and such segmented copolymer for example utilizes the living polymerization method shown in following to prepare.
The living polymerization method comprises living anion polymerization method, cation activity polymerization, radical living polymerization method.The polymerization activity kind is a negative ion in the living anion polymerization method, for example by following graphical presentation.
[changing 31]
Monomer (1)
Under the situation of monomer (2)
The polymerization activity kind is a group in the radical living polymerization method, is for example represented by following diagram.
[changing 32]
Monomer (1)
Under the situation of monomer (2)
[changing 33]
Monomer (1)
Under the situation of monomer (2)
When synthetic such acrylic acid series spreading agent, can adopt japanese kokai publication hei 9-62002 communique or P.Lutz.P.Massoneta]., Polym.Bull.12,79 (1984), B.C.Ande:rson, G.D.Andrews etc., Macromolecules, 14,1601 (1981), K.Hatada, K.Ute, etc., great one,
Tagayasu Den one of Polym.J.17,977 (1985), 18,1037 (1986), the right hand, Process Technology of Polymer, 36,366 (1987), East Village quickly prolong, the known method put down in writing among damp wooden light man, macromolecule collection of thesis, 46,189 (1989), M.Kuroki, T.Aida, J.Am.Chem.Sic, 109,4737 (1987), phase field table three, aboveground auspicious flat, Synthetic Organic Chemistry, 43,300 (1985), D.Y.Sogoh, W.R.H ertieretal, the Macromolecules, 20,1473 (1987) etc.
No matter be that the spreading agent that uses in second embodiment is the A-B segmented copolymer; Or B-A-B segmented copolymer; A block/B the block that constitutes said multipolymer is generally more than 1/99 than (mass ratio), and is wherein preferred more than 5/95, in addition; Be generally below 80/20 wherein preferred scope below 60/40.Under this extraneous situation, can not have both good thermotolerance and dispersiveness sometimes.
In addition, the amount of the quaternary ammonium salt base among the A-B segmented copolymer of second embodiment, the B-A-B segmented copolymer 1g is preferred 0.1～10mmol usually, under this extraneous situation, can not have both good thermotolerance and dispersiveness sometimes.
Also have, in such segmented copolymer, contain the amino that in manufacture process, produces sometimes usually, but its amine value is about 1～100mg-KOH/g.Also have, the amine value is through utilizing acid with the amino acid-base titration of alkalescence, corresponding to acid number, and the value of representing with the mg acid of KOH.
In addition; The acid number of this segmented copolymer depends on the kind that has that it's too late of the acid root in the source that becomes this acid number; A but usually preferred low side; Be generally below the 100mg-KOH/g, its molecular weight is generally the scope more than 1000, below 100000 by the weight-average molecular weight (Mw) of the polystyrene conversion of utilizing GPC to measure.If the molecular weight of segmented copolymer is too small, then dispersion stabilization reduces, and as if excessive, then is in the tendency of development property, the reduction of exploring degree.
In second embodiment,, can also be suitable for and have the commercially available of the structure identical and/or acrylic acid series spreading agent with above-mentioned substance as spreading agent.
As urethane is spreading agent, especially preferably in a part, has dispersion resin that the amino compound reaction of active hydrogen and uncle obtains etc. through compound, (3) that make (1) polyisocyanate compounds, (2) in a part, have one or two hydroxyl.
(1) polyisocyanate compounds
Example as polyisocyanate compounds; Can enumerate PPDI, 2,4-inferior cresyl vulcabond, 2,6-inferior cresyl vulcabond, 4; 4 '-two methyl diphenylene diisocyanates, naphthalene-1; Aromatic diisocyanate, hexamethylene diisocyanate, lysine methyl ester diisocyanate, 2,4 such as 5-diisocyanate, triazine diisocyanate, aliphatic diisocyanate, IPDIs, 4 such as 4-trimethyl hexamethylene diisocyanate, dipolymer acid diisocyanate; 4 '-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate), ω; ω '-ester ring type diisocyanate, eylylene diisocyanate, α such as diisocyanate methylcyclohexane, α, α '; α '-tetramethyl eylylene diisocyanate etc. has aliphatic diisocyanate, the lysine ester triisocyanate, 1 of aromatic rings; 6,11-undecane triisocyanate, 1,8-diisocyanate-4-isocyanates methyloctane, 1; 3, triisocyanates such as 6-hexa-methylene triisocyanate, bicycloheptane triisocyanate, three (isocyanate benzene methylmethane), three (isocyanate phenyl) Thiophosphonate, and their trimer, water addition product, and their polyvalent alcohol addition product etc.
As gathering the preferably trimer of organic diisocyanate of diisocyanate, the most preferably trimer of inferior cresyl vulcabond and Trimerization of Isophorone Diisocyanate thing.These can use a kind of separately, and it is two or more also can to mix use.
Trimeric manufacturing approach as isocyanates; Can enumerate use with said polyisocyanate the class suitably catalyzer, for example tertiary amines, phosphine class, pure salt, metal oxide, metal carboxylate etc. of trimerizing, carry out the trimerizing of the part of NCO, through the interpolation of catalyst poison; After stopping trimerizing; The polyisocyanate of extraction end reaction utilizes thin-film distillation to remove, and obtains the method that purpose contains the polyisocyanate of cyamelide ester group.
(2) in a part, has the compound of one or two hydroxyl
As the compound that in a part, has one or two hydroxyl, can enumerate polyethers glycol (polyetherglycol), polyester glycol (polyesterglycol), polycarbonate glycol (polycarbonateglycol), polyolefin glycol (polyolefinglycol) etc., and these a terminal hydroxyl of compound by the alkyl alkoxylated material of carbon number 1-25 and these two or more potpourris.
As the polyethers glycol, can enumerate PTMEG, polyether ester glycol, reach these two or more potpourris.
As PTMEG, can enumerate and make that oxyalkylene homopolymerization or copolymerization obtain, for example polyglycol, polypropylene glycol, tygon-propylene glycol, polyoxygenated tetramethylene glycol, polyoxygenated hexamethylene glycol, polyoxygenated eight methylene glycols and their two or more potpourri.
As the polyether ester glycol, can enumerate make the glycol that contains ether or with the potpourri of other glycol, with dicarboxylic acid or their anhydride reactant, or make polyester glycol and reactions of alkylene oxide obtain, for example gather (polyoxygenated tetramethylene) adipate etc.
As the polyethers glycol, most preferably a terminal hydroxyl of polyglycol, polypropylene glycol, polyoxygenated tetramethylene glycol or these compounds is by the alkyl alkoxylated compound of carbon number 1～25.
As the polyester glycol, can enumerate and make dicarboxylic acid (succinic acid, glutaric acid, hexane diacid, decanedioic acid, fumaric acid, maleic acid, phthalandione etc.) or their acid anhydride and glycol (monoethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, DPG, tripropylene glycol, 1,2-butylene glycol, 1; 3-butylene glycol, 1,4-butylene glycol, 2,3-butylene glycol, 3-methyl isophthalic acid; 5-pentanediol, neopentyl glycol, 2-methyl isophthalic acid; 3-propane-glycol, 2-methyl-2-propyl group-1,3-propane-glycol, 2-butyl-2-ethyl-1,3-propane-glycol, 1; 5-pentanediol, 1; 6-hexanediol, 2-methyl-2,4-pentanediol, 2,2; 4-trimethyl-1; 3-pentanediol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2; 5-hexanediol, 1; 8-eight methylene glycols, 2-methyl isophthalic acid, 8-eight methylene glycols, 1, N-alkyl two alkanolamines such as aromatic diols such as ester ring type glycol such as aliphatic diols such as 9-nonane glycol, two hydroxymethyl cyclohexanes, xylylene glycol, two hydroxyl-oxethyl benzene, N-methyl-diethanolamine etc.) material that obtains of polycondensation, for example the monohydroxy alcohol of polyethylene adipate, polybutylene adipate, polyhexamethylene adipate, tygon/propylene adipate etc. or said glycols or carbon number 1～25 is used the polylactone glycol or polylactone list alcohol, the for example polycaprolactone glycol that obtain, gathers methylpent lactone and their two or more potpourri as initiating agent.
As the polyester glycol,, more particularly be most preferably with the 6-caprolactone open loop with the alcohol of polycaprolactone glycol or carbon number 1-25 polycaprolactone as initiating agent, and the compound that obtains with single pure addition polymerization.
As the polycarbonate glycol; Can enumerate and gather (1,6-hexylidene) carbonic ester, gather (3-methyl isophthalic acid, 5-pentylidene) carbonic ester etc.; As polyolefin diols, can enumerate polybutadiene diol, hydrogenation type polybutadiene diol, hydrogenation type polyisoprene glycol etc.
In with a part, have in the compound of one or two hydroxyl, especially preferred, polyethers glycol and polyester glycol.
The number-average molecular weight that in a part, has the compound of one or two hydroxyl is 300～10000, and is preferred 500～6000, and then preferred 1000～4000.
(3) in a part, has the amino compound of reactive hydrogen and uncle
The compound that in a part, has active hydrogen and uncle's amino that explanation is used in second embodiment.As reactive hydrogen, the hydrogen atom that promptly directly combines with oxygen atom, nitrogen-atoms or sulphur atom, can enumerate the hydrogen atom in functional group's bases such as hydroxyl, amino, mercapto, wherein preferred amino, the hydrogen atom of especially preferred primary amino radical.
Uncle's amino does not limit especially.In addition,, the amino or the heterocycle structure of alkyl can be enumerated, more particularly, imidazole ring or triazole ring can be enumerated with carbon number 1～4 as uncle's amino.
If the compound that in a part, has active hydrogen and uncle's amino that illustration is so then can be enumerated N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, N; N-dipropyl-1,3-propanediamine, N, N-dibutyl-1,3-propanediamine, N; N-dimethyl ethylene diamine, N, N-diethyl ethylene diamine, N, N-dipropyl ethylene diamine, N, N-dibutyl ethylene diamine, N; N-dimethyl 1,4-butane diamines, N, N-diethyl-1,4-butane diamines, N; N-dipropyl-1,4-butane diamines, N, N-dibutyl-1,4-butane diamines etc.
In addition; As uncle's amino is nitrogenous heterocyclic material; Can enumerate pyrazoles ring, imidazole ring, triazole ring, tetrazole ring, indole ring, carbazole ring, indazole ring, benzene imidazole ring, benzotriazole ring, benzoxazole ring, benzothiazole ring, diazosulfide ring etc. and contain the assorted 5 yuan of rings of N, pyridine ring, pyridazine ring, pyrimidine ring, triazine ring, quinolizine ring, acridine ring, isoquinoline ring etc. contain 6 yuan of rings of azepine.As these nitrogen heterocyclic ring preferably imidazole ring or triazole ring.
If these have the compound of imidazole ring and primary amino radical concrete illustration, then can enumerate 1-(3-aminopropyl) imidazoles, histidine, 2-aminooimidazole, 1-(2-amino-ethyl) imidazoles etc.
In addition, if concrete illustration has triazole ring and amino compound, then can enumerate 3-amino-1,2; 4-triazole, 5-(2-amino-5-chlorphenyl)-3-phenyl-1H-1,2,4-triazole, 4-amino-4H-1,2; 4-triazole-3,5-glycol, 3-amino-5-phenyl-1H-1,3,4-triazole, 5-amino-1; 4-diphenyl-1,2,3 triazoles, 3-amino-1-benzyl-1H-2,4-triazole etc.Wherein, preferred N, N-dimethyl-1,3-propanediamine, N, N-diethyl-1,3-propanediamine, 1-(3-aminopropyl) imidazoles, 3-amino-1,2,4-triazole.
With regard to above-mentioned urethane is the preferred cooperation ratio of spreading agent raw material; With respect to polyisocyanate compounds 100 mass parts; The compound that in a part, has the number-average molecular weight 300～10000 of one or more hydroxyl is 10～200 mass parts, preferred 20～190 mass parts, and then preferred 30～180 mass parts; In with a part, having the amino compound of active hydrogen and uncle is 0.2～25 mass parts, preferred 0.3～24 mass parts.
Such urethane is that the polystyrene conversion weight-average molecular weight (Mw) of utilizing GPC to measure of spreading agent is generally 1000～200000, and is preferred 2000～100000, more preferably 3000～50000 scope.Under the situation of the scope of this molecular weight, dispersiveness and dispersion stabilization are superior, dissolubility or dispersed also superior time the, control reaction easily.
Such urethane is that the manufacturing of spreading agent is to carry out according to the known method of urethane resin manufacturing.Solvent during as manufacturing; Usually use ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, isophorone; Ester classes such as acetic acid ethyl ester, acetic acid butyl ester, oxytol acetate; Hydro carbons such as benzene,toluene,xylene, hexane, a part of alcohols such as diacetone alcohol, isopropyl alcohol, sec-butyl alcohol, the tert-butyl alcohol, chlorides such as methylene chloride, chloroform; Ethers such as tetrahydrofuran, Anaesthetie Ether, one or more of aprotic polarity solvents such as dimethyl formamide, N-Methyl pyrrolidone, dimethyl sulfoxide (DMSO) etc.
When above-mentioned manufacturing, use common urethane catalysts.As this catalyzer, for example, can enumerate tertiary amine systems such as iron system, triethylamine, triethylene diamine such as tin systems such as dibutyl tin dilaurate, dioctyl two lauric acid tin, dibutyl two tin octoates, stannous octoate, pentanedione acid iron, iron chloride etc.
The import volume that in a part, has the amino compound of active hydrogen and uncle preferably is controlled to be the scope of 1～100mg-KOH/g by reacted amine value.The more preferably scope of 5～95mg-KOH/g.The amine value is through utilizing acid with the basic group acid-base titration, corresponding to acid number, and the value of representing with the mg acid of KOH.If the amine value is lower than above-mentioned scope, then be in the tendency that dispersibility reduces, in addition, if surpass above-mentioned scope, then development property reduces easily.
Also have, in the dispersion resin that obtains through above reaction under the residual situation that NCO arranged, and if then destroy NCO with alcohol or amino-compound, then the ageing stability of product uprises, therefore preferably.
As the graft copolymer spreading agent, preferably has the graft copolymer spreading agent of the repetitive that comprises nitrogen-atoms at main chain.Wherein preferably has the repetitive of representing by (12) by the repetitive or the formula of formula (11) expression.
[changing 34]
General formula (11)
In general formula (11), R
1The alkylidene of expression carbon number 1～5, A representes any of hydrogen atom or formula (13)～(15).
In the above-mentioned general formula (11), R
1The alkylidene of straight chain shape such as expression methylene, ethylidene, propylidene or branched carbon number 1～5, preferred carbon number 2～3, and then preferred ethylidene.A representes any of hydrogen atom or formula (13)～(15), but preferred formula (13).
[changing 35]
General formula (12)
In above-mentioned general formula (12), R
1, A and formula (11) R
1, A is identical.
[changing 36]
General formula (13)
In above-mentioned formula (13), W
1The straight chain shape or the branched alkylidene of expression carbon number 2～10, the alkylidene of carbon numbers 4～7 such as wherein preferred butylidene, pentylidene, hexylidene.P representes 1～20 integer, preferred 5～10 integer.
[changing 37]
General formula (14)
In above-mentioned formula (14), Y
1The concatenating group of expression divalence, the alkylidene of carbon numbers 1～4 such as wherein preferred ethylidene, propylidene and the oxyalkylene group of carbon numbers such as oxirane, epoxypropane 1～4.
W
2The alkylidene of straight chain shape such as expression ethylidene, propylidene, butylidene or branched carbon number 2～10, the alkylidene of carbon numbers 2～3 such as wherein preferred propylidene, propylidene.
Y
2The expression hydrogen atom or-CO-R
2(R
2The expression ethyl-, the alkyl of carbon numbers 1～10 such as propyl group, butyl, amyl group, hexyl, the alkyl of carbon numbers 2～5 such as wherein preferred ethyl, propyl group, butyl, amyl group).
Q representes 1～20 integer, preferred 5～10 integer.
[changing 38]
General formula (15)
In above-mentioned formula (15), W
3The alkyl of expression carbon number 1～50 or have the hydroxy alkyl of the carbon number 1～50 of 1～5 hydroxyl, wherein the alkyl of carbon number 10～20 such as preferred stearyl, monohydroxy stearyl etc. have the hydroxy alkyl of the carbon number 10～20 of 1～2 hydroxyl.
The containing ratio by the repetitive of formula (11) or (12) expression in the said graft copolymer is preferably high, is generally 50 moles more than the %, preferred 70 moles more than the %.Share by the repetitive of formula (11) expression and by two sides of the repetitive of formula (12) expression also can, it contains qualification especially of ratio, but preferably contains a large amount of repetitives by formula (11).
Tale by the repetitive of formula (11) or formula (12) expression is generally 1～100, and is preferred 10～70, and then preferred 20～50.
In addition, contain formula (11) and formula (12) repetitive in addition also can, as other repetitives, for example, can the illustration alkylidene, oxyalkylene group etc.Preferred its end of the graft copolymer of second embodiment is-NH
2And-R
1-NH
2, at this R
1With said R
1Be equivalent).
Also have, under the situation of said graft copolymer, main chain can be the straight chain shape, also can be side chain.
The amine value of said graft copolymer is generally 5～100mg KOH/g, preferred 10～70mg KOH/g, and then below preferred 15～40mg KOH/g.If the amine value is in this scope, then dispersion stabilization is good, viscosity stabilization, and raffinate tails off, and has formed the electrical characteristics behind the liquid crystal panel and has also improved.
The weight-average molecular weight preferred 3000～100000, especially preferred 5000～50000 of utilizing GPC to measure as above-mentioned spreading agent.If weight-average molecular weight in this scope, then can prevent the cohesion of colorant, the viscosity of himself is high only, and is also good to the dissolubility of organic solvent.
The synthetic method of above-mentioned spreading agent can adopt known method, for example can use the method for putting down in writing in the special public clear 63-30057 communique of Japan.
Above-mentioned spreading agent can use a kind of separately, also can mix two or more uses.
The use level of preferred dispersants is selected with the scope of 0～30 quality % with respect to the total solid-state amount in the colored curable resin composition.
In addition, in the colored curable resin composition of second embodiment, spreading agent to contain proportional be 10～300 quality % with respect to the look material usually, preferred 20～100 quality %, especially preferred 30～80 quality %.If containing of spreading agent is proportional in this scope, then can prevent cohesion, thickness also becomes suitable thickness, and under the situation about in color filter, using, the unit interstices control that can suppress in the liquid crystal cells chemical industry preface is bad.
The colored curable resin composition of second embodiment except above-mentioned macromolecule dispersing agent, can also share shown in following, from began known spreading agent (pigment dispersing agent) in the past.
As known spreading agent (pigment dispersing agent); Macromolecule dispersing agent (for example, daiamid gathers (methyl) acrylic ester, (methyl) acrylic acid series copolymer with its salt, HMW unsaturated acid ester, modified polyurethane, modified poly ester, modification) be can enumerate, polyxyethylated phosphate, polyoxyethylene alkyl amine, alkanolamine, pigment derivative etc. reached.
Macromolecule dispersing agent is according to its structure, and then can be categorized as straight chain shape macromolecule, terminal-modified type macromolecule, graft type macromolecule, block type polymer.
Macromolecule dispersing agent is adsorbed in the surface of pigment, and performance prevents the effect of condensing again.Therefore, can the terminal-modified type macromolecule, graft type macromolecule, the block type polymer that have to the anchor site of surface of pigments be enumerated as preferred construction.On the other hand, pigment derivative has through to the surface of pigments modification, promotes the effect of the absorption of macromolecule dispersing agent.
As the concrete example of the known spreading agent (pigment dispersing agent) that can in second embodiment, use, can enumerate BYK Chemie corporate system " Disperbyk-107 (carboxylate), 130 (polyamide), 161,162,163,164,165,166,170 (high-molecular copolymers) ", EFKA corporate system " EFKA4047,4050,4010,4165 (polyurethane series), EFKA4330,4340 (segmented copolymer), 4400,4402 (modified polyacrylates), 5010 (polyesteramides), 6220 (fatty acid polyesters), 6745 (phthalocyanine derivates), 6750 (AZOpigments derivant) ", monosodium glutamate fine techniques corporate system " this handkerchief of Archie PB821, PB822 ", common prosperity company chemistry corporate system " Fu Lulong TG-710 (urethane oligomers) ", " Port リ Off ロ one No.50E, No.300 (acrylic acid series copolymer) ", nanmu originally changes into soap corporate system " this handkerchief silk 5000 (phthalocyanine derivates), 22000 (AZOpigments derivant) of Oulu, 13240 (polyesteramines), 3000,17000,27000 (portion has the macromolecule of function portion endways), 24000,28000,32000,38500 (graft type macromolecules) ", daylight chemicals corporate system " Nikkor T106 (polyoxyethylene sorbitan monoleate), MYS-IE X (polyoxyl 40 stearate) " etc. in corporate system " Di Sipalong #7004 (polyether ester), DA-703-50, DA-705, DA-725 ", KAO. Corp. SA's system " Chinese mugwort Viktor Markin 920,930,935,985 (polyoxyethylene nonylplenyl ether) ", " A Xitamin 86 (stearyl amine acetic acid esters) ", the rouble.
In second embodiment; Use under the situation of aforesaid known spreading agent; Can be that 20～300mg/g and weight-average molecular weight are the compound of 3000～100000 scope with respect to said acid number, with 10～100 quality %, promptly the scope of 1/10～1/1 (equivalent) is used.
(f-4) dispersing aid
As dispersing aid, can enumerate for example pigment derivative.
As pigment derivative, can enumerate azo system, phthalocyanine system, quinacridone, benzimidazolone system, Kui phthalein ketone system, isoindoline ketone and be 、 dioxazine system, anthraquinone system, indanthrene Xi 、 perylene system, purple cyclic ketones (ペ リ ノ Application) and be, diketopyrrolopyrrolecocrystals is 、 dioxazine series pigments etc.
Substituting group as pigment derivative; Can enumerate sulfonic group, sulfamoyl and quaternary salt thereof, phthalimide methyl, dialkyl aminoalkyl, hydroxyl, carboxyl, amide group etc. directly or the group that combines with the pigment skeleton through alkyl, aryl, heterocyclic radical etc.; Preferred sulfoamido and quaternary salt thereof, sulfonic group, more preferably sulfonic group.In addition, these substituting groups can be substituted with a plurality of at a pigment skeleton, also can be the potpourri of substituting group different compounds.
As the concrete example of pigment derivative, can enumerate the sulfonic acid etc. of sulfonic acid 、 triazine dioxin pigment of sulfonic acid, the diketo-pyrrolo pyrrole pigments of sulfonic acid, the quinacridone pigment of sulfonic acid, the anthraquinone pigment of sulfonic acid, the Kui phthalein ketone pigment of sulfonic acid, the phthalocyanine color of AZOpigments.
As commercially available pigment derivative, can enumerate this handkerchief silk 5000 of Oulu, Ai Fujia corporate system Ai Fujia 475 of this handkerchief silk 22000 of A Bixiya corporate system Oulu, the phthalocyanine system of azo system etc.These pigment derivative can be used a kind of separately, and it is two or more also can to mix use.
The use level of dispersing aid is selected with the scope of 0～20 quality % preferably with respect to the total solid-state amount in the colored curable resin composition.
(f-5) solvent
In the colored curable resin composition of second embodiment; In order to dissolve or to disperse (a) look material, (b) to have compound, (c) special adhesive resin, (d) Photoepolymerizationinitiater initiater, (e) the specific aggregation property compound of at least one ethene property unsaturated double-bond or the constituent that becomes to grade arbitrarily, can use solvent.
As said solvent, for example can enumerate glycol ethers and/or alkoxy ester class.
As the concrete example of glycol ethers, can enumerate propylene glycol monomethyl ether, propylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, glycol monomethyl-n-butyl ether acetic acid esters, glycol monomethyl-n-butyl ether, ethylene glycol ethyl ethers acid esters, ethylene acetate, ethylene glycol bisthioglycolate ethylether, propylene glycol list-n-butyl ether, propylene glycol-t-butyl ether, diethylene glycol diethyl ether, TC, TC acetic acid esters, diethylene glycol list-n-butyl ether acetic acid esters, dihydroxypropane single-ethyl ether, DPGME, DPGME acetic acid esters, tripropylene glycol methyl ether etc.
As the concrete example of alkoxy ester class, can enumerate acetic acid ethyl ester, methyl isobutyrate, 3-ethoxy-propionic acid ethyl ester, 3-ethoxy-propionic acid methyl ester, 3-methoxypropionic acid methyl ester, 3-methoxypropionic acid ethyl ester, 3-methoxypropionic acid propyl diester, 3-methoxypropionic acid butyl ester, butylacetic acid ester, acetic acid (n, sec, t-) butyl ester, butyl stearate, propionic acid ethyl ester, ethyl benzoate, ethyl orthoformate, ethyl caprylate, propyl-acetic acid ester etc.
In addition; For example, can enumerate Di Iso Propyl Ether, mineral spirits, n-pentanone, amyl ether, n-hexane, Anaesthetie Ether, isoprene, ethyl isobutyl ether, n-octane, Ba Er West Road #2, A Puke #18 solvent, diisobutylene, amyl group acetic acid esters, A Puke thinning agent (ア プ コ シ Application Na one), butyl ether, DIBK, methylcyclohexene, methyl nonyl ketone, propyl ether, decane, cable clamp that (ソ one カ Le) solvent No.1 and No.2, pentylformic acid ester, hexyl ether, diisopropyl ketone, this #150 of rope sieve, hexene, Xi Er TS 28 solvents, butyl chloride, ethyl pentyl group ketone, amyl group chloride, butylene glycol diacetate esters, methoxy pentanone, methyl butyl ketone, methyl hexyl ketone, benzonitrile, methylcellosolve acetate, methyl isoamyl ketone, methyl isobutyl ketone, amyl group acetic acid esters, pentylformic acid ester, dicyclohexyl, cinene, methoxy amylalcohol, methyl amyl ketone, methyl isopropyl Ketone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, ethyl cellosolve acetate, carbitol, cyclohexanone, lactic acid ethyl ester, propylene glycol, 3-methoxy propyl acid esters, 3-ethoxy-c acid esters, two symmetrical diol bisethers (ジ グ ラ イ system), ethyl carbitol, BC, 3-methyl-3-methoxybutanol, 3-methyl-3-methoxyl butylacetic acid ester etc.
Solvent can use a kind of separately, share two or morely also can.
Content shared, solvent was suitably set in the scope of 50～95 quality % corresponding to the ratio (concentration) of total solid-state amount usually during the colored curable resin composition of second embodiment was whole.And then 70～90 quality % preferably, especially preferred is the scope of 75～90 quality %.
Under the very few situation of the content of solvent, it is too high that viscosity becomes, and is difficult to apply, if too much, then be difficult to form coated film, therefore, preferably suitably regulates.
(preparation of colored curable resin composition)
The colored curable resin composition of second embodiment is as follows; Pigment preparation disperse object in advance; In this pigment dispersing thing; Make solvent contain (c) special adhesive resin, (b) polymerizable compound, (d) Photoepolymerizationinitiater initiater, and (e) specific aggregation property compound, as required to wherein mixing (f-1) alkoxysilane compound containing trialkylsilyl group in molecular structure or (f-2) adjuvant such as surfactant and preparing.
At this, the compound method of the pigment dispersing thing that is suitable in the colored curable resin composition of second embodiment is described.
Pigment dispersing thing in second embodiment for example can be through using vertical or horizontal sand mill, needle mill, slit grinding machine, ultrasonic dispersing machine etc.; With described (a) look material, (f-3) dispersion resin, and (f-5) potpourri of organic solvent, utilize pearl by generation such as the glass of the particle diameter of 0.01～1mm, zirconias to carry out loose processing and obtaining of differential.
In addition, also can before carrying out the pearl dispersion, use the extruder of two rollers, three rollers, bowl mill, rotating cylinder grinding machine, decollator, mixer, homogenizer, mixing machine, single shaft or twin shafts etc., when giving strong shear strength, carry out mixing dispersion treatment.
Also have, about mixing, the write up that disperses in T.C.Patton work " being coated with flow and pigment dispersing (Paint Flow and PigmentDispersion) " (John Wiley and Sons company printed in 1964) etc.
The colored curable resin composition of second embodiment that obtains like this keeps (a) look material with good disperse state through containing said each composition in composition, obtain good look characteristic; And; Use said composition, when for example having constituted color filter, can obtain high contrast.
< manufacturing approach of colored pattern formation method, color filter, and color filter >
Manufacturing approach, and the color filter of colored pattern formation method, the color filter of second embodiment are described.
In the colored pattern formation method of second embodiment, utilize the slit coating method through comprising, apply the operation of the colored curable resin composition of second embodiment, can form the colored pattern of expectation.When the coating speed of said coating process is 200mm/sec～400mm/sec, play the effect of second embodiment significantly.
The colored curable resin composition of said second embodiment is through forming said structure; Carrying out under the situation of slit coating with the high speed of coating speed 200mm/sec～400mm/sec; It is also few to apply inequality; Suppress to apply the generation of defective, thus can be with the few light-sensitive surface of efficient making defective.
This colored pattern formation method preferably is applicable to the manufacturing approach of color filter.
Below, the manufacturing approach (manufacturing approach of the color filter of second embodiment) of the color filter of the colored pattern formation method that has been suitable for second embodiment is described.
The manufacturing approach of the color filter of second embodiment comprises: with the colored curable resin composition of second embodiment directly or via other layers; On substrate, give; The operation of formation photosensitive film (below, suitably abbreviate " photosensitive film formation operation " as); The photosensitive film that forms is carried out (making public) operation (below, suitably abbreviate " exposure process " as) of pattern exposure across mask; Photosensitive film after the exposure is developed, the operation of formation colored pattern (below, suitably abbreviate " developing procedure " as).
Below, each operation in the manufacturing approach of second embodiment is described.
(photosensitive film formation operation)
In photosensitive film forms operation, directly or have on the substrate of other layers, apply the colored curable resin composition (giving) of second embodiment, form photosensitive film.
As the substrate that can in this operation, use; For example, can enumerate the photo-electric conversion element substrate that uses in the soda-lime glass, Pa Likesi (registered trademark) glass, the quartz glass that use in the liquid crystal display cells etc. and substrate that on them, has adhered to nesa coating or the imaging apparatus etc., for example silicone substrate etc. or auxilliary property burning film semiconductor (CMOS) etc. mutually.These substrate also is formed with the black streaking of isolating each pixel sometimes.
In addition, on these substrates, as required, for adhesion improvement, the diffusion preventing of material or the planarization of substrate surface of the layer on top, undercoat (other layer) is set also can.
In the manufacturing approach of the color filter of second embodiment; Coating method as the colored curable resin composition of second embodiment on substrate; Comprise the slit coating method of using; Under the situation of the operation that applies with coating speed 200mm/sec～400mm/sec, preferred from the viewpoint of efficiency.Colored curable resin composition according to second embodiment can be known; Can utilize the slit coating of such high speed to come high productivity ground to form the light-sensitive surface that applies the few homogeneous of defective; Therefore; Be used under the situation of manufacturing approach of color filter of second embodiment, its effect is remarkable, forms light-sensitive surface but certainly be suitable for various coating methods such as sputtering method, spin coating, the coating of stream curtain coating, roller coating, stencil printing in addition.
As the coating thickness of colored curable resin composition, can enumerate 0.1～10 μ m, more preferably 0.2～5 μ m, and then preferred 0.2～3 μ m.
With regard to the drying (prebake) of the photosensitive film that on substrate, applies, can carry out 10～300 seconds with 50 ℃～140 ℃ temperature in hot plate, baking box etc.
(exposure process)
In exposure process, said photosensitive film is formed the photosensitive film that forms in the operation and make public through mask and promptly carry out pattern exposure across mask pattern with regulation.
In this operation, for photosensitive film, make public via the mask pattern of stipulating as coated film, can only make partly solidified thus by light-struck coated film.
Radioactive ray as can when making public, using especially preferably use ultraviolet rays such as g ray, i ray.Preferred 5～the 1500mJ/cm of exposure
2, more preferably 10～1000mJ/cm
2, 10～500mJ/cm most preferably
2
Color filter making is under the situation of used for liquid crystal display element, preferred 5～200mJ/cm in above-mentioned scope
2, more preferably 10～150mJ/cm
2, 10～100mJ/cm most preferably
2In addition, be under the solid-state imager situation about using at the color filter of making, preferred 30～1500mJ/cm in above-mentioned scope
2, more preferably 50～1000mJ/cm
2, 80～500mJ/cm most preferably
2
(developing procedure)
Secondly, through carrying out development treatment, the wash-out in developer solution of the unexposed portion in the exposure process, the part that a residual light is solidified.As developer solution,, just can use developer solution arbitrarily as long as the film of the solidification compound in dissolving uncured on the other hand, does not dissolve solidified portion.Specifically, can use the combination of various organic solvents or the WS of alkalescence.
As development temperature, be generally 20 ℃～30 ℃, development time is 20～90 seconds.
As said organic solvent, can enumerate operable above-mentioned solvent when the colored curable resin composition of preparation second embodiment.
The WS as said alkalescence; For example; Alkaline aqueous solution below preferred the use is as developer solution; This alkaline aqueous solution is for to make NaOH, potassium hydroxide, sodium carbonate, soda mint, sodium silicate, sodium metasilicate, ammoniacal liquor, ethylamine, diethylamide, dimethylethanolamine, TMAH, tetraethyl ammonium hydroxide, choline, pyrroles, piperidines, 1,8-diaza-bicyclo-[5,4,0]-alkali compounds such as 7-undecylene be diluted to 0.001～10 quality % with pure water, preferably becomes the alkaline aqueous solution after the concentration of 0.01～1 quality %.
Also have, used under the situation of the developer solution that comprises such alkaline aqueous solution, after development, clean (spray) usually with pure water.
Behind developing procedure, clean and remove remaining developer solution, after having applied drying, carry out heat treated (afterwards curing).
After to cure be the heat treated after the development that is used for fully being cured, carry out 100 ℃～240 ℃ heat curing usually and handle.Substrate is under the situation of glass substrate or silicone substrate, in the said temperature scope preferred 200 ℃～240 ℃.
After this, cure in the processing,,, utilize heating arrangements such as hot plate or baking oven (heated air circulation type dryer), high frequency heating machine, carry out with continous way or batch type like above-mentioned condition for the coated film after developing.
The photosensitive film of counting the above explanation of degree through the form and aspect of expecting repeatedly forms operation, exposure process, reaches developing procedure (and then heating process as required), makes the color filter (color filter of second embodiment) of the form and aspect that comprise expectation.
Utilize color filter that the manufacturing approach of the color filter of aforesaid second embodiment obtains structure for the colored pattern that on substrate, has the colored curable resin composition that uses second embodiment and form, the contrast of said color filter is shockingly up to more than 5000.
At this, contrast is meant: about constituting R (red), G (green), the B (indigo plant) of color filter, and the contrast of individually estimating by each look.
The assay method of contrast is described below.With the overlapping polarization plates in the both sides of determinand, under the state that the direction of polarized light that makes polarization plates is parallel to each other,, measure the brightness Y1 of the light of the polarization plates of having passed through the opposing party from a side butt backlight of a side polarization plates.Then, make under the mutually orthogonal state of polarization plates, measuring the brightness Y2 of light.The measured value that use obtains is calculated contrast by Y1/Y2.At this, as polarization plates, use a day eastern electrician G1220DUN, the mensuration machine uses chroma-luminance meter BM-5 ((strain) topology is agree system).
The colored curable resin composition of second embodiment is formed under the situation of film to giving on the substrate, as the dry thickness of film, be generally 0.3～5.0 μ m, preferred 0.5～3.5 μ m expects 1.0～2.5 μ m most.
As substrate, can enumerate the alkali-free glass that uses in the liquid crystal display cells etc., soda-lime glass, Pa Likesi (registered trademark) glass, quartz glass and adhere to the photo-electric conversion element substrate that uses in substrate or the solid-state imager etc. of nesa coating, for example silicone substrate etc. and reach plastic base at them.Be formed with the black streaking of isolating each picture element on the substrate like this.
Preferably in plastic base, have gas-barrier layer and/or solvent resistance layer on its surface.
As the purposes of the colored curable resin composition of second embodiment, be that main body is narrated mainly, but can also be applicable to the black matrix that between the pixel of color filter, is provided with certainly with purposes to the pixel of color filter.With regard to black matrix, except using in the colored curable resin composition of second embodiment, as colorant; Added outside the material of colorant of black such as carbon black, titanium be black; Can also be identical with the method for making of above-mentioned pixel, carry out pattern exposure, alkali development, then; Cure after carrying out, promote being solidified to form of film.
< liquid crystal display cells >
The liquid crystal display cells of second embodiment possesses the color filter of second embodiment.
More particularly, form alignment films in the inner surface side of color filter, make itself and electrode base board opposed, in clearance portion, fill up liquid crystal and seal, thus, the liquid crystal display cells that obtains second embodiment is a panel.
Can know according to second embodiment, also can realize in the time of can being provided at high speed coating the coating characteristic of good face shape colored curable resin composition, have the colored pattern that uses said colored curable resin composition to carry out the colored pattern method of formationing of slit coating operation and utilize said colored pattern formation method formation.
In addition, can know, can provide and utilize the high speed coating operation also have manufacturing approach and the color filter that utilizes said manufacturing approach to make of the color filter of the good said colored pattern of face shape according to second embodiment.Especially can provide thickness deviation and film defective few, the color filter that contrast is high.
And then, the liquid crystal display cells that has used said color filter can be provided.
[embodiment]
Below, through embodiment first embodiment is described more specifically, but is not limited to following embodiment.Also have, under situation about not limiting especially, " % " " part " is a quality criteria.
[embodiment 1]
(the 1. preparation of cured composition for color A-1)
1-1. the preparation of dispersible pigment dispersion (P1)
To comprise 30/70 (mass ratio) potpourri, 40 mass parts as the C.I. pigment green 36 of pigment and C.I. pigment yellow 219, as BYK 2001 (Disperbyk: Bick chemicals (BYK) corporate system, solid component concentration 45.1 quality %) 10 mass parts of spreading agent (solid state component convert about 4.51 mass parts), and utilized the ball mill mixed and dispersed 15 hours as the mixed liquor of 3-ethoxy-propionic acid ethyl 150 mass parts of solvent, prepared dispersible pigment dispersion (P1).
Dispersible pigment dispersion (P1) about obtaining utilizes dynamic light scattering method, and the result who measures the mean grain size of pigment is 200nm.
1-2. the preparation of cured composition for color A-1 (coating liquid)
The composition that mixes following composition A-1, and dissolving have been prepared cured composition for color A-1.
< forming A-1 >
63.0 parts of dispersible pigment dispersions (P1)
2.2 parts of dipentaerythritol acrylates
2.2 parts of specific aggregation property compound: M-1
1.6 parts of 1-(4-(phenyl sulfo-)-phenyl)-2-(O-benzoyl group oxime)
2.5 parts of specific alkali soluble resin A (containing ethene property unsaturated group)
2.5 parts of alkali soluble resins
(benzyl methacrylate (BzMA)/methacrylic acid (MAA) multipolymer, mol ratio: 7/3, Mw:5000)
Like 0.1 part of a cron N-695
(O-cresol-novolak varnish type epoxy resin, big Japanese ink chemical industry (strain) system)
25.9 parts of propylene glycol monomethyl ether
(the 2. work system of color filter)
2-1. the formation of cured composition for color layer
To contain cured composition for color A-1 through the above-mentioned pigment that obtains as Photoresist solution; Be coated on the glass substrate of 550mm * 650mm with following condition after; Make its standby 10 minutes with original state; It is coated on new glass substrate, implements vacuum drying and prebake (prebake) (100 ℃ 80 seconds), formed cured composition for color coated film (cured composition for color layer).
(slit coating condition)
Apply the gap of the peristome of a front end: 50 μ m
Coating speed: 100mm/ second
Substrate and the gap that applies head: 150 μ m
Applied thickness (dry thickness): 2 μ m
Application temperature: 23 ℃
2-2. exposure, development
Then; Use the ultrahigh pressure mercury lamp of 2.5kW, the cured composition for color coated film is made public with pattern-like, after exposure; With whole 10% WS lining of coated film, static 60 seconds with organic system developer solution (trade name: CD, Fujiphoto electronic equipment malleable iron Leah (strain) system).
2-3. heat treated
After static, pure water is sprayed with the spray shape, developer solution is flow through, photocuring is handled and the coated film of development treatment heats 1 hour (afterwards curing) in 220 ℃ baking box with having implemented.Thus, obtained on glass substrate, forming the color filter that colored pattern forms.
(3. performance evaluation)
The cured composition for color A-1 that use is prepared in above-mentioned (coating liquid), the pattern of having estimated the cured composition for color coated film (dyed layer) that on glass substrate, forms becomes second nature with being described below, substrate adhesiveness, mask rugosity amount and surfaceness.The result is illustrated in the table 1.
3-1. pattern becomes second nature
Utilize scanning electron microscope (SEM), observed the section shape of the pattern that forms.This assessment item is estimated based on following metewand.Also have, the pattern section is forward taper most preferably, its less preferred rectangle.Not preferred undercut (back taper).
< metewand >
A is taper forward: the angle that forms with the plane of substrate is less than 75 degree
The B rectangle: the angle that forms with the plane of substrate is less than 75 degree
The C back taper: the angle that forms with the plane of substrate surpasses 90 degree
3-2. substrate adhesiveness
In the adhering evaluation of substrate, scanning electron microscope (SEM) has observed whether pattern to have taken place damaged.This assessment item is based on following metewand and estimates.
< metewand >
A: it is damaged not observe pattern fully
B: it is damaged almost not observe pattern, but it is damaged to observe a part
C: it is damaged to observe a large amount of patterns significantly
3-3. mask rugosity amount
With regard to mask rugosity amount, utilize sizing appearance (ICRON, Olympus (strain) system) to measure the very little method of the pattern of formation.This assessment item is based on following metewand and estimates.
< metewand >
A: with respect to mask is the rugosity amplitude more than+5 μ m
B: with respect to mask be more than+2 μ m, less than the rugosity amplitude of 5 μ m
C: with respect to mask is the rugosity amplitude less than+2 μ m
3-4. surfaceness
With regard to surfaceness, utilize AFM (the miniature analyser of atomic force (ア ト ミ Star Network Off オ one ス マ イ ロ ア Na ラ イ ザ one)) to come the surfaceness of the pattern of instrumentation formation.This assessment item is based on following metewand and estimates.
A:Ra=15
(1.5nm) below
B:Ra=16
(1.6nm) above～below 30 (3.0nm)
C:Ra=31
(3.1nm) more than
[embodiment 2～6, comparative example 1,2]
In embodiment 1; Composition among the composition A-1 that uses in the preparation with cured composition for color A-1 replaces being the material shown in the below table 1; In addition; All with embodiment 1 identical ground, preparation cured composition for color A-2～A-8 has obtained having the color filter that uses its colored pattern that forms.And then, carried out the evaluation identical with embodiment 1.The result is illustrated in the table 1.
[table 1]
(3) shown in the table 1 composition is that M-1～M-6 is the compound that synthesizes with being described below.
[synthetic routine 1:M-1's is synthetic]
M1 be as alcoholic compound said exemplary compounds (MA-2), (MA-3), and as the reaction product of the said exemplary compounds (MU-22) of isocyanate compound.
After MA-2 (0.1 mole) and MA-3 (0.2 mole) be dissolved in acetonitrile 100ml, (trade name: 100mg Ni Angsitan U-600 (day east change into strain formula can corporate system)) had formed the solution of homogeneous to add bismuth three (2 ethyl hexanoic acid ester).Be heated to 60 ℃, splash into the acetonitrile 10ml solution of MU-22 (0.1 mole).After drippage finishes, stirred 8 hours down at 55 ℃～65 ℃.After reaction finishes, reactant liquor is cooled to room temperature after, heat up in a steamer solvent, utilize silica gel column chromatography to carry out purifying, having obtained (3) specific aggregation property compound is M-1.
[synthetic routine 2:M-2's is synthetic]
M2 is as the said exemplary compounds (MA-8) of alcoholic compound with as the condensation reaction products of the said exemplary compounds (MU-27) of isocyanate compound.
After MA-8 (0.2 mole) was dissolved in acetonitrile 100ml, (trade name: 100mg Ni Angsitan U-600 (day east change into strain formula can corporate system)) had formed uniform solution to add bismuth three (2 ethyl hexanoic acid ester).Be heated to 60 ℃, splash into the acetonitrile 10ml solution of MU-27 (0.1 mole).Drippage stirred 8 hours at 55 ℃～65 ℃ after finishing.After reaction finishes, reactant liquor is cooled to room temperature after, heat up in a steamer solvent, utilize silica gel column chromatography to carry out purifying, having obtained (3) specific aggregation property compound is M-2.
Equally, make following exemplary compounds reaction, having obtained (3) specific aggregation property compound is M-3～M-6.
M-3: as the said exemplary compounds (MA-2) of alcoholic compound, (MA-3), and as the reaction product of the said exemplary compounds (MU-27) of isocyanate compound.
M-4: as the said exemplary compounds of amines (A-2) with as the reaction product of the said exemplary compounds (C-2) of halogen contained compound.
M-5: as the said exemplary compounds (MA-1) of alcoholic compound with as the reaction product of the said exemplary compounds (MU-21) of isocyanate compound.
M-6: as the said exemplary compounds (MA-11) of alcoholic compound with as the reaction product of the said exemplary compounds (MU-23) of isocyanate compound.
In addition, (1) composition shown in the table 1 is that the structure of specific alkali soluble resin A is as follows.
[changing 39]
Specific alkali soluble resin A
As shown in table 1; Distinguish as follows; That is: use the cured composition for color of each embodiment; Under the situation that has formed colored pattern on the support, obtained with respect to use not containing arbitrary side or two sides' of composition (1) and composition (2) in first embodiment the comparative example 1,2 of extraneous cured composition for color of first embodiment, become second nature in pattern, all superior color filter in any evaluation of substrate adhesiveness, mask rugosity amount, surfaceness.
Below, through embodiment, second embodiment is described more specifically, but is not limited to following embodiment.Also have, under situation about not limiting especially, " % " " part " is a quality criteria.
(embodiment 7)
Mix the composition of following composition, prepared dispersible pigment dispersion.
(dispersible pigment dispersion)
(a) pigment
C.I. paratonere 254 ... 10 parts
C.I. paratonere 177 ... 4 parts
(f-2) dispersion resin
Bick chemicals corporate system byk-161 (effective constituent 30 weight %)
13.3 part
(f-5) solvent
Propylene glycol monomethyl ether ... 32.7 part
In addition, mix following compositions separately, prepared transparent Photoresist liquid.
(transparent Photoresist liquid)
(b) polymerizable compound
Dipentaerythritol acrylate ... 4.0 part
(c) special adhesive resin
The acrylic resin of representing by following structure ... 4.0 part
(d) Photoepolymerizationinitiater initiater
2-(2-chlorphenyl)-4,5-diphenyl-imidazole dimer ... 0.4 part
4,4 '-two (diethylamino) benzophenone ... 0.2 part
The 2-methylbenzothiazole ... 0.4 part
(e) have at least one ethene property unsaturated double-bond, in molecule, have the compound that is selected from urethane, acid amides, reaches the part-structure of urea
(compound shown in the table 2) (... Amount shown in the table 2)
(f-2) surfactant
Sumitomo 3M corporate system FC430 ... 0.04 part
(f-5) solvent
Propylene glycol monomethyl ether ... 50 parts
[changing 40]
[a: b: c: d=55: 15: 20; 10 (mole %), Mw:12,000]
Mix above-mentioned dispersible pigment dispersion and transparent Photoresist liquid, after the stirring homogenization, add the zirconium oxide bead 300g of particle diameter 0.5mm, in paint regulator, shook 5 hours, carried out dispersion treatment.Then, filter, obtained colored pattern formation property composition (colored curable resin composition) of homogeneous.
Composition is used in colored pattern formation about obtaining, has carried out following evaluation.
[evaluation]
(applying planar)
Use slit coating machine (coating machine, Fa Site corporate system head carry), the colored pattern that obtains is formed use composition,, be coated on 550mm * 650mm glass substrate (1737, Kening Co.,Ltd's system) with 200mm/ second.Then, in 90 ℃ baking box dry 60 seconds (prebake).The thickness of desciccator diaphragm is 1.2 μ m.
Under these conditions, implemented 200 coating (applying 20 seconds at interval), utilized optical microscope, the coating of having observed the 200th is planar.
A: at each 0.25 square metre, number of defects is less than one
B: at each 0.25 square metre, number of defects is more than one and less than five
C: at each 0.25 square metre, number of defects is more than five
(thickness deviation)
The colored pattern that will in above-mentioned, obtain form with composition 16 from the pad that has projection 10 shown in Figure 1 as Fig. 2 organize saidly into the discharge opening of slot die 12 of 550mm width spray; With coating speed 100mm/s, apply slit 100 μ m, after cure processing after, thickness is coated on glass substrate 14 (Kening Co.,Ltd's system 1737,0.7mm thick) with becoming 2.0 μ m.Also have, the dimensional units among Fig. 1 is mm.
At this moment, the change of the thickness deviation 18 of the muscle shape that causes for the jut of pad 10, after cure processing after, utilize the contact pin type film thickness gauge DECTAC-3 of Aruba's gram corporate system to measure.The result is illustrated in the table 2.
Metewand is described below, and B is the permissible range in the practicality.
A: the thickness deviation is in ± 1%
B: the thickness deviation surpass ± 1% and ± 2% in
C: the thickness deviation surpasses ± 2%.
(contrast)
Use slit coating machine (coating machine, Fa Site corporate system head carry), on 550mm * 650mm glass substrate (1737, Kening Co.,Ltd's system),, applied the colored pattern that in above-mentioned, obtains and formed and use composition with coating speed 200mm/ second.Then, in 90 ℃ baking box dry 60 seconds (prebake).The thickness of desciccator diaphragm is 1.2 μ m.
On whole of filming, with 200mJ/cm
2(illumination 20mW/cm
2) make public, cover filming after the exposure with 1% WS of alkaline developer CDK-1 (Fujiphoto electronic equipment malleable iron Leah (strain) system), static 60 seconds.After static, with spray shape spreading, developer solution is flow through pure water.The film heat treated 1 hour (afterwards curing) in 220 ℃ baking box that to implement exposure more as described above and develop has formed the pigmentary resin tunicle (colored pattern) that color filter is used on glass substrate, made painted filter substrate (color filter).
Go up the placement polarization plates at the pigmentary resin tunicle (colored pattern) of painted filter substrate; Sandwich the pigmentary resin tunicle; The value that the brightness of the brightness that the BM-5 that uses topology to agree corporate system measures polarization plates when being parallel during with quadrature, the brightness when parallel brightness during divided by quadrature obtains (brightness during=brightness when parallel/quadrature) is as the index of contrast evaluation.With regard to contrast, numerical value is high more, representes good more.
(evaluation of color filter)
The colored curable resin composition of estimating adjusting in above-mentioned applies the storage stability of liquid, reaches and use this colored curable resin composition, exposure light sensitivity, substrate adhesiveness, development property and the pattern section shape of the solidification compound coated film (dyed layer) that on glass substrate, forms with being described below.The result is illustrated in the table 2.
< the exposure light sensitivity of coated film (dyed layer) >
With exposure at 10～200mJ/cm
2Scope in change and making public, with after pattern lines width after the curing exposure that becomes 20 μ m estimate as the exposure light sensitivity.The value of exposure light sensitivity is more little, and the expression light sensitivity is high more.
< development property, pattern section shape, substrate adhesiveness >
Substrate surface and section shape after curing after utilizing optical microscope and SEM photo to observe to have confirmed.
In exposure process, observe the having or not of residue of not zone of irradiates light (unexposed portion), estimated development property.
< development property >
A: do not confirm residue fully at unexposed.
B: confirm residue slightly at unexposed, but do not become problem in the practicality.
C: confirm residue significantly at unexposed.
Observed the section shape of the pattern that forms.The pattern section shape is forward taper most preferably, its less preferred rectangle.Not preferred back taper.
As the adhering evaluation of substrate, observed whether pattern to have taken place damaged.About these assessment items, estimate based on following benchmark.
<substrate adhesiveness >
A: it is damaged not observe pattern fully
B: it is damaged almost not observe pattern, but it is damaged to observe a part
C: it is damaged to observe a large amount of patterns significantly.
< pattern section shape >
A: angle of taper is 30～70 degree scopes (forward tapers)
B: angle of taper is 70～90 degree scopes (forward tapers)
C: angle of taper is 90 degree (rectangle)
D: angle of taper surpasses 90 degree (back taper)
(embodiment 8～12)
In embodiment 7, (e) had at least-individual ethene property unsaturated double-bond, in molecule, have the compound that is selected from urethane, acid amides, reaches the part-structure of urea and change as shown in table 2ly; In addition; With embodiment 7 identical ground, prepared colored pattern formation and used composition, and estimated.
(comparative example 3)
In embodiment 7, do not add (e) composition, in addition,, prepared colored pattern formation and used composition, and estimated with embodiment 7 identical ground.
[table 2]
As (e) composition in the table 2, use the compound that obtains with being described below.
[synthetic example 3]: (M1's is synthetic)
M1 is the reaction product of alcoholic compound (MA-2), (MA-3) and isocyanate-based (MU-22).
After MA-2 (0.1 mole) and MA-3 (0.2 mole) be dissolved in acetonitrile 100ml, (trade name: 100mg Ni Angsitan U-600 (day east change into strain formula can corporate system)) had formed uniform solution to add bismuth three (2 ethyl hexanoic acid ester).Be heated to 60 ℃, the acetonitrile 10ml solution of drippage MU-22 (0.1 mole).After drippage finishes, under 55 ℃～65 ℃, stirred 8 hours.After reaction finishes, reactant liquor is cooled to room temperature after, heat up in a steamer solvent, utilize silica gel column chromatography to carry out purifying, obtained (E) and in molecule, had and be selected from urethane, acid amides, and the compound of the part-structure of urea i.e. (M1).
[synthetic example 4]: (M2's is synthetic)
M2 is the condensation reaction products of alcoholic compound (MA-8) and isocyanates based compound (MU-27) と.
After MA-8 (0.2 mole) was dissolved in acetonitrile 100ml, (trade name: 100mg Ni Angsitan U-600 (day east change into strain formula can corporate system)) had formed uniform solution to add bismuth three (2 ethyl hexanoic acid ester).Be heated to 60 ℃, the acetonitrile 10ml solution of drippage MU-27 (0.1 mole).After drippage finishes, under 55 ℃～65 ℃, stirred 8 hours.After reaction finishes, reactant liquor is cooled to room temperature after, heat up in a steamer solvent, utilize silica gel column chromatography to carry out purifying, obtained (E) composition i.e. (M2).
Equally, make following compound reaction, obtained (M3)～(M6).
M3: the reaction product of amines (A-2) and isocyanates based compound (MU-27).
M4: the reaction product of amines (A-2) and halogen contained compound (C-2).
M5: the reaction product of alcoholic compound (MA-1) and isocyanates based compound (MU-21).
M6: the reaction product of alcoholic compound (MA-11) and isocyanates based compound (MU-23).
Clearly can know from table 2, use the colored pattern formation of embodiment 7～12 to use colored curable resin composition, carry out not having face uneven under the situation of slit coating machine coating, it applies planar good.Can know in addition, can solidify with ISO.
Can know that on the other hand the colored pattern of comparative example 3 forms planar and the uneven part omitted of face is poor, substrate adhesiveness, pattern section shape extreme difference with the coating of composition under the situation of having carried out said coating.
In addition, it is superior to have a contrast of color filter of second embodiment that the colored pattern that uses embodiment 7～12 forms the colored pattern that forms with colored curable resin composition.
Disclosed content whole is included in this instructions as reference among number of patent application 2007-147350 of Japan and the 2007-230668.
Claims (17)
1. a color filter is used cured composition for color, wherein, contains following (1), (2), (3), and each composition of (4):
(1) is selected from side chain and has (methyl) acrylic copolymer of ester ring type (methyl) acryloyl group and have 0.001～0.20eq/g (methyl) acryloyl group and acid number is at least a alkali soluble resin of 10～150 multipolymer;
(2) Photoepolymerizationinitiater initiater;
(3) have ethene property unsaturated double-bond urethane compound, have the amide compound of ethene property unsaturated double-bond or have the urea compounds of ethene property unsaturated double-bond;
(4) colorant.
2. color filter according to claim 1 is used cured composition for color, wherein,
It is said that to have 0.001～0.20e q/g (methyl) acryloyl group and acid number be that 10～150 multipolymer is the compound of formula (1-1) expression, the compound of formula (1-2) expression or the compound of formula (1-3) expression,
[changing 1]
At general formula (1-1), (1-2) or (1-3), R representes hydrogen atom or methyl, R
1Phenyl, the aryl of carbon number 6～12 or the aralkyl of carbon number 7～12 of alkyl, the alkyl that contains carbon number 1～4 or the alkoxy of expression carbon number 1～18, R
2The alkylidene of 1～18 of carbon number of expression, contain carbon number 1～4 alkyl phenyl carbamate or contain the carbamate of the ester ring type base of carbon number 3～18, R
3The expression carbon number is the alkylidene of 2～16 straight or branched, and a～e in a～d in the general formula (1-1), the general formula (1-2), a～e in the general formula (1-3) represent the mole percent level of repetitive, and a～d:b in the general formula (1-1) representes 3～50; C representes 3～40, and d representes 2～60, a+b+c+d=100; A～e:b in general formula (1-2) and the general formula (1-3) representes 0～85, and c representes 3～50, and d representes 3～40; E representes 2～60, and a+b+c+d+e=100, n are 2～16.
3. color filter according to claim 1 is used cured composition for color, wherein,
Said (3) have ethene property unsaturated double-bond urethane compound, have the amide compound of ethene property unsaturated double-bond or have in the urea compounds of ethene property unsaturated double-bond, have nitrogen heterocyclic ring.
4. color filter according to claim 1 is used cured composition for color, wherein,
Said (3) have ethene property unsaturated double-bond urethane compound, have the amide compound of ethene property unsaturated double-bond or have in the urea compounds of ethene property unsaturated double-bond, also have the isocyanuric acid ester skeleton.
5. color filter according to claim 1 is used cured composition for color, wherein,
Said (3) have ethene property unsaturated double-bond urethane compound, have the amide compound of ethene property unsaturated double-bond or have in the urea compounds of ethene property unsaturated double-bond, also have oxyalkylene group.
6. color filter wherein, has:
Use the colored pattern that each described color filter forms with cured composition for color in the claim 1～5.
7. the manufacturing approach of a color filter wherein, comprising:
Each described color filter is used cured composition for color in the coating claim 1～5 on supporter, forms the operation of cured composition for color layer;
The operation that said cured composition for color layer is made public across mask;
Said cured composition for color layer after the exposure is developed, form the operation of colored pattern.
8. colored curable resin composition wherein, comprises:
(a) look material;
(b) has the compound of at least one ethene property unsaturated double-bond;
(c) adhesive resin, it contains (methyl) acrylic copolymer that has ester ring type (methyl) acryloyl group at side chain;
(d) Photoepolymerizationinitiater initiater; And
(e) have ethene property unsaturated double-bond urethane compound, have the amide compound of ethene property unsaturated double-bond or have the urea compounds of ethene property unsaturated double-bond.
9. colored curable resin composition according to claim 8 is characterized in that,
Have compound 100 weight portions of at least one ethene property unsaturated double-bond with respect to said (b), to contain urethane compound that said (e) have ethene property unsaturated double-bond, have the amide compound of ethene property unsaturated double-bond or to have the urea compounds of ethene property unsaturated double-bond more than 5 mass parts and less than the amount of 25 mass parts.
10. solidification compound according to claim 8, wherein,
Said (e) have ethene property unsaturated double-bond urethane compound, have the amide compound of ethene property unsaturated double-bond or have the urea compounds of ethene property unsaturated double-bond, for having the compound of isocyanuric acid ester skeleton.
11. solidification compound according to claim 8, wherein,
Said (e) have ethene property unsaturated double-bond urethane compound, have the amide compound of ethene property unsaturated double-bond or have the urea compounds of ethene property unsaturated double-bond; Reaction product for the alcoholic compound of compound with isocyanic acid ester bond and formula (I) expression
[changing 2]
General formula (I)
In said general formula (I), R
1, R
2Represent hydrogen atom or alkyl, R respectively independently
3The functional group of expression hydrogen atom, alkyl, alkoxy, allyl, aryl, formula (II) expression or the functional group of formula (III) expression,
[changing 3]
General formula (II) general formula (III)
In said general formula (II), n representes 1～10 integer, in addition, in general formula (II) and general formula (III), R
4Expression hydrogen atom or alkyl, in general formula (III), the R of a plurality of existence in molecule
4Can be identical, also can be inequality.
12. solidification compound according to claim 8 is characterized in that,
Also contain (f-1) alkoxysilane compound containing trialkylsilyl group in molecular structure.
13. a colored pattern formation method wherein, comprising:
Utilize the slit coating method, apply the operation of each described colored curable resin composition in the claim 8～12.
14. a colored pattern, it utilizes claim 13 described colored pattern formation method and forms.
15. the manufacturing approach of a color filter wherein, has:
Utilize the slit coating method, each described colored curable resin composition in the claim 8～12 is coated on substrate surface, form the operation of colored pattern.
16. a color filter, wherein,
Utilize the described manufacturing approach of claim 15 to make, and its contrast is more than 5000.
17. a liquid crystal display cells, wherein,
Used the described color filter of claim 16.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007147350A JP5535430B2 (en) | 2007-06-01 | 2007-06-01 | Curable composition for color filter, color filter, and method for producing the same |
| JP147350/2007 | 2007-06-01 | ||
| JP230668/2007 | 2007-09-05 | ||
| JP2007230668A JP2009063767A (en) | 2007-09-05 | 2007-09-05 | Colored curable resin composition, method for forming colored pattern, colored pattern, method for producing color filter, color filter, and liquid crystal display element |
| PCT/JP2008/059212 WO2008149662A1 (en) | 2007-06-01 | 2008-05-20 | Curable composition for color filter, method for producing curable composition for color filter, colored curable resin composition, method for forming colored pattern, colored pattern, method for producing color filter, color filter, and liquid crystal display device |
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| JP4890388B2 (en) * | 2007-08-22 | 2012-03-07 | 富士フイルム株式会社 | Colored photosensitive composition, color filter and method for producing the same |
| KR101279877B1 (en) * | 2009-03-24 | 2013-07-01 | 디아이씨 가부시끼가이샤 | Photocurable composition for liquid crystal display panel seal, and liquid crystal display panel |
| KR101904761B1 (en) * | 2011-03-29 | 2018-10-08 | 토요잉크Sc홀딩스주식회사 | Red colored composition for color filter, and color filter |
| CN102830589B (en) * | 2012-08-23 | 2014-12-17 | 京东方科技集团股份有限公司 | Resin composition of negative photoresist and preparation method thereof |
| KR102138381B1 (en) * | 2012-11-02 | 2020-07-27 | 닛테츠 케미컬 앤드 머티리얼 가부시키가이샤 | Light-shielding resin composition for touch panel and touch panel using the same |
| KR101985769B1 (en) * | 2013-03-15 | 2019-06-04 | 동우 화인켐 주식회사 | Method of manufacturing color filter using maskless digital exposure |
| JP6277142B2 (en) * | 2015-02-02 | 2018-02-07 | 富士フイルム株式会社 | Functional composite film and quantum dot film |
| KR102202279B1 (en) * | 2015-03-20 | 2021-01-13 | 동우 화인켐 주식회사 | Colored photosensitive resin composition |
| JP7249119B2 (en) * | 2018-09-27 | 2023-03-30 | 東京応化工業株式会社 | Photosensitive resin composition, method for producing patterned cured film, and cured film |
| CN115073703B (en) * | 2022-06-29 | 2023-05-23 | 江西辙炜新材料科技有限公司 | Ultraviolet light curing water-based colorant, and preparation method and application thereof |
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| JP2000338322A (en) * | 1999-05-26 | 2000-12-08 | Mitsubishi Chemicals Corp | Photopolymerizable composition for color filter and color filter |
| JP2005017441A (en) * | 2002-07-18 | 2005-01-20 | Mitsubishi Chemicals Corp | Method for producing photosensitive colored resin composition, colored resin composition, photosensitive colored resin composition, color filter and liquid crystal display |
| JP4338479B2 (en) * | 2003-09-04 | 2009-10-07 | 富士フイルム株式会社 | Color filter and manufacturing method thereof |
| JP5140903B2 (en) * | 2004-07-02 | 2013-02-13 | 三菱化学株式会社 | Colored resin composition, color filter, and liquid crystal display device |
| WO2006064873A1 (en) * | 2004-12-15 | 2006-06-22 | Mitsubishi Chemical Corporation | Resin composition for liquid crystal panel, and color filter and liquid crystal panel using the same |
| JP5292708B2 (en) * | 2006-03-10 | 2013-09-18 | 三菱化学株式会社 | Curable composition, color filter, and liquid crystal display device |
| JP4710703B2 (en) * | 2006-04-21 | 2011-06-29 | Ｊｓｒ株式会社 | Radiation-sensitive composition for forming colored layer, color filter, and color liquid crystal display element |
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| TWI440902B (en) | 2014-06-11 |
| KR101490224B1 (en) | 2015-02-05 |
| WO2008149662A1 (en) | 2008-12-11 |
| CN101680984A (en) | 2010-03-24 |
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| TW200905267A (en) | 2009-02-01 |
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