CN104460230A - Coloring composition, colored cured film and display device - Google Patents
Coloring composition, colored cured film and display device Download PDFInfo
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- CN104460230A CN104460230A CN201410460962.5A CN201410460962A CN104460230A CN 104460230 A CN104460230 A CN 104460230A CN 201410460962 A CN201410460962 A CN 201410460962A CN 104460230 A CN104460230 A CN 104460230A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B47/00—Porphines; Azaporphines
- C09B47/04—Phthalocyanines abbreviation: Pc
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B25/00—Quinophthalones
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B45/00—Complex metal compounds of azo dyes
- C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
- C09B45/04—Azo compounds in general
- C09B45/08—Copper compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0033—Blends of pigments; Mixtured crystals; Solid solutions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
- C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
- C09B67/0084—Dispersions of dyes
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/22—Absorbing filters
- G02B5/223—Absorbing filters containing organic substances, e.g. dyes, inks or pigments
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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
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- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Optics & Photonics (AREA)
- Dispersion Chemistry (AREA)
- Materials For Photolithography (AREA)
- Polymerisation Methods In General (AREA)
- Paints Or Removers (AREA)
- Optical Filters (AREA)
Abstract
The invention provides a coloring composition suitable for forming a colored cured film with good chromaticity even high film brightness and contrast ratio. The coloring composition comprises (A) a coloring agent, (B) adhesive resin and (C) polymerizable compound, the (A) coloring agent includes zinc halide phthalocyanine paint, quinophthalone paint and azomethine copper paint, and a ratio of a content w2 of the quinophthalone paint and a content w3 of the azomethine copper paint is, by mass ratio, w2/w3=70/30-85/15.
Description
Technical field
The present invention relates to coloured composition, color solidification film and display element, more specifically, relate to the coloured composition of the color solidification film used in the color liquid crystal display device, solid-state imager, organic EL display element, Electronic Paper etc. for the formation of transmission-type or reflection-type, use the color solidification film that this coloured composition is formed, and possess the display element of this color solidification film.
Background technology
When using the sensitivity composition of colored radiation to manufacture color filter, there will be a known following method, namely, the sensitivity composition of the colored radiation of coating pigment decentralized on substrate after drying, dry coating pattern form is desirably irradiated (hereinafter referred to as " exposure ") radioactive ray, develops, obtain the method (for example, referring to patent documentation 1 ~ 2) of assorted pixel thus.In addition, the optical polymerism composition that also known utilization is dispersed with carbon black forms the method (for example, referring to patent documentation 3) of black matrix.Further, also the colored resin composition of known use pigment-dispersing type utilizes ink-jetting style to obtain the method (for example, referring to patent documentation 4) of assorted pixel.
In recent years, society strengthens day by day to energy-conservation requirement, such as, require to get both the display performance of high-quality and the display element of power saving.In order to adapt to this requirement, attempting suppressing the brightness of backlight and reducing power consumption, improving the brightness of color filter, contrast simultaneously.
As the colorant used in color filter, from the view point of thermotolerance and solvent resistance, mostly use pigment.When forming the coloured composition of green pixel, known zinc halide phthalocyanine color and various yellow uitramarine to be combinationally used, such as, disclose in patent documentation 5 ~ 6 and zinc halide phthalocyanine color and quinophthalone pigments are combinationally used.In addition, Patent Document 7 discloses zinc bromide phthalocyanine color, pigment Y (C.I. pigment yellow 150) and C.I. pigment yellow 13 8 are combinationally used.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2-144502 publication
Patent documentation 2: Japanese Unexamined Patent Publication 3-53201 publication
Patent documentation 3: Japanese Unexamined Patent Publication 6-35188 publication
Patent documentation 4: Japanese Unexamined Patent Publication 2000-310706 publication
Patent documentation 5: Japanese Unexamined Patent Publication 2012-098712 publication
Patent documentation 6: Japanese Unexamined Patent Publication 2013-011867 publication
Patent documentation 7: Japanese Unexamined Patent Publication 2013-037276 publication
Summary of the invention
But, for the situation of the coloured composition recorded in patent documentation 5 ~ 7, find to have to make the thickness of color solidification film thickening to improve the colorimetric properties such as brightness, contrast.If the thickness of color solidification film is thicker, then display element is also thickening, so easily become obstacle in lightening, the lightness of development display element.Therefore, even if present situation is strongly required the coloured composition that exploitation is suitable for being formed the good color solidification film of film brightness, colorimetric properties that contrast is also high.
Therefore, even if problem of the present invention is to provide the coloured composition being suitable for being formed the good color solidification film of film brightness, colorimetric properties that contrast is also high.Further, problem of the present invention is to provide the color solidification film using this coloured composition to be formed and the display element possessing this color solidification film.
The present inventor etc. further investigate, and found that by using specific colorant with certain amount ratio, can solve above-mentioned problem.
Namely, the invention provides a kind of coloured composition, it is characterized in that, containing (A) colorant, (B) resin glue and (C) polymerizable compound, (A) colorant contains zinc halide phthalocyanine color, quinophthalone pigments and azomethine copper pigment, the content w of quinophthalone pigments
2with the content w of azomethine copper pigment
3ratio be w by quality ratio
2/ w
3=70/30 ~ 85/15.
In addition, the invention provides color solidification film and the display element possessing this color solidification film, this color solidification film contains zinc halide phthalocyanine color, quinophthalone pigments and azomethine copper pigment, the content w of quinophthalone pigments
2with the content w of azomethine copper pigment
3ratio be w by quality ratio
2/ w
3=70/30 ~ 85/15." color solidification film " mentioned here refers to the green pixel etc. used in display element, solid-state imager.
If use coloured composition of the present invention, even if the also high color solidification film of film brightness, contrast can be formed.In addition, the coloured composition of the application of the invention, can also form the color solidification film of thermotolerance and excellent solvent resistance.
Therefore, coloured composition of the present invention extremely can be suitable for the making of the solid-state imager of the display element, cmos image sensor etc. of color liquid crystal display device, organic EL display element, Electronic Paper etc.
Embodiment
Below, the present invention is described in detail.
coloured composition
Below, the constituent of coloured composition of the present invention is described in detail.
-(A) colorant-
Coloured composition of the present invention contains zinc halide phthalocyanine color, quinophthalone pigments and azomethine copper pigment as (A) colorant, the content w of quinophthalone pigments
2with the content w of azomethine copper pigment
3ratio be w by quality ratio
2/ w
3=70/30 ~ 85/15.
As zinc halide phthalocyanine, preferred zinc bromide phthalocyanine or bromination chlorination ZnPc.Bromination chlorination ZnPc is the pigment being categorized as C.I. naphthol green 58 in color index (C.I.) name, is preferably the structure that following formula (1) represents.
(in formula (1), X represents hydrogen atom, chlorine atom or bromine atoms independently of each other, and in whole X, 10 ~ 15 is bromine atoms, and 1 ~ 6 is chlorine atom.)
As quinophthalone system yellow uitramarine, be not particularly limited, preferred C.I. pigment yellow 13 8.
As azomethine copper pigment, C.I. pigment yellow 117, C.I. pigment Yellow 12 9 etc. can be enumerated, wherein, preferred C.I. pigment Yellow 12 9.
In the present invention, the content w of quinophthalone pigments
2with the content w of azomethine copper pigment
3need than by quality ratio for w
2/ w
3=70/30 ~ 85/15, this ratio is more preferably w
2/ w
3=70/30 ~ 80/20, more preferably 70/30 ~ 75/25.By being set to such mode, even if film brightness, contrast also high, thermotolerance and all excellent color solidification film of solvent resistance can be formed.
The content w of zinc halide phthalocyanine color
1with the content w of azomethine copper pigment
3containing mass ratio (w
1/ w
3) can suitably select, from the view point of improving brightness and contrast further, be preferably w
1/ w
3=65/35 ~ 90/10, be more preferably 70/30 ~ 90/10, more preferably 75/25 ~ 88/12, be particularly preferably 80/20 ~ 86/14.
Coloured composition of the present invention is generally used for forming green pixel.At this moment, also other colorant and zinc halide phthalocyanine color, quinophthalone pigments and azomethine copper pigment can be mixed together.As other colorant, be not particularly limited, can suitably select color, material according to purposes.
As other colorant, can enumerate pigment and dyestuff, other colorant can be used alone or in combination of two or more kinds.Wherein, from the aspect obtaining the high pixel of brightness, contrast and colouring power, as pigment, preferred organic pigment, in addition, as dyestuff, preferably has organic dye.
As organic pigment, such as, color index (C.I. can be enumerated; The Society of Dyersand Colourists corporation issues) in be classified as the compound of pigment, namely by the pigment being accompanied by following color index (C.I.) and numbering.
C.I. the red pigment such as paratonere 166, C.I. paratonere 177, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 254, C.I. paratonere 264;
C.I. the viridine green such as pigment Green 7, C.I. pigment green 36;
C.I. pigment blue 15: 6, the blue pigment such as C.I. pigment blue 16, C.I. alizarol saphirol 80;
C.I. the yellow uitramarine such as pigment yellow 83, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. pigment yellow 17 9, C.I. pigment yellow 180, C.I. pigment yellow 185, C.I. pigment yellow 211, C.I. pigment yellow 215;
C.I. orange pigment such as pigment orange 38 grade;
C.I. the violet pigment such as pigment Violet 23.
In addition, the mordant pigment that Japanese Unexamined Patent Publication 2001-081348 publication, Japanese Unexamined Patent Publication 2010-026334 publication, Japanese Unexamined Patent Publication 2010-191304 publication, Japanese Unexamined Patent Publication 2010-237384 publication, Japanese Unexamined Patent Publication 2010-237569 publication, Japanese Unexamined Patent Publication 2011-006602 publication, Japanese Unexamined Patent Publication 2011-145346 publication etc. are recorded can be enumerated.
In addition, as above-mentioned dyestuff, preferably
ton based dye, triarylmethane based dye, cyanines based dye, anthraquinone based dye, azo based dye etc.More specifically, the organic dyestuff that Japanese Unexamined Patent Publication 2010-32999 publication, Japanese Unexamined Patent Publication 2010-254964 publication, Japanese Unexamined Patent Publication 2011-138094 publication, International Publication No. 10/123071 pamphlet, Japanese Unexamined Patent Publication 2011-116803 publication, Japanese Unexamined Patent Publication 2011-117995 publication, Japanese Unexamined Patent Publication 2011-133844 publication, Japanese Unexamined Patent Publication 2011-174987 publication etc. are recorded can be enumerated.
In the present invention, pigment and dyestuff can be used alone respectively or mix two or more and use.
Wherein, as other colorant, the yellow colorants beyond the green colourant beyond preferred zinc halide phthalocyanine color, quinophthalone pigments and azomethine copper pigment.
In the present invention, zinc halide phthalocyanine color, quinophthalone pigments, azomethine copper pigment and other pigment mixed arbitrarily can be carried out refining using by recrystallization method, reprecipitation method, solvent cleaning method, sublimed method, vaccum heating method or their combination.In addition, these pigment can carry out modification to use to its particle surface with resin as required.As the resin particle surface of pigment being carried out to modification, such as, the resin of the vehicle resin recorded in Japanese Unexamined Patent Publication 2001-108817 publication or commercially available various pigment dispersions can be enumerated.In addition, primary particle miniaturization can be used by so-called salt mill by organic pigment.As the method for salt mill, such as, method disclosed in Japanese Unexamined Patent Publication 08-179111 publication can be adopted.
In addition, also can further containing known spreading agent and dispersing aid together with zinc halide phthalocyanine color, quinophthalone pigments, azomethine copper pigment and other colorant mixed arbitrarily in the present invention.
As known spreading agent, such as, polyurethane series spreading agent can be enumerated, polyethyleneimine system spreading agent, polyoxyethylene alkyl ether system spreading agent, polyoxyethylene alkyl phenyl ether system spreading agent, polyethylene glycol di system spreading agent, sorbitan fatty acid ester system spreading agent, Polyester spreading agent, dispersant containing acrylics etc., as commercially available product, such as, can use Disperbyk-2000, Disperbyk-2001, BYK-LPN6919, (methyl) dispersant containing acrylics such as BYK-LPN21116 (being BYK Inc. above), Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (being BYK Inc. above), the polyurethane series spreading agents such as Solsperse 76500 (Lubrizol Co., Ltd. system), the polyethyleneimine system spreading agents such as Solsperse 24000 (Lubrizol Co., Ltd. system), Ajisper PB821, Ajisper PB822, Ajisper PB880, the spreading agents such as Polyester spreading agent and BYK-LPN21324 (BYK Inc.) such as Ajisper PB881 (being Ajinomoto Fine-Techno Co., Ltd. system above).
Wherein, as spreading agent, be preferably selected from least a kind in (methyl) dispersant containing acrylic, polyurethane series spreading agent and Polyester spreading agent, more preferably (methyl) dispersant containing acrylic.
In (methyl) dispersant containing acrylic, preferably there is (methyl) dispersant containing acrylic of cross-linking functional group.As this cross-linking functional group, Oxyranyle, oxetanyl, tetrahydrofuran base, THP trtrahydropyranyl etc. can be enumerated containing oxygen saturation heterocyclic radical, ethylenic unsaturated group, epithio base, (two sulfo-s) carbonate group etc.Preferably containing oxygen saturation heterocyclic radical, more preferably oxetanyl, tetrahydrofuran base, THP trtrahydropyranyl in these cross-linking functional group, preferred oxetanyl, tetrahydrofuran base further.
(methyl) dispersant containing acrylic with cross-linking functional group refers to the compound be made up of (being total to) polymkeric substance of (methyl) acrylic monomer with cross-linking functional group.In addition, " (methyl) acrylic monomer " refers to the polymerizable compound in molecule with (methyl) acryloyl group, and " (methyl) acryloyl group " refers to acryloyl group or methacryl.
As (methyl) dispersant containing acrylic with cross-linking functional group, such as, (methyl) acrylic monomer with cross-linking functional group can be enumerated and other can the multipolymer of (methyl) acrylic monomer of copolymerization.Can (methyl) acrylic monomer of copolymerization as other, such as, (methyl) acrylate with oxyalkylene group, (methyl) acrylate with hydroxyl, (methyl) acrylate with primary amino radical ~ tertiary amino, (methyl) alkyl acrylate, (methyl) benzyl acrylate etc. can be enumerated, they can have a kind or two or more.
The ratio with (methyl) acrylic monomer of cross-linking functional group is preferably 5 ~ 50 quality %, more preferably 10 ~ 30 quality % in whole monomer.Should illustrate that there is (methyl) dispersant containing acrylic of cross-linking functional group, such as, can utilize the method synthesis recorded in Japanese Unexamined Patent Publication 2012-118505 publication.
By such mode, desired effect of the present invention can be obtained further.
In the present invention, the content of (B) spreading agent relative to (A) colorant 100 mass parts preferably 5 ~ 300 mass parts, more preferably 10 ~ 200 mass parts, further preferred 20 ~ 100 mass parts.By being such mode, easily obtain the desired effect of the application.
In addition, as dispersing aid, pigment derivative etc. can be enumerated.As pigment derivative, specifically, the sulfonic acid etc. of copper phthalocyanine, diketopyrrolo-pyrrole, quinophthalone can be enumerated.
From the aspect forming the pixel that brightness is high, colouring power is excellent, (A) colorant in the solid constituent of coloured composition, be generally 5 ~ 70 quality % containing proportional, be preferably 5 ~ 60 quality %, be more preferably 10 ~ 50 quality %, be particularly preferably 20 ~ 50 quality %.Here solid constituent refers to the composition beyond solvent described later.
In addition, during containing other colorant, the proportional total content relative to colorant that contains of other colorant is preferably below 50 quality %, more preferably below 30 mass parts.Lower limit is not particularly limited, and is more than 0.01 quality %.
-(B) resin glue-
As (B) resin glue in the present invention, be not particularly limited, preferably there is the resin of the acidic functionality such as carboxyl, phenolic hydroxyl group.Wherein, the polymkeric substance preferably with carboxyl is (following, also referred to as " carbonyl bearing polymer "), such as, the ethylenically unsaturated monomers with more than one carboxyl can be enumerated (following, also referred to as " unsaturated monomer (b1) ") can the multipolymer of ethylenically unsaturated monomers (hereinafter also referred to as " unsaturated monomer (b2) ") of copolymerization with other.
As above-mentioned unsaturated monomer (b1), such as, can enumerate (methyl) acrylic acid, maleic acid, maleic anhydride, mono succinate (2-(methyl) acryloyl-oxyethyl) ester, ω-carboxy-polycaprolactone list (methyl) acrylate, to vinyl benzoic acid etc.
These unsaturated monomers (b1) can be used alone or mix two or more and use.
In addition, as above-mentioned unsaturated monomer (b2), such as, can enumerate:
The N-position substituted maleimide amine of N-phenylmaleimide, N-N-cyclohexylmaleimide and so on;
Styrene, α-methyl styrene, 4-Vinyl phenol, to hydroxy-alpha-methyl styrene, aromatic ethenyl compound to vinylbenzyl glycidyl ether, acenaphthylene and so on;
(methyl) methyl acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) allyl acrylate, (methyl) benzyl acrylate, polyglycol (degree of polymerization 2 ~ 10) methyl ether (methyl) acrylate, polypropylene glycol (degree of polymerization 2 ~ 10) methyl ether (methyl) acrylate, single (methyl) acrylate of polyglycol (degree of polymerization 2 ~ 10), single (methyl) acrylate of polypropylene glycol (degree of polymerization 2 ~ 10), (methyl) cyclohexyl acrylate, (methyl) isobornyl acrylate, (methyl) acrylic acid three ring [5.2.1.0
2,6] decane-8-base ester, (methyl) acrylic acid dicyclopentenyl ester, glycerine list (methyl) acrylate, (methyl) acrylic acid 4-hydroxylphenyl ester, p-cumylphenol (methyl) acrylate of ethylene-oxide-modified (methyl) acrylate, (methyl) glycidyl acrylate, 3,4-epoxycyclohexylmethyl (methyl) acrylate, 3-((methyl) acryloyloxymethyl) oxetanes, 3-((methyl) acryloyloxymethyl)-3-Ethyloxetane and so on,
Cyclohexyl vinyl ether, isobornyl vinyl ether, three ring [5.2.1.0
2,6] decane-8-base vinyl ether, pentacyclopentadecandimethanol base vinyl ether, 3-(ethyleneoxy methyl)-3-Ethyloxetane and so on vinyl ether;
The end of the polymer molecular chain of polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, polysiloxane and so on has the macromonomer etc. of list (methyl) acryloyl group.
These unsaturated monomers (b2), can be used alone or mix two or more use.
In the multipolymer of unsaturated monomer (b1) and unsaturated monomer (b2), copolymerization ratios preferably 5 ~ 50 quality % of the unsaturated monomer (b1) in this multipolymer, more preferably 10 ~ 40 quality %.By making unsaturated monomer (b1) copolymerization in such scope, the coloured composition of alkali-developable and excellent storage stability can be obtained.
As the concrete example of unsaturated monomer (b1) with the multipolymer of unsaturated monomer (b2), such as, multipolymer disclosed in Japanese Unexamined Patent Publication 7-140654 publication, Japanese Unexamined Patent Publication 8-259876 publication, Japanese Unexamined Patent Publication 10-31308 publication, Japanese Unexamined Patent Publication 10-300922 publication, Japanese Unexamined Patent Publication 11-174224 publication, Japanese Unexamined Patent Publication 11-258415 publication, Japanese Unexamined Patent Publication 2000-56118 publication, Japanese Unexamined Patent Publication 2004-101728 publication etc. can be enumerated.
In addition; in the present invention; such as; disclosed in Japanese Unexamined Patent Publication 5-19467 publication, Japanese Unexamined Patent Publication 6-230212 publication, Japanese Unexamined Patent Publication 7-207211 publication, Japanese Unexamined Patent Publication 9-325494 publication, Japanese Unexamined Patent Publication 11-140144 publication, Japanese Unexamined Patent Publication 2008-181095 publication etc., also can be used in side chain and there is the carbonyl bearing polymer of the polymerism unsaturated links such as (methyl) acryloyl group as resin glue.
Resin glue in the present invention, (following with gel permeation chromatography, referred to as GPC) (eluting solvent: tetrahydrofuran) weight-average molecular weight (Mw) of polystyrene conversion of measuring is generally 1000 ~ 100000, is preferably 3000 ~ 50000.By being such mode, the residual film ratio of tunicle, pattern form, thermotolerance, electrical characteristics, resolution are further enhanced, and in addition, can suppress the generation of dry foreign matter when being coated with high level.
In addition, the weight-average molecular weight (Mw) of the resin glue in the present invention is preferably 1.0 ~ 5.0 with the ratio (Mw/Mn) of number-average molecular weight (Mn), is more preferably 1.0 ~ 3.0.Should illustrate, Mn mentioned here refers to the number-average molecular weight of the polystyrene conversion measured with GPC (eluting solvent: tetrahydrofuran).
Resin glue in the present invention can be manufactured by known method, such as, method disclosed in Japanese Unexamined Patent Publication 2003-222717 publication, Japanese Unexamined Patent Publication 2006-259680 publication, International Publication No. 07/029871 pamphlet etc. also can be utilized to control its structure, Mw, Mw/Mn.
In the present invention, resin glue can be used alone or mixes two or more and uses.
In the present invention, the content of resin glue is generally 10 ~ 1000 mass parts relative to (A) colorant 100 mass parts, is preferably 20 ~ 500 mass parts.By being such mode, alkali-developable, the storage stability of coloured composition, pattern form, colorimetric properties can be improved further.
-(C) polymerizable compound-
In the present invention, polymerizable compound refers to the compound with more than 2 polymerisable groups.As polymerisable group, such as, ethylenic unsaturated group, Oxyranyle, oxetanyl, N-alkoxy methyl amino etc. can be enumerated.In the present invention, as polymerizable compound, preferably there is the compound of more than 2 (methyl) acryloyl groups or there is the compound of more than 2 N-alkoxy methyl amino.
As the concrete example of compound with more than 2 (methyl) acryloyl groups, multifunctional (methyl) acrylate that aliphatic polyhydroxy compound and (methyl) acrylic acid are obtained by reacting can be enumerated, multifunctional (methyl) acrylate of caprolactone modification, alkylen oxide-modified multifunctional (methyl) acrylate, make to have polyfunctional carbamate (methyl) acrylate that (methyl) acrylate of hydroxyl and polyfunctional isocyanate are obtained by reacting, make to have multifunctional (methyl) acrylate etc. with carboxyl that (methyl) acrylate of hydroxyl and anhydride reaction obtain.
Here, as aliphatic polyhydroxy compound, such as, the aliphatic polyhydroxy compound of the divalent of ethylene glycol, propylene glycol, polyglycol, polypropylene glycol and so on can be enumerated; Aliphatic polyhydroxy compounds more than 3 valencys of glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol and so on.As above-mentioned (methyl) acrylate with hydroxyl, such as, (methyl) acrylic acid 2-hydroxyl ethyl ester, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, glycerine dimethacrylate etc. can be enumerated.As above-mentioned polyfunctional isocyanate, such as, toluene diisocyanate, hexamethylene diisocyanate, MDI, isophorone diisocyanate etc. can be enumerated.As acid anhydrides, such as, the tetra-atomic acid dianhydride of the acid anhydrides of the dibasic acid of succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride and so on, pyromellitic acid anhydride, bibenzene tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride and so on can be enumerated.
In addition, as multifunctional (methyl) acrylate of caprolactone modification, such as, the compound recorded in paragraph (0015) ~ (0018) of Japanese Unexamined Patent Publication 11-44955 publication can be enumerated.As above-mentioned alkylen oxide-modified multifunctional (methyl) acrylate, bisphenol-A two (methyl) acrylate of at least a kind of modification be selected from oxirane and epoxypropane can be enumerated, be selected from isocyanuric acid three (methyl) acrylate of at least a kind of modification in oxirane and epoxypropane, be selected from trimethylolpropane tris (methyl) acrylate of at least a kind of modification in oxirane and epoxypropane, be selected from pentaerythrite three (methyl) acrylate of at least a kind of modification in oxirane and epoxypropane, be selected from pentaerythrite four (methyl) acrylate of at least a kind of modification in oxirane and epoxypropane, be selected from dipentaerythritol five (methyl) acrylate of at least a kind of modification in oxirane and epoxypropane, be selected from dipentaerythritol six (methyl) acrylate etc. of at least a kind of modification in oxirane and epoxypropane.
In addition, as the compound with more than 2 N-alkoxy methyl amino, such as, the compound etc. with melamine structure, benzoguanamine structure, urea structure can be enumerated.Should illustrate, melamine structure, benzoguanamine structure refer to that having more than 1 triazine ring or phenyl replaces the chemical constitution of triazine ring as basic framework, are the concepts comprising melamine, benzoguanamine or their condensation product.As the concrete example of compound with more than 2 N-alkoxy methyl amino, N can be enumerated, N, N', N', N ", N "-six (alkoxy methyl) melamine, N, N, N', N'-tetra-(alkoxy methyl) benzoguanamine, N, N, N', N'-tetra-(alkoxy methyl) glycoluril etc.
In these polymerizable compounds, multifunctional (methyl) acrylate preferably making the aliphatic polyhydroxy compound of more than 3 valencys and (methyl) acrylic acid be obtained by reacting, multifunctional (methyl) acrylate of caprolactone modification, polyfunctional carbamate (methyl) acrylate, there is multifunctional (methyl) acrylate, the N of carboxyl, N, N', N', N "; N "-six (alkoxy methyl) melamine, N, N, N', N'-tetra-(alkoxy methyl) benzoguanamine.The surface smoothness of, dyed layer high from the intensity of dyed layer excellent and not easily produce the substrate in unexposed portion and on light shield layer floating dirty, film is residual etc., and aspect is considered, in multifunctional (methyl) acrylate making the aliphatic polyhydroxy compound of more than 3 valencys and (methyl) acrylic acid be obtained by reacting, particularly preferably trimethylolpropane triacrylate, pentaerythritol triacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate; In multifunctional (methyl) acrylate with carboxyl, the compound particularly preferably making pentaerythritol triacrylate and succinic anhydride be obtained by reacting, the compound that Dipentaerythritol Pentaacrylate and succinic anhydride are obtained by reacting.
In the present invention, (C) polymerizable compound can be used alone or mixes two or more and uses.
The content of (C) polymerizable compound in the present invention is preferably 10 ~ 1000 mass parts relative to (A) colorant 100 mass parts, more preferably 20 ~ 700 mass parts, further preferred 80 ~ 500 mass parts.By being such mode, curability, alkali-developable are further enhanced, produce on the substrate that can suppress unexposed portion with high level or on light shield layer floating dirty, film is residual.
-(D) Photoepolymerizationinitiater initiater-
Photoepolymerizationinitiater initiater can be contained in coloured composition of the present invention.Thus, radioactive ray are given to coloured composition sensitivity.The Photoepolymerizationinitiater initiater used in the present invention is the compound being produced the spike of the polymerization that can cause above-mentioned polymerizable compound by the exposure of the radioactive ray such as visible ray, ultraviolet, far ultraviolet, electron beam, X ray.
As such Photoepolymerizationinitiater initiater, such as, can enumerate thioxanthone compounds, acetophenone compound, united imidazole, triaizine compounds, O-acyl group oxime compound,
salt compound, benzoin compound, benzophenone cpd, α-dione compounds, polynucleation quinone compound, diazo-compounds, acid imide sulfonate compound etc.
In the present invention, Photoepolymerizationinitiater initiater can be used alone or mixes two or more and uses.As Photoepolymerizationinitiater initiater, be preferably selected from least a kind in thioxanthone compounds, acetophenone compound, united imidazole, triaizine compounds, O-acyl group oxime compound.
In the present invention in preferred Photoepolymerizationinitiater initiater, as the concrete example of thioxanthone compounds, thioxanthones, CTX, 2-methyl thioxanthones, ITX, ITX, 2 can be enumerated, 4-bis-clopenthixal ketone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropylthioxanthone etc.
In addition, as the concrete example of above-mentioned acetophenone compound, 2-methyl isophthalic acid-(4-(methyl mercapto) phenyl)-2-morpholino propane-1-ketone, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butane-1-ketone, 2-(4-methyl-benzyl)-2-(dimethylamino)-1-(4-morphlinophenyl) butane-1-ketone etc. can be enumerated.
In addition, as the concrete example of above-mentioned united imidazole, two (the 2-chlorphenyl)-4 of 2,2'-can be enumerated, 4', 5,5'-tetraphenyl-1,2'-bisglyoxaline, 2, two (2, the 4-dichlorophenyl)-4,4', 5 of 2'-, 5'-tetraphenyl-1,2'-bisglyoxaline, 2,2'-two (2,4,6-trichlorophenyl)-4,4', 5,5'-tetraphenyl-1,2'-bisglyoxaline etc.
Should illustrate, when using united imidazole as Photoepolymerizationinitiater initiater, from the viewpoint of improving sensitivity, preferred and use hydrogen donor." hydrogen donor " mentioned here refers to can to the compound by exposing the free radical supply hydrogen atom produced by united imidazole.As hydrogen donor, such as, 2-mercaptobenzothiazole, 2-sulfydryl benzo can be enumerated
the mercaptan hydrogen donors such as azoles, 4,4'-two (dimethylamino) benzophenone, 4, the amine hydrogen donors such as two (diethylamino) benzophenone of 4'-.In the present invention, hydrogen donor can be used alone or mixes two or more and uses, and from the viewpoint of improving sensitivity further, preferably the mercaptan hydrogen donor of more than a kind and the amine hydrogen donor of more than a kind to be combinationally used.
In addition, as the concrete example of above-mentioned triaizine compounds, can 2 be enumerated, 4, 6-tri-(trichloromethyl) s-triazine, 2-methyl-4, two (trichloromethyl) s-triazine of 6-, 2-(2-(5-methylfuran-2-base) vinyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(2-(furans-2-base) vinyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(2-(4-diethylamino-2-aminomethyl phenyl) vinyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(2-(3, 4-Dimethoxyphenyl) vinyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(4-methoxyphenyl)-4, two (trichloromethyl) s-triazine of 6-, 2-(4-ethoxystyrene base)-4, two (trichloromethyl) s-triazine of 6-, 2-(4-n-butoxyphenyl)-4, two (trichloromethyl) s-triazine etc. of 6-has the triaizine compounds of halogenated methyl.
In addition, as the concrete example of O-acyl group oxime compound, 1-(4-(thiophenyl) phenyl)-1 can be enumerated, 2-acetyl caproyl 2-(O-benzoyl oxime), 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-ethyl ketone 1-(O-acetyl oxime), 1-(9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9H-carbazole-3-base)-ethyl ketone 1-(O-acetyl oxime), 1-(9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxolanes) methoxybenzoyl base }-9H-carbazole-3-base)-ethyl ketone 1-(O-acetyl oxime) etc.As the commercially available product of O-acyl group oxime compound, NCI-831, NCI-930 (above is Inc. of Asahi Denka Co., Ltd.) can be used, DFI-020, DFI-091 (being Daito Chemix Co., Ltd. system above) etc.
In the present invention, when using the Photoepolymerizationinitiater initiater beyond the united imidazoles such as acetophenone compound, also can be used together sensitizer.As such sensitizer; such as; can 4 be enumerated; two (dimethylamino) benzophenone, 4 of 4'-; two (diethylamino) benzophenone of 4'-, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino propiophenone, EDMAB, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, 2,5-two (4-diethylamino benzylidene) cyclohexanone, 7-diethylamino-3-(4-diethylamino benzoyl) cumarin, 4-(diethylamino) chalcone etc.
In the present invention, the content of (D) Photoepolymerizationinitiater initiater is preferably 0.01 ~ 120 mass parts relative to (C) polymerizable compound 100 mass parts, particularly preferably 1 ~ 100 mass parts.By being such mode, curability can be improved further, by membrane property.
-(E) solvent-
Other composition that coloured composition of the present invention contains above-mentioned (A) ~ (C) composition and adds arbitrarily, but usually coordinate solvent to be prepared into fluid composition.
As (E) solvent, as long as will (A) ~ (C) composition, the dispersion of other composition of coloured composition be formed or dissolve and react with these compositions, there is appropriate volatile solvent, just can suitable choice for use.
In such solvent, such as, can enumerate:
Glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list positive propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list positive propyl ether, propylene glycol mono-n-butyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol list positive propyl ether, dipropylene glycol mono-n-butyl ether, Tripropylene glycol monomethyl Ether, (gathering) alkylene glycol monoalkyl ethers such as tripropylene glycol list ether,
The lactic acid alkyl ester such as methyl lactate, ethyl lactate class;
(ring) alkyl alcohols such as methyl alcohol, ethanol, propyl alcohol, butanols, isopropyl alcohol, isobutyl alcohol, the tert-butyl alcohol, octanol, 2-Ethylhexyl Alcohol, cyclohexanol;
The ketols such as diacetone alcohol;
(gathering) alkylene glycol monoalkyl ether acetate classes such as ethylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, TC acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl acetic acid esters, dipropylene glycol monomethyl ether acetic acid esters, 3-methoxybutyl acetic acid esters, 3-methyl-3-methoxybutyl acetic acid esters;
Other ethers such as diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether, tetrahydrofuran;
The ketones such as methyl ethyl ketone, cyclohexanone, 2-HEPTANONE, 3-heptanone;
The diacetate esters classes such as propylene-glycol diacetate, 1,3-BDO diacetate esters, 1,6-hexanediol diacetate esters;
The alkoxyl carboxylate classes such as 3-methoxy methyl propionate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, ethoxy ethyl acetate, 3-methyl-3-methoxybutyl propionic ester; Other ester classes such as ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, propyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, methyl pyruvate, ethyl pyruvate, pyruvic acid n-propyl, methyl acetoacetate, ethyl acetoacetate, 2-Oxobutyric acid ethyl ester;
Toluene, dimethylbenzene etc. are aromatic hydrocarbon based;
Acid amides or the lactams etc. such as DMF, DMA, 1-METHYLPYRROLIDONE.
In these solvents, from dissolubility, pigment-dispersing, the viewpoints such as coating are set out, preferably (gathering) alkylene glycol monoalkyl ethers, lactic acid alkyl ester class, (gathering) alkylene glycol monoalkyl ether acetate class, other ethers, ketone, diacetate esters class, alkoxyl carboxylate class, other ester class, particularly preferably propylene glycol monomethyl ether, dihydroxypropane single-ether, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl acetic acid esters, 3-methoxybutyl acetic acid esters, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, cyclohexanone, 2-HEPTANONE, 3-heptanone, 1,3-BDO diacetate esters, 1,6-hexanediol diacetate esters, ethyl lactate, 3-methoxypropionate, 3-ethoxypropanoate, 3-ethoxyl ethyl propionate, 3-methyl-3-methoxybutyl propionic ester, n-butyl acetate, isobutyl acetate, formic acid n-pentyl ester, isoamyl acetate, n-butyl propionate, ethyl butyrate, isopropyl isobutyrate, the positive butyl ester of butyric acid, ethyl pyruvate etc.
In the present invention, solvent can be used alone or mixes two or more and uses.
(E) content of solvent is not particularly limited, and the total concentration of each composition except solvent of preferred coloured composition becomes the amount of 5 ~ 50 quality %, more preferably becomes the amount of 10 ~ 40 quality %.By being such mode, colorant dispersion dispersiveness can be obtained, having good stability, and coating, the coloured composition that has good stability.
-adjuvant-
Coloured composition of the present invention also can contain various adjuvant as required.
As adjuvant, such as, the filling agent such as glass, aluminium oxide can be enumerated, the macromolecular compounds such as polyvinyl alcohol (PVA), poly-(fluoroalkyl) class, the surfactants such as fluorine system surfactant, silicon system surfactant, vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxy ethoxy) silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, APTES, 3-glycidoxypropyltrime,hoxysilane, 3-glycidoxypropyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, the closely sealed promoter such as 3-mercaptopropyi trimethoxy silane, 2,2-thiobis (4-methyl-6-tert-butylphenol), 2,6-DI-tert-butylphenol compounds, pentaerythrite four [3-(3,5-bis--tert-butyl-hydroxy phenyl) propionic ester], 3, two [the 2-[3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl)-propionyloxy]-1 of 9-, 1-dimethyl ethyl]-2,4,8, the antioxidants such as 10-tetra-oxa-s-spiral shell [55] undecane, thiodiethylene two [3-(3,5-, bis--tert-butyl-hydroxy phenyl) propionic ester], 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl)-5-chlorobenzene is three thiazoles also, the ultraviolet light absorbers such as alkoxy benzophenone class, the condensation preventing agents such as polyacrylic acid acid sodium, malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-ethylaminoethanol, the residue improver such as 3-amino-1-propyl alcohol, 5-amino-1-amylalcohol, 3-amino-1,2-PD, 2-amino-1,3-propanediol, amino-1, the 2-butylene glycol of 4-, the developability improvers etc. such as mono succinate (2-(methyl) acryloyl-oxyethyl) ester, phthalic acid list (2-(methyl) acryloyl-oxyethyl) ester, ω-carboxy-polycaprolactone list (methyl) acrylate.
Coloured composition of the present invention can utilize suitable method preparation, as its preparation method, such as, (A) ~ (C) composition and (E) solvent, any other composition added can be mixed together and prepare.Wherein, be preferably as follows method: use such as ball mill, roller mill etc. according to circumstances to be pulverized together with a part for (B) composition under the existence of spreading agent by pigment and mix and be dispersed in (E) solvent and make dispersible pigment dispersion, then, in this dispersible pigment dispersion, add (B) ~ (C) composition and the solvent added further as required and other composition and carry out mixing and preparing.
color solidification film and manufacture method thereof
Color solidification film of the present invention uses coloured composition of the present invention to be formed, such as, have the green pixel used in color filter.
Below, color solidification film used in color filter and forming method thereof is described.
As the method forming the color solidification film forming color filter, the first, can following methods be enumerated.First, light shield layer (black matrix) is formed in the mode dividing the part forming pixel as required on a surface of a substrate.Then, after being coated with the fluid composition of the such as green sensitivity coloured composition of radioactive ray of the present invention on the substrate, carrying out prebake and solvent is evaporated, form film.Then, after exposing this film via photomask, use alkaline developer to develop, removing is dissolved in the unexposed portion of film.Thereafter, by after cure the pel array of the viridescent pattern of pixels that is arranged (color solidification film) formed with regulation.
Then, use the sensitivity coloured composition of each radioactive ray of redness or blueness, carry out in the same manner as described above the coating of the sensitivity coloured composition of each radioactive ray, prebake, exposure, development and after cure, the pel array of the pel array of redness and blueness is formed in same substrate successively.Thus, the color filter being configured with redness, green and blue trichromatic pel array on substrate is obtained.But in the present invention, the order forming assorted pixel is not limited to said sequence.
In addition, black matrix can utilize photoetching process to make to become desired pattern by the metallic film of the chromium etc. of sputtering, evaporation film-forming and be formed, also can use the sensitivity coloured composition of the radioactive ray being dispersed with black pigment, be identically formed with the situation of above-mentioned formation pixel.
As the substrate used when forming color solidification film, such as, glass, silicon, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc. can be enumerated.
In addition, the pre-treatment that the chemical treatment, Cement Composite Treated by Plasma, ion plating, sputtering, gas-phase reaction method, vacuum evaporation etc. that can implement in advance to utilize silane coupling agent etc. to carry out to these substrates be as required suitable.
When sensitivity for radioactive ray coloured composition is coated on substrate, the rubbing method that spray-on process, rolling method, method of spin coating (spin-coating method), slot die rubbing method (slot coated method), stick coating method etc. are suitable can be adopted, particularly preferably adopt spin-coating method, slot die rubbing method.
Drying under reduced pressure and heat drying combination carry out by prebake usually.Drying under reduced pressure usually proceeds to and reaches 50 ~ 200Pa.In addition, the condition of heat drying is generally 70 ~ 110 DEG C, about 1 ~ 10 minute.
Coating thickness, with dried film thickness gauge, is generally 0.6 ~ 8 μm, is preferably 1.2 ~ 5 μm.
As the light source of the radioactive ray used when forming at least a kind of being selected from pixel and black matrix, such as, the LASER Light Source etc. such as the lamp source such as xenon lamp, Halogen lamp LED, tungsten lamp, high-pressure sodium lamp, ultrahigh pressure mercury lamp, metal halide lamp, medium pressure mercury lamp, low pressure mercury lamp or argon laser, YAG laser, XeCl excimer laser, N_2 laser can be enumerated.As exposure light source, also ultraviolet LED can be used.Optimal wavelength is at the radioactive ray of the scope of 190 ~ 450nm.
The general preferably 10 ~ 10000J/m of exposure of radioactive ray
2.
In addition, as above-mentioned alkaline developer, such as, preferred sodium carbonate, sodium bicarbonate, NaOH, potassium hydroxide, Tetramethylammonium hydroxide, choline, 1,8-diazacyclo-[5.4.0]-7-undecylene, the aqueous solution of 1,5-diazacyclo-[4.3.0]-5-nonene etc.
Also the water-miscible organic solvent or surfactant etc. of such as methyl alcohol, ethanol etc. can be added in right amount in alkaline developer.Should illustrate, usually wash after alkali development.
As development treatment method, spray development method, spray development method, immersion (dipping) development method can be used, soak and put (puddle) development method etc.Under the preferred normal temperature of development conditions 5 ~ 300 seconds.
After the condition of curing be generally 180 ~ 280 DEG C, about 10 ~ 60 minutes.
The thickness of the pixel of such formation is generally 0.5 ~ 5 μm, is preferably 1.0 ~ 3 μm.
In addition, as the second method forming the color solidification film forming color filter, can adopt disclosed in Japanese Unexamined Patent Publication 7-318723 publication, Japanese Unexamined Patent Publication 2000-310706 publication etc. and utilize ink-jetting style to obtain the method for assorted pixel.In the method, first, the next door also having shade function concurrently is formed on a surface of a substrate.Then, after utilizing ink discharge device to spray the fluid composition of such as green Thermocurable coloured composition of the present invention in the next door formed, carry out prebake and solvent is evaporated.Then, after as required this film being exposed, by after cure and make it solidify, form green pattern of pixels.
Then, use each Thermocurable coloured composition of redness or blueness, in same substrate, form red pattern of pixels and blue pattern of pixels in the same manner as described above successively.Thus, the color filter being configured with redness, green and blue trichromatic pattern of pixels on substrate is obtained.But in the present invention, the order forming assorted pixel is not limited to said sequence.
Should illustrate, next door not only has shade function, also plays and makes the Thermocurable coloured composition being ejected into the colors in septal area that the function of colour mixture not occur, so the black matrix used in above-mentioned the first method of Film Thickness Ratio is thick.Therefore, next door uses the sensitivity composition of black radioactive ray to be formed usually.
The substrate used when forming color solidification film, the light source of radioactive ray and prebake, after method, the condition of curing identical with the first above-mentioned method.Like this, the thickness of pixel formed by ink-jetting style and the height in next door are equal extent.
After the pattern of pixels obtained like this forms diaphragm as required, form nesa coating by sputtering.After forming nesa coating, can separator be formed further and make color filter.Separator uses the sensitivity composition of radioactive ray to be formed usually, also can make the separator (black separator) with light-proofness.At this moment, the sensitivity composition of the colored radiation being dispersed with black colorant can be used.
The color filter containing color solidification film of the present invention of such formation, brightness, contrast and colouring power are high, exceedingly useful in color liquid crystal display device, colour pick-up tube element, color sensor, organic EL display element, Electronic Paper etc.
display element
Display element of the present invention possesses color solidification film of the present invention.As display element, color liquid crystal display device, organic EL display element, Electronic Paper etc. can be enumerated.
Possessing the color liquid crystal display device of color solidification film of the present invention, can be transmission-type also can be reflection-type, can adopt suitable structure.Such as, can adopt following structure: be formed in by color filter on the substrate different from the driving substrate being configured with thin film transistor (TFT) (TFT), driving substrate is opposed across liquid crystal layer with the substrate being formed with color filter; In addition, following structure can also be adopted: the substrate forming color filter on the surface of driving substrate being configured with thin film transistor (TFT) (TFT) is opposed across liquid crystal layer with the substrate being formed with ITO (being doped with the indium oxide of tin) electrode.The structure of the latter significantly improves aperture opening ratio, has and can obtain becoming clear and the advantage of the liquid crystal display cells of fine.Should illustrate, when adopting the structure of the latter, black matrix, black separator can be formed in the substrate-side and the either side be formed in the substrate-side of ITO electrode being formed with color filter.
Possess the color liquid crystal display device of color solidification film of the present invention, except can possessing cold cathode fluorescent tube (CCFL:Cold Cathode Fluorescent Lamp), can also possess with White LED is the backlight unit of light source.As White LED, such as, display predetermined colors in combination LED can be enumerated, green LED and blue led obtain the White LED of white light by colour mixture, combined blue LED, red LED and green-emitting phosphor obtain the White LED of white light by colour mixture, combined blue LED, red light-emitting phosphor and green-emitting phosphor body obtain the White LED of white light by colour mixture, the White LED of white light is obtained by the colour mixture of blue led and YAG system fluorophor, combined blue LED, orange luminescence fluorophor and green-emitting phosphor body obtain the White LED of white light by colour mixture, combination ultraviolet LED, red light-emitting phosphor, green-emitting phosphor body and blue-light-emitting fluorescent material obtain the White LED etc. of white light by colour mixture.
Possess in the color liquid crystal display device of color solidification film of the present invention, TN (twisted-nematic can be used, Twisted Nematic) type, (supertwist is to row for STN, Super TwistedNematic) type, IPS (switches in face, In-Planes Switching) type, VA is (vertical orientated, Vertical Alignment) type, the liquid crystal mode that OCB (optical compensation curved arrangement, OpticallyCompensated Birefringence) type etc. are suitable.
In addition, the organic EL display element possessing color solidification film of the present invention can adopt suitable structure, such as, can enumerate structure disclosed in Japanese Unexamined Patent Publication 11-307242 publication.
In addition, the Electronic Paper possessing color solidification film of the present invention can adopt suitable structure, such as, can enumerate structure disclosed in Japanese Unexamined Patent Publication 2007-41169 publication.
[embodiment]
Below, enumerate embodiment to be specifically described embodiments of the present invention further.But the present invention is not limited to following embodiment.
The synthesis > of < resin glue
Synthesis example 1
Resin glue (B-1)
In the flask possessing cooling tube and stirring machine, load propylene glycol methyl ether acetate 80 mass parts and carry out nitrogen displacement.Be heated to 80 DEG C, at such a temperature, mixed solution and propylene glycol methyl ether acetate 20 mass parts and 2 of propylene glycol methyl ether acetate 50 mass parts, methacrylic acid 20 mass parts, styrene 10 mass parts, 2-hydroxyethyl methacrylate 15 mass parts, 2-Ethylhexyl Methacrylate 28 mass parts, N-phenylmaleimide 12 mass parts and mono succinate (2-acryloyl-oxyethyl) ester 15 mass parts is dripped respectively through 2 hours, 2'-azo two (2,4-methyl pentane nitrile) mixed solution of 6 mass parts, keep this temperature polymerizations 1 hour.Thereafter, make the temperature to 90 DEG C of reaction solution, then be polymerized 1 hour, obtain resin glue (B-1) solution (solid component concentration=40 quality %) thus.The resin glue (B-1) obtained is Mw=10500, Mn=5900, Mw/Mn=1.78.
The synthesis > of < spreading agent
Synthesis example 2
Spreading agent (1)
In the flask of replacing through argon, add tetrahydrofuran 80 mass parts, dimethylaminoethyl methacrylate 45 mass parts, s-butyl lithium 5 mass parts, in the CoolNix taking ethylene glycol as cold-producing medium, keep-78 DEG C to carry out stirring for 3 hours.Then polyethylene glycol methacrylate-styrene polymer (Japan Oil Co's system of 23 mass parts methyl methacrylates, 17 mass parts methoxy group is added, goods name: BLENMER PME-200), 15 mass parts methacrylic acid tetrahydro furfuryl ester (Kyoeisha Chemical Co., Ltd., goods name: Light Ester THF) and 70 mass parts propylene glycol methyl ether acetates, this temperature is kept to carry out polymerization in 3 hours, after stopping reaction with methyl alcohol, 3 extracting and refinings are carried out with ultrapure water and ethyl acetate, reclaim organic layer, with evaporator, ethyl acetate decompression is heated up in a steamer.Dissolved dilution is carried out to the resin solid matter propylene glycol methyl ether acetate obtained, prepares in the mode that solid component concentration is 40%.The resin obtained is Mw=10000, Mn=7700, Mw/Mn=1.30.Using the resin solution that obtains as spreading agent (1) solution.Spreading agent (1) has tetrahydrofuran base as cross-linking functional group's (methyl) dispersant containing acrylic.
The preparation > of < colorant dispersion
Preparation example 1
Colorant dispersion (A-1)
Be used as the 7.33 mass parts C.I. naphthol greens 58 of (A) colorant, 0.94 mass parts C.I. pigment Yellow 12 9 and 4.46 mass parts C.I. pigment yellow 13 8, as 11.25 mass parts BYK-LPN21116 (the BYK Inc. of spreading agent, nonvolatile component 40 quality %), as 11.25 mass parts resin glue (B-1) solution (solid component concentration 40%) of (B) resin glue, and as propylene glycol methyl ether acetate 76.5 mass parts of (E) solvent and propylene glycol monomethyl ether 1.50 mass parts, ball mill is utilized to mix dispersion, the colorant dispersion (A-1) that preparation is green.
Preparation example 2 ~ 10
Colorant dispersion (A-2) ~ (A-10)
In preparation example 1, the kind of each composition and amount are changed by shown in table 1, in addition, carries out identically with preparation example 1, colorant dispersion (A-2) ~ (A-10) that preparation is green.
[table 1]
In table 1, each composition is as follows.
G58:C.I. naphthol green 58
Y138:C.I. pigment yellow 13 8
Y129:C.I. pigment Yellow 12 9
Y150:C.I. pigment yellow 150
LPN21116:BYK-LPN21116 (BYK Inc., nonvolatile component 40 quality %)
Spreading agent (1): spreading agent (1) solution (solid component concentration 40%) E-1 of synthesis in synthesis example 2: propylene glycol methyl ether acetate
E-2: propylene glycol monomethyl ether
The preparation of < coloured composition and evaluation >
Embodiment 1
The preparation of coloured composition
Will as the colorant dispersion of (A) colorant (A-1) 510 mass parts, as resin glue (B-1) solution 100 mass parts of (B) resin glue, as dipentaerythritol acrylate (Nippon Kayaku K. K's system of (C) polymerizable compound, trade name KAYARAD DPHA) 90 mass parts, as 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butane-1-ketone (the Ciba Specialty Chemicals Inc. of (D) Photoepolymerizationinitiater initiater, trade name IRGACURE 369) 3 mass parts and ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime)] (BASF AG's system, trade name IRGACURE OXE02) 12 mass parts, as 3-methacryloxypropyl trimethoxy silane 5 mass parts of closely sealed promoter, as propylene glycol methyl ether acetate 5 quality % solution 5 mass parts of the EMULGEN A-60 (Kao Corp's system) of surfactant, and as propylene glycol methyl ether acetate 155 mass parts of (E) solvent and the mixing of 3-ethoxyl ethyl propionate 420 mass parts, the coloured composition (S-1) that preparation is green.
(1) evaluation of colorimetric properties
Use spin coater by after coloured composition (S-1) coating on the glass substrate, carry out 1 minute prebake with the heating plates of 90 DEG C, form the film of thickness 2.5 μm.The rotating speed changing spin coater carries out identical operation, forms 3 films that thickness is different.
Then, after these substrates are cooled to room temperature, use high-pressure sodium lamp not via photomask with illumination 35mW, 600J/m
2exposure the radioactive ray of each wavelength of 365nm, 405nm and 436nm are comprised to the film exposure on substrate.Thereafter, to develop, 1kgf/cm is pressed to the film on substrate
2(nozzle diameter 1mm) sprays the developer solution be made up of 0.04 quality % potassium hydroxide aqueous solution of 25 DEG C, carries out spray development thus.Thereafter, clean these substrates with ultrapure water, after air-dry, cure after carrying out 20 minutes further in the cleaning oven of 230 DEG C, make green cured film thus.
To 3 cured film obtained, use color analysis instrument (Otsuka Electronics Co., Ltd. MCPD2000), under the condition of illuminant-C, 2 degree of visual fields, measure the chromaticity coordinate value (x, y) in CIE color specification system and values (Y).Chromaticity coordinate value x when obtaining chromaticity coordinate value y=0.590 according to measurement result and values (Y).Evaluation result is shown in table 3.Can say that values (Y) larger brightness is higher.
In addition, the thickness of KLA-Tencor Alpha-Step IQ to the cured film obtained is used to measure.Using the thickness of comparative example 1 as 100, be summarized in table 3 as the relative value relative to this thickness.Can say that the colouring power of the thinner colorant of thickness is larger.
(2) contrast evaluation
The substrate of cured film is formed with 2 polaroid clampings, rotate the polaroid of front face side while to irradiate from rear side with fluorescent light (wavelength coverage 380 ~ 780nm), utilize nitometer LS-100 (Minolta Co., Ltd. system) mensuration through the maximal value of light intensity and minimum value.So to each cured film, value maximal value obtained divided by minimum value spends ratio as a comparison.The contrast ratio at chromaticity coordinate value y=0.590 is obtained according to measurement result.Evaluation result is shown in table 3.Should illustrate, the larger expression of numerical value of contrast ratio is better.
(3) evaluation of thermotolerance
Use slot die coating machine by after coloured composition (S-1) coating on the glass substrate, carry out 4 minutes prebake with the heating plates of 90 DEG C, form the film of thickness 2.0 μm.Then, after this substrate is cooled to room temperature, high-pressure sodium lamp is used via photomask with 400J/m
2exposure the exposure of each film is comprised to the radioactive ray of each wavelength of 365nm, 405nm and 436nm.Thereafter, the 0.04 quality % potassium hydroxide aqueous solution of 25 DEG C is used to carry out spray development in 90 seconds to these substrates.Thereafter, clean this substrate with ultrapure water, after air-dry, then cure carry out 30 minutes in the cleaning oven of 230 DEG C after, on substrate, form green dot pattern thus.
Color analysis instrument (Otsuka Electronics Co., Ltd. MCPD2000 is used to the dot pattern that obtains) under the condition of illuminant-C, 2 degree of visual fields, measure chromaticity coordinate value (x, y) in CIE color specification system and values (Y).Then, after carrying out adding for 90 minutes cure at 230 DEG C, measure chromaticity coordinate value (x, y) and values (Y), evaluate and add the color before and after curing and change, be i.e. Δ E
ab.Its result, Δ E
abvalue be less than 2 be evaluated as " ◎ ", more than 2 and be less than 3 be evaluated as "○", more than 3 and be less than 5 be evaluated as " △ ", more than 5 be evaluated as "×".Evaluation result is shown in table 3.Δ E can be said
abthe less thermotolerance of value better.
(4) evaluation of solvent resistance
Use coloured composition (S-1) and above-mentioned " evaluation of thermotolerance " to carry out in the same manner, substrate is formed green dot pattern.The substrate defining dot pattern to be immersed in the 1-METHYLPYRROLIDONE of 25 DEG C 30 minutes, to evaluate the Δ E before and after flooding in the same manner with above-mentioned " evaluation of thermotolerance "
ab.Its result, Δ E
abvalue be less than 3 be evaluated as "○", being evaluated as " △ " between 3 ~ 5, be greater than 5 be evaluated as "×".Evaluation result is shown in table 3.Δ E can be said
abthe less solvent resistance of value better.
Embodiment 2 ~ 5 and comparative example 1 ~ 5
In embodiment 1, the kind of colorant dispersion, solvent and amount are changed by shown in table 2, in addition, prepares coloured composition (S-2) ~ (S-10) identically with embodiment 1.Then, to the coloured composition obtained (S-2) ~ (S-10) identical with embodiment 1 evaluate.
Show the result in table 3.
[table 2]
In table 2, each composition is as follows.
C-1: dipentaerythritol acrylate (Nippon Kayaku K. K's system, trade name KAYARADDPHA)
D-1:2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butane-1-ketone (Ciba SpecialtyChemicals Inc., trade name IRGACURE 369)
D-2: ethyl ketone-1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime)] (BASF AG's system, trade name IRGACURE OXE02)
F-1:3-methyclyloxypropyl trimethoxy silane
The propylene glycol methyl ether acetate 5 quality % solution of F-2:EMULGEN A-60 (Kao Corp's system)
E-1: propylene glycol methyl ether acetate
E-3:3-ethoxyl ethyl propionate
E-4: methoxybutyl acetic acid esters
[table 3]
※ thickness: using the thickness of comparative example 1 as 100 time relative value
Claims (5)
1. a coloured composition, containing (A) colorant, (B) resin glue and (C) polymerizable compound,
(A) colorant contains zinc halide phthalocyanine color, quinophthalone pigments and azomethine copper pigment, the content w of quinophthalone pigments
2with the content w of azomethine copper pigment
3ratio be w by quality ratio
2/ w
3=70/30 ~ 85/15.
2. coloured composition according to claim 1, wherein, the content w of zinc halide phthalocyanine color
1with the content w of azomethine copper pigment
3ratio be w by quality ratio
1/ w
3=65/35 ~ 90/10.
3. coloured composition according to claim 1 and 2, wherein, further containing (methyl) dispersant containing acrylic with cross-linking functional group.
4. a color solidification film, containing zinc halide phthalocyanine color, quinophthalone pigments and azomethine copper pigment, the content w of quinophthalone pigments
2with the content w of azomethine copper pigment
3ratio be w by quality ratio
2/ w
3=70/30 ~ 85/15.
5. a display element, possesses color solidification film according to claim 4.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013191348 | 2013-09-17 | ||
| JP2013-191348 | 2013-09-17 |
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|---|---|
| CN104460230A true CN104460230A (en) | 2015-03-25 |
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ID=52906505
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410460962.5A Pending CN104460230A (en) | 2013-09-17 | 2014-09-11 | Coloring composition, colored cured film and display device |
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|---|---|
| JP (1) | JP6303936B2 (en) |
| KR (1) | KR102288373B1 (en) |
| CN (1) | CN104460230A (en) |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116848199A (en) * | 2021-02-03 | 2023-10-03 | 富士胶片株式会社 | Coloring composition, film, optical filter, solid-state imaging element, image display device, and compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6707818B2 (en) * | 2014-08-06 | 2020-06-10 | 三菱ケミカル株式会社 | Pigment dispersion, colored resin composition, color filter, liquid crystal display device, and organic EL display device |
| JP6824079B2 (en) * | 2017-03-16 | 2021-02-03 | 東洋インキＳｃホールディングス株式会社 | Photosensitive coloring compositions and color filters for color filters |
| TW202231789A (en) * | 2021-02-03 | 2022-08-16 | 日商富士軟片股份有限公司 | Coloring composition, film, optical filter, solid-state imaging element, image display device, and compound |
| TW202231790A (en) * | 2021-02-03 | 2022-08-16 | 日商富士軟片股份有限公司 | Colored composition, film, optical filter, solid imaging element, image display device, and compound |
| WO2023228791A1 (en) * | 2022-05-25 | 2023-11-30 | 富士フイルム株式会社 | Coloring composition, film, optical filter, solid-state imaging element and image display device |
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- 2014-09-10 JP JP2014183847A patent/JP6303936B2/en active Active
- 2014-09-11 CN CN201410460962.5A patent/CN104460230A/en active Pending
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| JP2015083664A (en) | 2015-04-30 |
| KR102288373B1 (en) | 2021-08-11 |
| JP6303936B2 (en) | 2018-04-04 |
| KR20150032175A (en) | 2015-03-25 |
| TW201518865A (en) | 2015-05-16 |
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