CN104714367A - Coloring composition, coloring cured film and display device - Google Patents

Coloring composition, coloring cured film and display device Download PDF

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Publication number
CN104714367A
CN104714367A CN201410781873.0A CN201410781873A CN104714367A CN 104714367 A CN104714367 A CN 104714367A CN 201410781873 A CN201410781873 A CN 201410781873A CN 104714367 A CN104714367 A CN 104714367A
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compound
coloured composition
formula
group
integer
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CN104714367B (en
Inventor
服部清太郎
面手真人
和田夏子
间嶋宽
松本龙
伊藤淳史
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JSR Corp
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JSR Corp
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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
    • G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/0007—Filters, e.g. additive colour filters; Components for display devices
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds

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  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Polymerisation Methods In General (AREA)
  • Liquid Crystal (AREA)
  • Graft Or Block Polymers (AREA)
  • Paints Or Removers (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

The invention provides a coloring cured film excellent in adhesion and solvent resistance, a coloring composition used for forming the cured film and a display device having the cured film. The coloring composition is characterized by comprising a colorant A, adhesive resin B, a radical polymerized compound C, a photo-radical generating agent D and a compound E with the structure in which a radial represented in the following formula E0 is directly combined on an aromatic nucleus. In the formula E0 of *-(CRII2)x-O-RI (E0), RI is an alkyl group with the hydrogen atom or carbon number of 1-4, RII is an alkyl group with the hydrogen atom or carbon number of 1-4, x is 1 or 2, and * represents a bonding key which is directly combined on an aromatic nucleus.

Description

Coloured composition, painted cured film and display element
Technical field
The present invention relates to coloured composition, color solidification film and display element.In detail, the coloured composition of the color solidification film for the formation of solid-state imagers such as display element and cmos image sensor such as applicable transmission-type or reflection type color liquid crystal display, organic EL display element, Electronic Paper, the color solidification film formed by this coloured composition and the display element with this color solidification film is related to.
Background technology
Coloured composition is used to manufacture colored filter, there will be a known following method: on substrate after coating pigment decentralized radiation-sensitive coloured composition, formation film, this film exposed into desired pattern form and develops, obtaining the pattern-like pixel (patent documentation 1 and 2) of shades of colour thus.As the manufacture method of black matrix", there will be a known the method (patent documentation 3) using carbon dispersion radiation-sensitive coloured composition to carry out same operation, formation pattern-like black matrix".Also know and have by pigment-dispersing type coloured composition ink-jetting style being coated with and being cured, being formed the method (patent documentation 4) of the pattern-like pixel of shades of colour.
In above-mentioned sequence of operations, for film is exposed into pattern-like, usually adopt the method for photomask to film irradiation light via having desired pattern.Now, the proximity gap (exposing clearance) of regulation is set between film and photomask.Here, it is desirable that make the light of irradiation directly pass through at the peristome of photomask, in the portion of remaining silent, photoresistance is broken.But at the edge part of photomask, light can diffraction, therefore, the film near the peristome being arranged in the portion of remaining silent can be irradiated to the light (light leak) of the intensity more weak than regulation exposure.
In film, for the above-mentioned zone line being irradiated to light leak, be requirement its there is the proterties identical with peristome region (exposure area), still requiring that it has the proterties identical with closing mouth area (dark areas), different depending on the formation of operation, the object of product etc.Namely, for minus coloured composition, require that it is the coloured composition that above-mentioned zone line can occur to solidify, luminous sensitivity is high in the same manner as exposure portion sometimes, on the other hand, sometimes also can require that it is the coloured composition that above-mentioned zone line does not solidify (namely developing), mask misalignment little (repeatability forming the mask size of pattern is high) in the same manner as non-exposed portion.High and the mask misalignment of luminous sensitivity is little is the characteristic of conflicting, and is usually difficult to take into account.
For in the past known coloured composition, know that it is that luminous sensitivity high type or mask misalignment are small-sized, can only trial and error being passed through, being difficult to separately make highly sensitive degree type coloured composition and low mask misalignment type coloured composition when maintaining the congruency of other characteristics.
But, point out in patent documentation 5, about the coloured composition containing specific phenolic compounds in coloured composition, when using said composition, can be formed accurately and there is excellent pattern form, the color solidification film high with the adhesiveness of substrate.This technology is a kind of technology of the excellence be improved in adhesiveness and pattern form really, but present inventor is found by research, and the solvent resistance of color solidification film formed by shape is not enough.
Therefore, this area has recognized that the necessity of the color solidification film that can form adhesiveness and solvent resistance two aspect excellence.
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 2009-204895 publication
Summary of the invention
The present invention makes to break above-mentioned present situation.
Therefore, the object of the present invention is to provide the color solidification film of adhesiveness and solvent resistance excellence, form the coloured composition of this color solidification film and there is the display element of this cured film.
Above-mentioned coloured composition preferably can selective light sensitivity high type and mask misalignment small-sized in any one, at random separately make.
According to the present invention, above object and advantages of the present invention 1st are realized by following coloured composition:
Described coloured composition contains:
(A) colorant,
(B) binder resin,
(C) free-radical polymerised compound,
(D) optical free radical generation agent,
(E) there is the compound that group that following formula (E0) represents directly is combined in the structure on aromatic rings,
＊－(CR II 2)x－O－R I(E0)
(in formula (E0),
R ithe alkyl of hydrogen atom or carbon number 1 ~ 4,
R iIseparately represent the alkyl of hydrogen atom or carbon number 1 ~ 4,
X is 1 or 2,
" * " represents the associative key be directly combined on aromatic rings.〕
Above object and advantages of the present invention 2nd are realized by the color solidification film using above-mentioned coloured composition to be formed.
Above object and advantages of the present invention 3rd are realized by the display element with above-mentioned color solidification film.
According to the present invention, the color solidification film of adhesiveness and solvent resistance excellence is provided, forms the coloured composition of this color solidification film and there is the display element of this cured film.
Above-mentioned coloured composition by select above-mentioned (E) compound, can separately make luminous sensitivity high type and mask misalignment small-sized in any one.
Embodiment
< (A) colorant >
(A) colorant contained in coloured composition of the present invention in use can not be subject to particular restriction.The color of (A) colorant, material etc. is suitably selected to use according to the purposes of coloured composition of the present invention.
As (A) colorant, more than a kind of being selected from pigment and dyestuff can be used.
When each color pixel using coloured composition of the present invention for the formation of formation colored filter, when using more than a kind conduct (A) colorant be selected from organic pigment and organic dyestuff, easily can obtain the high pixel of brightness, contrast and excitation, thus preferably.On the other hand, black matrix" (matrix) or black interval part (spacer is formed at use coloured composition; Or claim " chock insulator matter ") when, preferably use inorganic pigment as (A) colorant.
As pigment, can be organic pigment and inorganic pigment.
As the preferred example of organic pigment, such as, can be that name is called C.I. paratonere 166, C.I. paratonere 177, C.I. paratonere 224, C.I. paratonere 242, C.I. paratonere 254, C.I. pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58, C.I. pigment blue 15: 6, the pigment of pigment index (C.I.) name such as C.I. alizarol saphirol 80, 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, C.I. pigment yellow 211, C.I. pigment orange 38, C.I. pigment Violet 23;
Mordant pigment etc.As mordant pigment, such as, can be triarylmethane class dyestuff isopolyacid, heteropoly acid etc. are carried out color lake and the triarylmethane system mordant pigment obtained like that disclosed in Japanese Unexamined Patent Publication 2011-186043 publication etc.;
Xanthene based dye isopolyacid, heteropoly acid etc. are carried out color lake and the xanthene class mordant pigment obtained like that disclosed in Japanese Unexamined Patent Publication 2010-191304 publication etc.; Etc..
As the preferred example of inorganic pigment, such as, can be that carbon black, titanium are black etc.
Pigment uses after can carrying out in the combination by such as recrystallization method, reprecipitation method, solvent wash method, sublimed method, vaccum heating method etc. or these methods refining;
Also usable resins carries out modified use to its particle surface;
Also can use after by such as such disclosed in Japanese Unexamined Patent Publication 08-179111 publication etc. salt mill method its primary particle being carried out miniaturization.
In addition, pigment also can use as required together with spreading agent, dispersing aid etc.As spreading agent, such as, the spreading agent that cationic, anionic species, nonionic class etc. are suitable be can use, but preferably polymeric dispersant or pigment derivative used.As polymeric dispersant, such as, can be acrylic acid series copolymer (acrylic dispersants), polyurethane (polyurethanes spreading agent), polyesters spreading agent, polyethyleneimine, polyallylamine class spreading agent etc.
Above-mentioned polymeric dispersant can obtain from commercial channels.As its object lesson, can be listed below respectively:
As aforesaid propylene acids spreading agent, such as, there are Disperbyk-2000, Disperbyk-2001, BYK-LPN 6919, BYK-LPN 21116, BYK-LPN 22102 (above is Bi Ke chemistry (BYK) Products) etc.;
As polyurethanes spreading agent, such as, there are Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (above is Bi Ke chemistry (BYK) Products), Solsperse 76500 (Japanese Lubrizol Corp. product) etc.;
As above-mentioned polyesters spreading agent, such as, there are Ajisper-PB821, Ajisper-PB822, Ajisper-PB880, Ajisper-PB881 (above is Ajinomoto Fine-Techno Products) etc.;
As above-mentioned polyethyleneimine: amine spreading agent, such as, there is Solsperse-24000 (Japanese Lubrizol Corp. product) etc., in addition, also can enumerate BYK-LPN21324 (Bi Ke chemistry (BYK) Products).
As above-mentioned pigment derivative, such as, it can be the sulfonic acid etc. of pigment.Specifically, the sulfonic acid etc. of copper phthalocyanine sulfonic acid, diketopyrrolopyrrolecocrystals sulfonic acid, quinophthalone can such as be enumerated.
Relative to pigment 100 mass parts in (A) colorant, the use amount of spreading agent as described above, preferably below 60 mass parts, is more preferably 5 ~ 50 mass parts, is especially preferably 10 ~ 40 mass parts.
As above-mentioned dyestuff, preferably use organic dyestuff, such as, can enumerate xanthene class dyestuff, triarylmethane class dyestuff, cyanine class dyestuff, anthraquinone dyes, azo dyes etc. as preferred example.More specifically, such as disclosed in Japanese Unexamined Patent Publication 2010-32999 publication, Japanese Unexamined Patent Publication 2010-254964 publication, Japanese Unexamined Patent Publication 2011-138094 publication, PCT application No. 2010/123071 Publication, 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., organic dyestuff is suitable.Specifically, can be such as the compound etc. that following formula (A-2-1) ~ (A-2-9) represents respectively.
(chemical formula 1)
(chemical formula 2)
In above-mentioned chemical formula, the compound that (A-2-1) and (A-2-3) ~ (A-2-5) represents respectively is xanthene class dyestuff;
(A-2-2) and (A-2-6) compound of representing respectively be triarylmethane class dyestuff;
(A-2-7) and (A-2-8) compound of representing respectively be cyanine class dyestuff;
(A-2-9) compound represented is anthraquinone dyes.
As pigment and the dyestuff of (A) colorant in coloured composition of the present invention, can individually use a kind, also can mix arbitrarily that two or more uses.In addition, also can by pigment and dyestuff used in combination.
In this technical field, it has been generally acknowledged that, the color solidification film shortcoming solvent resistance using the coloured composition containing dyestuff to be formed.But, even coloured composition of the present invention when containing dyestuff as (A) colorant, also can form the color solidification film of excellent solvent resistance.In this case, relative to the total amount of (A) colorant, dye content in (A) colorant can be made at more than 10 quality % and then at more than 20 quality %, especially, even if at more than 30 quality %, the color solidification film of excellent solvent resistance also can be obtained.
(composition beyond desolventizing is referred in coloured composition with the solid constituent of coloured composition, lower with) add up to benchmark, containing of (A) colorant in coloured composition of the present invention is proportional preferably at more than 5 quality %, more preferably at more than 10 quality %, and then preferably at more than 15 quality %, particularly preferably in more than 20 quality %, and preferably at below 80 quality %, more preferably at below 60 quality %, and then preferably at below 55 quality %, preferred at below 50 quality % further, especially preferred at below 45 quality %, particularly preferably in below 40 quality %.As (A) colorant in coloured composition of the present invention containing proportional scope, add up to benchmark with the solid constituent of coloured composition, be preferably 5 ~ 80 quality %, be more preferably 5 ~ 60 quality %, especially preferably 10 ~ 50 quality %, particularly preferably 15 ~ 45 quality %.By making containing of (A) colorant proportional in above-mentioned scope, when the color solidification film formed is pixel, its brightness is high, excitation and excellent heat resistance, when formed color solidification film be black matrix" or black interval part, its thermotolerance and light-proofness excellence, from this point of view, for preferably.
In addition, consider from the angle obtaining the more excellent coloured composition of sensitivity, benchmark is added up to the solid constituent of coloured composition, (A) colorant in coloured composition of the present invention containing proportional be preferably 10 ~ 50 quality %, be more preferably 15 ~ 45 quality %, especially preferably 20 ~ 40 quality %.
On the other hand, consider from the angle obtaining the less coloured composition of mask misalignment, benchmark is added up to the solid constituent of coloured composition, (A) colorant in coloured composition of the present invention containing proportional be preferably 5 ~ 50 quality %, be more preferably 10 ~ 50 quality %, be especially preferably 15 ~ 45 quality %.
Even if the color solidification film containing proportional height, still can form solvent resistance and adhesiveness excellence of coloured composition colorant of the present invention, therefore, can well for the formation of there is colorant usually containing green pixel, the red pixel of proportional high tendency, especially can well for the formation of green pixel.
< (B) binder resin >
To (B) binder resin in coloured composition of the present invention without particular restriction, but preferably there is the resin of acidic functionality.Be more preferably the resin with carboxyl or phenolic hydroxyl group, especially preferably there is the resin of carboxyl.
As (B) binder resin in the present invention, especially preference as:
(b1) ethylene unsaturated monomer with more than 1 carboxyl with
(b2) other can the ethylene unsaturated monomer of copolymerization
Multipolymer (carbonyl bearing polymer (1));
There is the polymkeric substance (carbonyl bearing polymer (2)) of carboxyl and polymerism unsaturated link, etc.
As the unsaturated monomer (b1) of the raw material of carbonyl bearing polymer (1), can be such as (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) separately or can mix two or more and use.
As unsaturated monomer (b2), such as, can be N-position substituted maleimide amine, aromatic ethenyl compound, (methyl) acrylate, vinyl ether, macromonomer etc.As the object lesson of these monomers, can be listed below respectively:
As above-mentioned N-position substituted maleimide amine, such as, there are N-phenylmaleimide, N-N-cyclohexylmaleimide etc.;
As above-mentioned aromatic ethenyl compound, such as, there are styrene, α-methyl styrene, 4-Vinyl phenol, to hydroxy-alpha-methyl styrene, to vinylbenzyl glycidyl ether, acenaphthylene etc.;
As above-mentioned (methyl) acrylate, such as there is (methyl) acrylate, (methyl) n-butyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid 2-hydroxyl ethyl ester, (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 is 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 three ring (5.2.1.0 2,6) decene-8-base ester, glycerine list (methyl) acrylate, (methyl) acrylic acid 4-oxybenzene ester, ethylene-oxide-modified (methyl) acrylate, (methyl) glycidyl acrylate, (methyl) acrylic acid 3,4-epoxy cyclohexyl, 3-((methyl) acryloyloxymethyl) oxetanes, 3-((methyl) acryloyloxymethyl)-3-Ethyloxetane etc. of p-cumylphenol,
As above-mentioned vinyl ether, such as, there are cyclohexyl vinyl ether, isobornyl vinyl ether, three ring (5.2.1.0 2,6) compound etc. that represents of decane-8-base vinyl ether, 3-(ethyleneoxy methyl)-3-Ethyloxetane, following formula;
(chemical formula 3)
As above-mentioned macromonomer, such as, there is the macromonomer etc. at polymer molecule chain end with list (methyl) acryloyl group that polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butyl acrylate, polysiloxane are such.
These unsaturated monomers (b2) separately or can mix two or more and use.
Basis is added up to unsaturated monomer (b1) and unsaturated monomer (b2), the copolymerization ratios of the unsaturated monomer (b1) in carbonyl bearing polymer (1) is preferably 5 ~ 50 quality %, is more preferably 10 ~ 40 quality %.Consider, preferably containing making unsaturated monomer (b1) with the coloured composition of the carbonyl bearing polymer (1) obtained with above-mentioned copolymerization ratios copolymerization from the angle of storage stability and alkali-developable excellence.
As the object lesson of carbonyl bearing polymer (1), such as existing open 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.
As carbonyl bearing polymer (2), such as, can use polymkeric substance 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.
About (B) binder resin in coloured composition of the present invention, the weight-average molecular weight (Mw) of the polystyrene conversion recorded using tetrahydrofuran as stripping solvent, by gel permeation chromatography (GPC) is preferably 1,000 ~ 100,000, be more preferably 3,000 ~ 50,000.Use (B) binder resin of this Mw can suppress as much as possible to occur dry foreign matter during coating, the pattern-like cured film with excellent in shape is formed with high resolving power and high residual film ratio, and the thermotolerance, electrical characteristics, solvent resistance, adhesiveness etc. of gained cured film can be improved further, from this point of view, for preferably.
(B) Mw of binder resin is preferably 1.0 ~ 5.0 with the ratio (Mw/Mn) of number-average molecular weight Mn, is more preferably 1.0 ~ 3.0.Here, Mn is the number-average molecular weight of the polystyrene conversion recorded using tetrahydrofuran as stripping solvent, with GPC.
(B) as described above binder resin is by being raw material with suitable unsaturated monomer or its potpourri, manufacturing by known method.The binder resin suitably controlled such as is obtained by method manufacturing structure, Mw/Mn etc. disclosed in Japanese Unexamined Patent Publication 2003-222717 publication, Japanese Unexamined Patent Publication 2006-259680 publication, PCT application No. 2007/029871 Publication etc.
As (B) binder resin in coloured composition of the present invention, can by polymkeric substance as described above separately or mix two or more and use.
Relative to (A) colorant 100 mass parts, the content of (B) binder resin in coloured composition of the present invention is preferably 10 ~ 1,000 mass parts, and being more preferably is 20 ~ 500 mass parts.The excellent storage stability of coloured composition containing (B) binder resin in above-mentioned scope, the alkali-developable of film is good, and the solvent resistance of gained cured film, adhesiveness, colorimetric properties improve further, from this point of view, for preferably.
< (C) free-radical polymerised compound >
(C) free-radical polymerised compound in coloured composition of the present invention is the compound of the group in molecule with more than 2 free redical polymerizations.As the group of free redical polymerization, such as, can be ethene unsaturated group, Oxyranyle, oxetanyl, N-alkoxy methyl amino etc.As above-mentioned ethene unsaturated group, be preferably (methyl) acryloyl group.
As (C) free-radical polymerised compound in the present invention, preferably have in molecule in the compound of more than 2 (methyl) acryloyl groups and molecule and there is choice for use the compound of more than 2 N-alkoxy methyl amino.
As the above-mentioned compound in molecule with more than 2 (methyl) acryloyl groups, multifunctional (methyl) acrylate that can be such as aliphatic polyhydroxy compound react with (methyl) acrylic acid and obtain, caprolactone modification multifunctional (methyl) acrylate, alkylene oxide modification multifunctional (methyl) acrylate, there is polyfunctional carbamate (methyl) acrylate that (methyl) acrylate of hydroxyl and polyfunctional isocyanate react and obtain, there is (methyl) acrylate of hydroxyl and anhydride reaction and multifunctional (methyl) acrylate etc. with carboxyl obtained.
As above-mentioned aliphatic polyhydroxy compound, can be such as the such divalent aliphatic polyhydroxy compound of ethylene glycol, propylene glycol, polyglycol, polypropylene glycol, aliphatic polyhydroxy compounds etc. more than 3 valencys that glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol are such.
As above-mentioned (methyl) acrylate with hydroxyl, such as, can be (methyl) acrylic acid 2-hydroxyl ethyl ester, trimethylolpropane two (methyl) acrylate, pentaerythrite three (methyl) acrylate, dipentaerythritol five (methyl) acrylate, glycerol dimethacrylate etc.;
As above-mentioned polyfunctional isocyanate, such as, can be toluene diisocyanate, hexamethylene diisocyanate, MDI, isophorone diisocyanate etc.
As above-mentioned acid anhydrides, such as, can be the acid anhydrides of dibasic acid, the acid dianhydride etc. of tetra-atomic acid, as the object lesson of these acid anhydrides, can be listed below respectively:
As the acid anhydrides of above-mentioned dibasic acid, such as, there are succinic anhydride, maleic anhydride, glutaric anhydride, itaconic anhydride, phthalic anhydride, hexahydrophthalic anhydride etc.;
As the acid dianhydride of above-mentioned tetra-atomic acid, such as, there are pyromellitic acid anhydride, bibenzene tetracarboxylic dianhydride, benzophenone tetracarboxylic dianhydride etc.
As above-mentioned caprolactone modification multifunctional (methyl) acrylate, such as, it can be the compound etc. recorded in paragraph (0015) ~ (0018) of Japanese Unexamined Patent Publication 11-44955 publication.As above-mentioned alkylene oxide modification multifunctional (methyl) acrylate, such as, can be
By at least a kind of modification be selected from oxirane and epoxypropane bisphenol-A two (methyl) acrylate,
Isocyanuric acid three (methyl) acrylate by least a kind of modification be selected from oxirane and epoxypropane, trimethylolpropane tris (methyl) acrylate by least a kind of modification be selected from oxirane and epoxypropane,
By at least a kind of modification be selected from oxirane and epoxypropane pentaerythrite three (methyl) acrylate,
By at least a kind of modification be selected from oxirane and epoxypropane pentaerythrite four (methyl) acrylate,
By at least a kind of modification be selected from oxirane and epoxypropane dipentaerythritol five (methyl) acrylate,
By dipentaerythritol six (methyl) acrylate etc. of at least a kind of modification be selected from oxirane and epoxypropane.
As the above-mentioned compound in molecule with more than 2 N-alkoxy methyl amino, such as, it can be the compound etc. with melamine structure, benzoguanamine structure or urea structures.Here, melamine structure refers to have the chemical constitution of more than 1 triazine ring as basic framework, benzoguanamine structure refers to that having more than 1 phenyl replaces the chemical constitution of triazine ring as basic framework, and this concept comprises melamine, benzoguanamine and their condensation product.As the object lesson of compound in molecule with more than 2 N-alkoxy methyl amino, such as, can be N, N, N ', N ', N ", N "-six (alkoxy methyl) melamine, N, N, N ', N '-four (alkoxy methyl) benzoguanamine, N, N, N ', N '-four (alkoxy methyl) glycoluril etc.
As (C) free-radical polymerised compound in the present invention, in above-claimed cpd, preferred compound group is that the aliphatic polyhydroxy compound of more than 3 valencys reacts with (methyl) acrylic acid multifunctional (methyl) acrylate obtained, caprolactone modification multifunctional (methyl) acrylate, polyfunctional carbamate (methyl) acrylate, there is multifunctional (methyl) acrylate of carboxyl, N, N, N ', N ', N ", N "-six (alkoxy methyl) melamine, N, N, N ', N '-four (alkoxy methyl) benzoguanamine.Trimethylolpropane triacrylate, pentaerythritol triacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate in multifunctional (methyl) acrylate that aliphatic polyhydroxy compounds more than 3 valencys and (methyl) acrylic acid react and obtains, and
There is compound and Dipentaerythritol Pentaacrylate that five pentaerythritol triacrylates in multifunctional (methyl) acrylate of carboxyl and succinic anhydride react and obtain and the compound that succinic anhydride reacts and obtains is high in the intensity of the color solidification thing formed, surface smoothness is excellent and not easily occur on the substrate in unexposed portion and on light shield layer that dirty version, film are especially preferred in residual etc.
In coloured composition of the present invention, (C) free-radical polymerised compound separately or can mix two or more and use.
Relative to (A) colorant 100 mass parts, the content of (C) free-radical polymerised compound in coloured composition of the present invention is preferably 10 ~ 1,000 mass parts, is more preferably 20 ~ 700 mass parts, is especially preferably 50 ~ 500 mass parts.
Coloured composition containing (C) free radical polymerization compounds in above-mentioned scope, the developability of its film is excellent, can control as much as possible on the substrate in unexposed portion or on light shield layer, to occur the unfavorable conditions such as dirty version, film remain, and the curability of film is also excellent, thus preferably.
< (D) optical free radical propellant >
(D) optical free radical propellant contained in coloured composition of the present invention produces the compound of energy as the free radical of the spike of the free radical polymerization of initiation above-mentioned (C) free-radical polymerised compound.
As this (D) optical free radical propellant, such as, can be thioxanthones compounds, acetophenone compounds, bisglyoxaline compounds, compound in triazine class, O-acyl group oxime compound, salt compounds, benzoin compounds, benzophenone compound, α-cyclohexadione compounds, multinuclear quinones, diazo-compounds, acid imide sulfonates compounds etc.
In coloured composition of the present invention, (D) optical free radical propellant separately or can mix two or more and use.
As (D) optical free radical propellant in the present invention; preferred use is selected from least one in thioxanthones compounds, acetophenone compounds, bisglyoxaline compounds, compound in triazine class, O-acyl group oxime compound, especially preferably containing O-acyl group oxime compound.
(D) object lesson of optical free radical propellant is as follows.
As above-mentioned thioxanthones compounds, such as there are thioxanthones, CTX, 2-methyl thioxanthones, ITX, ITX, 2,4-bis-clopenthixal ketones, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropylthioxanthone etc.;
As above-mentioned acetophenone compounds, such as, there are 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.;
As above-mentioned bisglyoxaline compounds, such as, have 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4-dichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline, 2,2 '-bis-(2,4,6-trichlorophenyl)-4,4 ', 5,5 '-tetraphenyl-1,2 '-bisglyoxaline etc.;
As above-mentioned compound in triazine class, such as have 2, 4, 6-tri-(trichloromethyl)-s-triazine, 2-methyl-4, two (the trichloromethyl)-s-triazine of 6-, 2-(2-(5-methylfuran-2-base) vinyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(2-(furans-2-base) vinyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(2-(4-diethylamino-2-aminomethyl phenyl) vinyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(2-(3, 4-Dimethoxyphenyl) vinyl)-4, 6-bis-(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-ethoxystyrene base)-4, two (the trichloromethyl)-s-triazine of 6-, 2-(4-n-butoxyphenyl)-4, two (the trichloromethyl)-s-triazines of 6-etc. have the compound in triazine class of halomethyl,
As above-mentioned O-acyl group oxime compound, such as have 1, 2-acetyl caproyl, 1-(4-(thiophenyl) phenyl)-, 2-(O-benzoyl oxime), ethyl ketone, 1-(9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base)-, 1-(O-acetyl oxime), ethyl ketone, 1-(9-ethyl-6-(2-methyl-4-tetrahydrofuran base methoxybenzoyl base)-9H-carbazole-3-base)-, 1-(O-acetyl oxime), ethyl ketone, 1-(9-ethyl-6-{2-methyl-4-(2, 2-dimethyl-1, 3-dioxolanyl) methoxybenzoyl base }-9H-carbazole-3-base)-, 1-(O-acetyl oxime) etc.As the commercially available product of O-acyl group oxime compound, such as, can enumerate NCI-831, NCI-930 (above is ADEKA Products), DFI-020, DFI-091 (above is Daito Chemix Products) etc.
When using bisglyoxaline compounds as (D) optical free radical propellant in the present invention, considering from the angle that can improve luminous sensitivity further, preferably using hydrogen donor simultaneously.Here, " hydrogen donor " refers to the compound that can supply hydrogen atom to the free radical produced by bisglyoxaline compounds by illumination.As this hydrogen donor, it can be such as the thio-alcohol hydrogen donor and 4 such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, the amine hydrogen donors such as 4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(diethylamino) benzophenone.These hydrogen donors separately or can mix two or more and use, and have the angle greatly improved to consider, preferably by least a kind of use that combines at least a kind in thio-alcohol hydrogen donor and amine hydrogen donor from making luminous sensitivity.
On the other hand; when use the optical free radical propellant beyond bisglyoxaline compounds, preferably use be selected from thioxanthone compounds, acetophenone compound, triaizine compounds and O-acyl group oxime compound at least a kind as (D) optical free radical propellant in the present invention, sensitizer can be used together with these optical free radical propellants.As this sensitizer, can be such as 4, 4 '-bis-(dimethylamino) benzophenone, 4, 4 '-bis-(diethylamino) benzophenone, 4-diethyl amino benzoylformaldoxime, 4-dimethylamino propiophenone, EDMAB, 4-dimethylaminobenzoic acid 2-Octyl Nitrite, 2, two (the 4-diethylamino benzal) cyclohexanone of 5-, 7-diethylamino-3-(4-diethylamino benzoyl) cumarin, 4-(diethylamino) chalcone etc., at least a kind that is selected from these compounds can be used.
Relative to (C) free-radical polymerised compound 100 mass parts, (D) optical free radical propellant in coloured composition of the present invention containing proportional be preferably 0.01 ~ 120 mass parts, be more preferably 1 ~ 100 mass parts.By being set in above-mentioned scope by (D) optical free radical propellant containing proportional, the curability of coloured composition can be made better, from this point of view, for preferably.
When using bisglyoxaline compounds as (D) optical free radical propellant and use hydrogen donor while using this bisglyoxaline compounds, relative to bisglyoxaline compounds 100 mass parts, the content of preferred hydrogen donor, below 500 mass parts, is more preferably 50 ~ 300 quality.
When using the optical free radical propellant beyond bisglyoxaline compounds as (D) optical free radical propellant and use sensitizer while using this optical free radical propellant, relative to optical free radical propellant 100 mass parts beyond bisglyoxaline compounds, the content of sensitizer, preferably below 300 mass parts, is more preferably 50 ~ 150 mass parts.
< (E) compound >
(E) compound in the present invention has group that above-mentioned formula (E0) represents and is connected directly between structure on aromatic rings.
As the R in above-mentioned (E0) ialkyl, can be such as methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, sec-butyl, the tert-butyl group etc.R ibe preferably alkyl, be more preferably methyl or ethyl.
R iIit can be separately hydrogen atom and as R ialkyl and any one in the group that lists above, be preferably hydrogen atom.
X is preferably 1.
(E) compound in the present invention is preferably in molecule the compound with the group that more than 2 above-mentioned formulas (E0) represent, is more preferably the compound with more than 4 above-mentioned groups.Especially preferably there is the compound of 6 ~ 10 above-mentioned groups.Also the group that more than 2 above-mentioned formulas (E0) represent can be combined with on 1 aromatic rings.
(E) compound in the present invention preferably has the compound of at least a kind of group be selected from 1 valency group that following formula (E0-1) represents and the divalent group that following formula (E0-2) represents.
(chemical formula 4)
(E0 in formula (E0-1) and (E0-2) is respectively the group that above-mentioned formula (E0) represents,
Z separately represents hydroxyl or 1 valency organic group,
"+" represents associative key respectively;
In formula (E0-1), a1 is the integer of 1 ~ 5, and b1 is the integer of 0 ~ 4, and meets the relation of a1+b1=1 ~ 5; And,
(E0-2), in, a2 is the integer of 1 ~ 4, and b2 is the integer of 0 ~ 3, but meets the relation of a2+b2=1 ~ 4.〕
A1 in preferred above-mentioned formula (E0-1) and the a2 in above-mentioned formula (E0-2) separately represents 1 or 2, is more preferably 2.
Z in a1 in above-mentioned formula (E0-1) and above-mentioned formula (E0-2) is hydroxyl or 1 valency organic group.As this organic group, such as, can be the alkoxy of carbon number 1 ~ 6, the alkoxyalkoxy group of carbon number 2 ~ 8, the acyloxy, 2,3-glycidoxies, 2,3-dihydroxy propoxyl group etc. of carbon number 2 ~ 6.As Z, consider from the angle making the stability of gained coloured composition higher, be preferably the acyloxy of hydroxyl, the alkoxy of carbon number 1 ~ 4, the alkoxyalkoxy group of carbon number 2 ~ 6 or carbon number 2 ~ 4.As the object lesson of these groups, as alkoxy, such as, there are methoxyl, ethoxy, propoxyl group, butoxy etc.;
As alkoxyalkoxy group, such as, there are 1-methoxyethoxy, 2-methoxyethoxy, 1-ethoxyethoxy, 2-ethoxyethoxy, 1-fourth oxygen ethoxy etc.;
As acyloxy, such as, there is acetoxyl group etc.
B1 in preferred above-mentioned formula (E0-1) and the b2 in above-mentioned formula (E0-2) separately represents 0 or 1.
(E) compound had in the present invention of group as described above is preferably selected from least a kind of compound in the compound that following formula (E-1) ~ (E-5) represent respectively.
(chemical formula 5)
(chemical formula 6)
(E0 and Z in formula (E-1) ~ (E-5) respectively with E0 and the Z synonym in above-mentioned formula (E0-1) and (E0-2),
R separately represents alkyl, the acyl group of carbon number 2 ~ 6, the phenyl or naphthyl of hydrogen atom, carbon number 1 ~ 6,
A separately represents singly-bound ,-O-,-S-,-CO-,-COO-,-OCO-,-SO-,-SO 2-,-CR 2-(wherein, R and above-mentioned synonym)) or the group that represents of following formula (T-1);
(chemical formula 7)
(in above-mentioned formula (T-1), the Z synonym in Z and above-mentioned formula (E0-1) and (E0-2), n is the integer of 0 ~ 4, and "+" represents associative key.)
C1, c2, d1 and d2 in formula (E-1) separately represent the integer of 0 ~ 5, but meet the condition of c1+d1=0 ~ 5 and c2+d2=0 ~ 5, and in c1 and c2 at least 1 is not 0;
E1 ~ e3 in formula (E-2) and f1 ~ f3 separately represents the integer of 0 ~ 5, but meets the condition of e1+f1=0 ~ 5, e2+f2=0 ~ 5 and e3+f3=0 ~ 5, and in e1 ~ e3 at least 1 is not 0;
G1 ~ g4 in formula (E-3) and h1 ~ h4 separately represents the integer of 0 ~ 5, but meets the condition of g1+h1=0 ~ 5, g2+h2=0 ~ 5, g3+h3=0 ~ 5 and g4+h4=0 ~ 5, and in g1 ~ g4 at least 1 is not 0;
I1 ~ i3 in formula (E-4) and j1 ~ j3 separately represents the integer of 0 ~ 5, i4 and j4 separately represents the integer of 0 ~ 4, but meet the condition of i1+j1=0 ~ 5, i2+j2=0 ~ 5, i3+j3=0 ~ 5 and i4+j4=0 ~ 4, and in i1 ~ i4 at least 1 is not 0;
K1, k2, L1 and L2 in formula (E-5) separately represent the integer of 0 ~ 5, k3 and L3 separately represents the integer of 0 ~ 4, but meet the condition of k1+L1=0 ~ 5, k2+L2=0 ~ 5 and k3+L3=0 ~ 4, and in k1 ~ k3 at least 1 is not 0;
M is the integer of 1 ~ 5.〕
As the R in above-mentioned formula (E-2) ~ (E-5), be preferably the alkyl of hydrogen atom or carbon number 1 ~ 4, be more preferably hydrogen atom or methyl, be especially preferably hydrogen atom.
As A, be preferably the group that singly-bound, methylene, propane-2,2-bis-base or above-mentioned formula (T-1) represent.
C1, c2, e1 in above-mentioned formula (E-1) ~ (E ~ 5) ~ e3, g1 ~ g4, i1 ~ i3 and k1 ~ k3 is preferably 1 or 2 respectively, is more preferably 2;
I4 is preferably 0;
D1, d2, f1 ~ f3, h1 ~ h4, j1 ~ j3 and L1 ~ L3 is preferably 0 or 1 respectively, is more preferably 1.
As the object lesson of this (E) compound, can be listed below respectively: as above-claimed cpd (E-1), such as, have the compound etc. that following formula (E-1-1) ~ (E-1-3) represents respectively;
As above-claimed cpd (E-2), such as, there is the compound etc. that following formula (E-2-1) and (E-2-2) represent respectively;
As above-claimed cpd (E-3), such as, there is the compound etc. that following formula (E-3-1) represents;
As above-claimed cpd (E-4), such as, there is the compound etc. that following formula (E-4-1) ~ (E-4-8) represents respectively;
As above-claimed cpd (E-5), such as, there is the compound etc. that following formula (E-5-1) represents.
(chemical formula 8)
(chemical formula 9)
(chemical formula 10)
(chemical formula 11)
(in formula (E-5-1),
M, n, r and s separately represent the integer of 0 ~ 5,
P and q separately represents the integer of 0 ~ 4,
L is the random natural number of 0 or expression number of repeat unit,
But m+n and r+s is respectively in the scope of 0 ~ 5, p+q is in the scope of 0 ~ 4, and in m, r and p at least 1 is not 0.〕
Relative to (B) binder resin 100 mass parts, the use amount of (E) compound in coloured composition of the present invention is preferably 0.1 ~ 50 mass parts, is more preferably 1 ~ 45 mass parts, is preferably 3 ~ 40 mass parts.
As mentioned above, preferred (E) compound in the present invention has the group and group Z two side that above-mentioned (E0) represent.Here, the compound that group Z is hydroxyl if use as (E) compound, then can obtain the little coloured composition of mask misalignment.Relative to (B) binder resin 100 mass parts, the use amount of (E) compound is in this case preferably more than 1 mass parts, more preferably more than 2 mass parts, and then preferably more than 3 mass parts, especially preferred more than 5 mass parts, and preferably below 40 mass parts, more preferably below 35 mass parts, especially preferred below 30 mass parts.As the content range of (E) compound in coloured composition of the present invention, relative to (B) binder resin 100 mass parts, be preferably 1 ~ 40 mass parts, be more preferably 2 ~ 35 mass parts, be especially preferably 3 ~ 30 mass parts.
On the other hand, if use group Z be the compound of 1 valency organic group as (E) compound, then can obtain the high coloured composition of luminous sensitivity.Relative to (B) binder resin 100 mass parts, the use amount of (E) compound is in this case preferably more than 1 mass parts, more preferably more than 2 mass parts, especially preferred more than 3 mass parts, and preferably below 45 mass parts, more preferably below 43 mass parts, and then preferably below 40 mass parts, especially preferred below 35 mass parts.As the content range of (E) compound in coloured composition of the present invention, relative to (B) binder resin 100 mass parts, be preferably 1 ~ 45 mass parts, be more preferably 2 ~ 40 mass parts, and then be preferably 3 ~ 35 mass parts, in addition, also can be 20 ~ 45 mass parts, and then be 25 ~ 43 mass parts, be especially 30 ~ 40 mass parts.
Other compositions of < >
Coloured composition of the present invention contains above-mentioned (A) ~ (E) composition as neccessary composition, but in the scope not damaging effect of the present invention, also can contain other compositions arbitrarily.As other compositions this kind of, such as, it can be the packing material such as glass, aluminium oxide;
The macromolecular compound such as polyvinyl alcohol (PVA), poly-(fluoroalkyl);
The surfactants such as fluorine class surfactant, silicone surfactant;
Vinyltrimethoxy silane, vinyltriethoxysilane, vinyl three (2-methoxyethoxy) silane, N-(2-amino-ethyl)-3-amino propyl methyl dimethoxysilane, N-(2-amino-ethyl)-3-TSL 8330, APTES, 3-(2, 3-glycidoxy) propyl trimethoxy silicane, 3-(2, 3-glycidoxy) hydroxypropyl methyl dimethoxysilane, 2-(3, 4-epoxycyclohexyl) ethyl trimethoxy silane, 3-chloropropylmethyldimethoxysilane, 3-r-chloropropyl trimethoxyl silane, 3-methacryloxypropyl trimethoxy silane, the adhesion promoters 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-di-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-oxaspiro (5.5) undecane, thiodiethylene two (3-(3,5-di-tert-butyl-hydroxy phenyl) propionic ester);
The ultraviolet light absorbers such as 2-(the 3-tert-butyl group-5-methyl-2-hydroxy phenyl) the chloro-benzotriazole of-5-, alkoxy benzophenone;
The anti-coagulants such as sodium polyacrylate;
Malonic acid, hexane diacid, itaconic acid, citraconic acid, fumaric acid, mesaconic acid, 2-ethylaminoethanol, 3-amino-1-propyl alcohol, 5-amino-1-amylalcohol, 3-amino-1,2-propylene glycol, 2-amino-1, the residue improvers such as amino-1, the 2-butylene glycol of ammediol, 4-;
The developability improvers such as mono succinate (2-(methyl) acryloyl-oxyethyl) ester, phthalic acid list (2-(methyl) acryloyl-oxyethyl) ester, ω-carboxy-polycaprolactone list (methyl) acrylate, etc.
< solvent >
Coloured composition of the present invention contains above-mentioned (A) ~ (E) composition as neccessary composition, and at random containing other compositions, is preferably modulated into the liquid composition also containing solvent.
Here, as solvent, preferably can disperse or dissolve mentioned component, do not react with these compositions and there is appropriate volatile material, can from the solvent with this characteristic suitable choice for use.
As solvent contained in coloured composition of the present invention, can be listed below: such as glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol list n-propyl ether, ethylene glycol list n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol list n-propyl ether, diethylene glycol list n-butyl ether, triethylene glycol monomethyl ether, Triethylene glycol ethyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether, propylene glycol list n-propyl ether, propylene glycol list n-butyl ether, dipropylene glycol monomethyl ether, DPE, dipropylene glycol list n-propyl ether, dipropylene glycol list n-butyl ether, Tripropylene glycol monomethyl Ether, (many) alkylene glycol monoalkyl ethers classes 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;
(many) alkylene glycol monoalkyl ethers acetic acid esters such as ethylene glycol monomethyl ether acetic acid ester, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetic acid esters, diethylene glycol monoethyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, 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;
The aromatic hydrocarbons such as toluene, dimethylbenzene;
Acid amides or the lactams such as DMF, DMA, 1-METHYLPYRROLIDONE; Etc..
In these solvents, from dissolubility, the angle of coating etc. and the dispersiveness containing pigment during this solvent is considered, preferably uses (gathering) alkylene glycol monoalkyl ethers class, lactic acid alkyl ester class, (many) alkylene glycol monoalkyl ethers acetate esters, other ethers, ketone, diacetate esters class, alkoxyl carboxylate class, other ester classes, especially preferably use propylene glycol monomethyl ether, dihydroxypropane single-ether, ethylene glycol monomethyl ether acetate, propylene glycol methyl ether acetate, propylene glycol monoethyl ether acetate, 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 coloured composition of the present invention, solvent separately or can mix two or more and use.
As the solvent of coloured composition of the present invention, most preferably, containing at least one be selected from (many) alkylene glycol monoalkyl ethers class and (many) alkylene glycol monoalkyl ethers acetate esters or
The potpourri of (many) alkylene glycol monoalkyl ethers class and (many) alkylene glycol monoalkyl ethers acetate esters.
To the solvent in coloured composition of the present invention without particular restriction, preferred solvent-laden amount makes the solid component concentration of coloured composition (the total quality of the composition beyond desolventizing in coloured composition accounts for the ratio of the gross mass of this coloured composition) be 5 ~ 50 quality %, is more preferably 10 ~ 40 quality %.Contain in the coloured composition of solvent with above-mentioned amount, the excellent dispersion of contained each composition, the stability thus as composition is also excellent, and in addition, coating is also excellent, from this point of view, for preferably.
The modulator approach > of < coloured composition
Coloured composition of the present invention is modulated by suitable method.Such as modulate by above-mentioned (A) ~ (E) composition is mixed together with other compositions arbitrary and solvent.
Such as, (A) colorant in coloured composition of the present invention contains pigment, by preferably such as using the equilateral pulverizing limit of ball mill, roller mill to mix, disperse in a solvent together with a part (B) binder resin under the existence of spreading agent, optionally (A) colorant, form dispersible pigment dispersion, then, in this dispersible pigment dispersion, add (B) binder resin and (C) ~ (E) composition and other compositions, the mixing arbitrarily of surplus, modulate.
The formation method > of < color solidification film
Use the coloured composition of the invention described above can form color solidification film.The concept of color solidification film of the present invention comprises in display element and solid-state imager each color pixel, black matrix", black interval part etc. that use.
Coloured composition of the present invention is used to form color solidification film, preferably by any one method following.
First method: be coated with coloured composition of the present invention on substrate, forms film, then penetrates the illumination of carrying out at least partially of this film, develop afterwards, preferably carries out further heating (toasting afterwards);
Second method: by ink-jetting style, coloured composition of the present invention is coated into pattern-like on substrate, forms film, at random carries out illumination to this film and penetrate, and carries out further heating (toasting afterwards) preferably.
In above-mentioned either method, red, green and blue three look or green grass or young crops can be used, color solidification film that the coloured composition of fuchsin and Huang Sanse is formed into each color pixel successively, form colored filter thus.On the other hand, by using Black coloring compositions to form black colorant cured film, black matrix" or black interval part can be formed.
As aforesaid substrate, such as, it can be the substrate formed by glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc.Also can as required in advance to the pre-treatment that these substrates are suitable for, such as chemicals (such as silane coupling agent) process, Cement Composite Treated by Plasma, ion plating process, sputter process, the process utilizing gas-phase reaction method to carry out, the process etc. that utilizes vacuum vapour deposition to carry out.
On the substrate will used during the pixel of coloured composition of the present invention for the formation of colored filter, be preferably formed black matrix", pixel region is divided.This black matrix" can be metal (the such as chromium etc.) film with predetermined pattern, the color solidification film etc. formed by coloured composition.The metallic film of pattern-like is such as formed by carrying out photoetching to the metallic film utilizing sputtering method, vapour deposition method etc. to be formed on substrate.The color solidification film of the pattern-like formed by coloured composition is by using Black coloring compositions, utilizing the method same with the present invention and formed.In the second method using ink-jetting style, above-mentioned black matrix", beyond shade function, also plays barrier action, makes the assorted composition ejected by ink-jetting style colour mixture not occur.Therefore, preferably black matrix" in this case has the thickness of more than certain thickness, and therefore, preferably black matrix" is in this case the black cured film using Black coloring compositions to be formed.
Coloured composition of the present invention is preferably the substrate not yet forming the black matrix" dividing pixel region for the formation of the substrate used during black matrix".
And then, coloured composition of the present invention is preferably formed for the formation of the substrate used during black interval part and divides the black matrix" of pixel region and the substrate of pixel.
In above-mentioned first method, as the method being coated with coloured composition on substrate, such as, can be spraying process, rolling method, method of spin coating (spin-coating method), slot coating processes (slot coated method), stick coating method etc.In these methods, preferably adopt spin-coating method or slot coating processes.
After being coated with by method as described above or ink-jetting style, it be made to form film, can preferably use the coloured composition after to coating to heat (prebake conditions), method except desolventizing.The condition of this prebake conditions is preferably preferably about 1 ~ 10 minute at 70 ~ 110 DEG C, and prebake conditions is preferably under reduced pressure carried out.As degree of decompression, preferably setting extreme pressure (absolute pressure) is 50 ~ 200Pa.
The thickness of film, with the thickness gauge after desolventizing, is preferably 0.6 ~ 12 μm, is more preferably 1.2 ~ 10 μm.
As the light source carrying out using when illumination is penetrated to the film formed, can be 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, argon laser, YAG laser, XeCl excimers laser, N_2 laser, ultraviolet LED etc.As the light irradiated, preferably there is within the scope of 190 ~ 450nm the light of bright line.Light exposure is preferably 10 ~ 10,000J/m 2, be more preferably 50 ~ 5,000J/m 2.
Above-mentioned development uses alkaline developer to carry out.By development treatment, the unexposed portion in removing film, forms the film of pattern-like.As this alkaline developer, preferred use is sodium carbonate, sodium bicarbonate, NaOH, potassium hydroxide, tetramethylammonium hydroxide, choline, 1 such as, the aqueous solution of 8-diazabicyclo-(5.4.0)-7-undecylene, 1,5-diazabicyclo-(4.3.0)-5-nonene etc.Also in proper range, the such as water-miscible organic solvent such as methyl alcohol, ethanol can be added in this aqueous solution as required, surfactant etc.
As developing method, such as, can adopt spray development method, spray development method, immersion development method, soak and put formula (covering liquid) development method etc.Development conditions preferably carries out 5 ~ 300 seconds at normal temperatures.Film after development is preferably washed.
Above-mentioned rear baking such as such as can be carried out 10 ~ 60 minutes at the temperature of 180 ~ 280 DEG C.
Its purposes is looked and in following scope by the thickness of above-mentioned such color solidification film formed.
Pixel: be preferably 0.5 ~ 5 μm, be more preferably 1 ~ 3 μm
Black matrix": be preferably 0.5 ~ 10 μm, be more preferably 0.8 ~ 5 μm
Black interval part: be preferably 0.5 ~ 10 μm, be more preferably 1 ~ 7 μm
Form each color pixel and the pattern of pixels that obtains forms nesa coating and distance piece after forming diaphragm thereon as required, successively like that by above-mentioned, thus can use as the colored filter of display element.
< display element >
Display element of the present invention has at least one color solidification film be selected from above-mentioned such pixel, colored filter, black matrix" and black interval part formed.As above-mentioned display element, such as, can be color liquid crystal display device, organic EL display element, Electronic Paper etc.
Above-mentioned color liquid crystal display device can adopt the known suitable liquid crystal mode such as TN (twisted-nematic) type, STN (supertwist is to row) type, IPS (coplanar switch) type, VA (vertical orientated) type, OCB (optical compensation birefringence) type.
Above-mentioned color liquid crystal display device can be transmission-type, also can be reflection-type, can have the liquid crystal cell of suitable configurations.As the structure of liquid crystal cell, such as, structure can be listed below: the driving substrate being configured with thin film transistor (TFT) (TFT) and the substrate in opposite directions that is formed with colored filter are used in pairs and sandwich by the structure of liquid crystal layer between this is to substrate;
The substrate with thin film transistor (TFT) (TFT) and colored filter and the substrate that is formed with ITO (indium oxide doped with tin) electrode are used in pairs and between this is to substrate, sandwiches the structure of liquid crystal layer, etc.
Color liquid crystal display arrangement also can have back light unit outside above-mentioned liquid crystal cell.As the light source in back light unit, such as, can be cold cathode fluorescent tube, White LED etc.
Above-mentioned organic EL display element can adopt suitable structure, such as, can adopt structure etc. disclosed in Japanese Unexamined Patent Publication 11-307242 publication.
Above-mentioned Electronic Paper can adopt suitable structure, such as, can adopt structure etc. disclosed in Japanese Unexamined Patent Publication 2007-41169 publication.
Above-mentioned solid-state imager can adopt suitable structure, such as, can adopt structure etc. disclosed in Jap.P. No. 4480740 instructions.
(embodiment)
Below by enumerating embodiment, more specific description is carried out to embodiments of the present invention.But the present invention is not limited to following embodiment.The synthesis > of < (B) binder resin
Synthesis example B1
In the flask with cooling tube and stirring machine, drop into propylene glycol methyl ether acetate 100 mass parts, carry out nitrogen displacement.Beaker contents is heated to 80 DEG C, dripped by propylene glycol methyl ether acetate 100 mass parts, methacrylic acid 20 mass parts, styrene 10 mass parts, benzyl methacrylate 5 mass parts, HEMA 15 mass parts, 2-Ethylhexyl Methacrylate 23 mass parts, N-phenylmaleimide 12 mass parts, mono succinate (2-acryloyl-oxyethyl) ester 15 mass parts and 2 with 1 hour at the same temperature, 2 '-azo two (2,4-methyl pentane nitrile) 6 mass parts form mixed solution, keep at such a temperature be polymerized 2 hours.Then, by the temperature to 100 of reaction solution DEG C, keep being polymerized 1 hour further at such a temperature, obtain the solution (solid component concentration is 33 quality %) containing binder resin (B-1) thus.The Mw of gained binder resin (B-1) is 12,200, Mn is 6,500.The modulation > of < dispersible pigment dispersion
Modulate routine P1
Will by the C.I. pigment yellow 13 8 of C.I. naphthol green 58 and 3.9 mass parts of 9.1 mass parts as (A) colorant, as BYK-LPN21116 (the Bi Ke chemistry Products of the solution shape of spreading agent, solid component concentration is 40 quality %) 12.5 mass parts, as solution 15.2 mass parts containing the binder resin (B-1) obtained in above-mentioned synthesis example B1 and the mixed liquor formed as methyl proxitol acetate 59.3 mass parts of solvent of the part of (B) binder resin, use ball mill mixes, disperse 12 hours, modulate dispersible pigment dispersion (A-1-1) thus.
Modulate routine P2 ~ P6
Except using the pigment of kind and the amount recorded in table 1 as except (A) colorant in above-mentioned modulation example P1, modulate dispersible pigment dispersion (A-1-2) ~ (A-1-6) respectively in the same manner as the routine P1 of modulation.
Table 1
The kind of pigment and amount (mass parts) Dispersible pigment dispersion title
Modulate routine P1 G58/Y138＝9.1/3.9 A-1-1
Modulate routine P2 G58/G7/Y129＝3.9/5.2./3.9 A-1-2
Modulate routine P3 G7/Y185＝9.1/3.9 A-1-3
Modulate routine P4 R254/R177＝6.5/6.5 A-1-4
Modulate routine P5 R254＝13 A-1-5
Modulate routine P6 B15∶6=13 A-1-6
Pigment abbreviation in table 1 is expressed as follows respectively.
G58:C.I. naphthol green 58
Y138:C.I. pigment yellow 13 8
G7:C.I. pigment Green 7
Y129:C.I. pigment Yellow 12 9
Y185:C.I. pigment yellow 185
R254:C.I. paratonere 254
R177:C.I. paratonere 177
B15 ︰ 6:C.I. pigment blue 15 ︰ 6
The synthesis > of < dyestuff
Synthesis example SD1
The compound (compound (A-2-1)) that above-mentioned formula (A-2-1) represents is synthesized according to the synthesis example 1 of Japanese Unexamined Patent Publication 2013-190776 publication.
Synthesis example SD2
The compound (compound (A-2-2)) that above-mentioned formula (A-2-2) represents is synthesized according to the method recorded in the colorant synthesis example 3 of Japanese Unexamined Patent Publication 2012-108469 publication.
The modulation > of < dye solution
Modulate routine SD1
The compound obtained in above-mentioned synthesis example SD1 (A-2-1) 10 mass parts is dissolved in propylene glycol monomethyl ether 90 mass parts, modulates dye solution (A-2-1) thus.
Modulate routine SD2
The compound obtained in above-mentioned synthesis example SD2 (A-2-2) 10 mass parts is dissolved in propylene glycol monomethyl ether 90 mass parts, modulates dye solution (A-2-2) thus.
Embodiment 1
The modulation > of < coloured composition
By dispersible pigment dispersion (A-1-1) 100 mass parts obtained in above-mentioned modulation example P1, solution 15 mass parts contained as the binder resin (B-1) of (B) binder resin obtained in above-mentioned synthesis example B1, as the KAYARAD DPHA (trade name of (C) free-radical polymerised compound, Japan's chemical drug Products, the potpourri of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate) 13 mass parts, as the IRGACURE 369 (trade name of (D) optical free radical propellant, BASF AG's product, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butanone-1) 0.7 mass parts and ADEKA arc Luz NCI-831 (trade name, O-acyl group oxime compound, ADEKA Products) 0.6 mass parts, compound 1.0 mass parts represented as the above-mentioned formula (E-4-1) of (E) compound and the Megafac F-554 (trade name as fluorine class surfactant, DIC Products) 0.05 mass parts mixing, add 3-methoxyacetic acid butyl ester (MBA) and propylene glycol methyl ether acetate (PGMEA) again, the solvent composition modulated containing the composition brought into by dispersible pigment dispersion is MBA ︰ PGMEA=15 ︰ 85 (mass parts), solid component concentration is the coloured composition (S-1) of 17 quality %.
This coloured composition is evaluated in the steps below.
Evaluation result is shown in table 5.
< coloured composition evaluates >
(1) evaluation of solvent resistance
After use spin-coating method is coated with above-mentioned coloured composition (S-1) on the glass substrate, carries out 100 seconds prebake conditions with the hot plates of 90 DEG C, form the film of thickness 2.5 μm.The substrate of this band film is let cool to room temperature, via there is the photomask of space of lines pattern of seam wide 90 μm and space width 210 μm with 400J/m 2exposure to this film irradiate high-pressure mercury-vapor lamp (exposure gap=300 μm).Then, above-mentioned light postradiation band film substrate is developer solution with the aqueous solutions of potassium of temperature 23 DEG C, concentration 0.04 quality %, is sprayed 60 seconds under the condition of pressure 110KPa and developer solution flow 1.2 liters/min of developing, carries out spray development.By development after band film substrate ultrapure water cleaning, air-dry, then, carry out in the cleaning oven of 230 DEG C after 30 minutes toast, on substrate, form the pattern of pixels be made up of space of lines pattern thus.
The substrate being formed with pattern of pixels with said method is flooded 30 minutes in the 1-METHYLPYRROLIDONE of 25 DEG C, with shape and the thickness of the pattern of pixels before and after sem observation dipping, evaluates by following standard.
Evaluation criterion
Pattern of pixels have no defect and dipping after the thickness of thickness before dipping more than 95% situation: solvent resistance " well "
Pattern of pixels segmental defect or dipping after the thickness of thickness before dipping more than 80%, be less than 95% situation: solvent resistance " bad "
Pattern of pixels segmental defect and thickness after dipping are less than the situation of 80% of the thickness before dipping: solvent resistance " can not "
(2) evaluation of sensitivity and mask misalignment
With above-mentioned " (1) solvent resistance evaluation " in the same manner as operate, on substrate, form the pattern of pixels be made up of space of lines pattern thus.
Observe the pattern of pixels optical microscope of above-mentioned gained, there is N/D at check pattern edge, and evaluates by following standard.
Evaluation criterion
Pattern has no the situation of defect: sensitivity " excellent "
The situation of defect is slightly shown in by pattern: sensitivity " well "
The situation of many places defect is shown in by pattern: sensitivity " bad "
In addition, measure the live width of above-mentioned gained pattern of pixels, obtain the value after the seam deducting photomask by this live width measured value wide (90 μm), according to this value, mask misalignment is evaluated.
Mask misalignment can roughly be evaluated by following standard.
Evaluation criterion
Subtract the situation that rear value is negative value: solidify bad, sensitivity is obviously poor.
Subtract rear value more than 0 μm, be less than the situation of 10 μm: mask misalignment little (mask misalignment is excellent)
Subtract the situation of rear value more than 10 μm: mask misalignment large (mask misalignment is poor)
Here, if the luminous sensitivity of coloured composition is enough high, then can form the pattern (color solidification film) of curability and the adhesiveness excellence to substrate, in the pattern formed, thus can't see defect and peel off.
On the other hand, if mask misalignment is little, then can form the pattern of the size of reappearing photomask size.
Thus, as long as either party excellent of the above-mentioned luminous sensitivity of coloured composition and mask misalignment, just can be used well on the basis of the purposes of the process step design selecting adopt, liquid crystal display cells etc.
Embodiment 2 ~ 4,8 ~ 10 and 12 ~ 15
Except except making the kind of (A) ~ (E) composition and measure described in table 2 in above-described embodiment 1, modulate coloured composition similarly to Example 1, and carried out various evaluation.
Evaluation result is shown in table 5.
Embodiment 5
By dispersion liquid (A-1-5) 85 mass parts (containing pigment 11 mass parts and binder resin (B-1) 4.2 mass parts) of gained in above-mentioned modulation example P5 and in above-mentioned modulation example SD1 dye solution (A-2-1) 20 mass parts (containing dyestuff 2 mass parts) of gained, (bonding agent (B-1) resin is converted into containing solution 31 mass parts of the binder resin as (B) binder resin (B-1) of gained in above-mentioned synthesis example B1, be equivalent to 10.2 mass parts), as the KAYARAD DPHA (trade name of (C) free-radical polymerised compound, Japan's chemical drug Products, the potpourri of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate) 19 mass parts, as the IRGACURE 369 (trade name of (D) optical free radical propellant, BASF AG's product, 2-hexyl-2-dimethylamino-1-(4-morphlinophenyl) butanone-1) 1.0 mass parts and ADEKA arc LuzNCI-831 (trade name, O-acyl group oxime compound, ADEKA Products) 0.9 mass parts, compound 1.5 mass parts represented as the above-mentioned formula (E-4-1) of (E) compound and the Megafac F-554 (trade name as fluorine class surfactant, DIC Products) 0.05 mass parts mixing, add MBA again, PGMEA and propylene glycol monomethyl ether (PGME), the solvent composition modulated containing the composition brought into by dispersible pigment dispersion is MBA ︰ PGMEA ︰ PGME=15 ︰ 75 ︰ 10 (mass parts), solid component concentration is the coloured composition of 17 quality %.
This coloured composition is used to carry out various evaluation similarly to Example 1.
Evaluation result is shown in table 5.
Embodiment 6
Except making the kind of (A) composition and amount as except described in table 2 in above-described embodiment 5, modulating coloured composition similarly to Example 5, and having carried out various evaluation.
Evaluation result is shown in table 5.
Embodiment 7
By dye solution (A-2-2) 130 mass parts (containing dyestuff 13 mass parts) of gained in above-mentioned modulation example SD2, (binder resin (B-1) is converted into containing solution 62 mass parts of the binder resin as (B) binder resin (B-1) of gained in above-mentioned synthesis example B1, be equivalent to 20.5 mass parts), as the KAYARAD DPHA (trade name of (C) free-radical polymerised compound, Japan's chemical drug Products, the potpourri of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate) 27 mass parts, as the IRGACURE 369 (trade name of (D) optical free radical propellant, BASF AG's product, 2-hexyl-2-dimethylamino-1-(4-morphlinophenyl) butanone-1) 2.5 mass parts and ADEKA arc Luz NCI-831 (trade name, O-acyl group oxime compound, ADEKA Products) 2.2 mass parts, compound 2.0 mass parts represented as the above-mentioned formula (E-4-1) of (E) compound and the Megafac F-554 (trade name as fluorine class surfactant, DIC Products) 0.05 mass parts, add MBA again, PGMEA and PGME, the solvent composition modulated containing the composition brought into by dispersible pigment dispersion is MBA ︰ PGMEA ︰ PGME=15 ︰ 40 ︰ 45 (mass parts), solid component concentration is the coloured composition of 17 quality %.
This coloured composition is used to carry out various evaluation similarly to Example 1.
Evaluation result is shown in table 5.
Embodiment 11
Except making the kind of (E) composition and amount as except described in table 2 in above-described embodiment 7, modulating coloured composition similarly to Example 7, and having carried out various evaluation.
Evaluation result is shown in table 5.
Embodiment 16,17 and 20 ~ 24 and comparative example 1 and 4
Except making the kind of (A) ~ (E) composition and amount as except described in table 3 in above-described embodiment 1, modulating coloured composition similarly to Example 1, and having carried out various evaluation.
Evaluation result is shown in table 6.
Embodiment 18 and 25 and comparative example 2 and 5
Except making the kind of (A) ~ (E) composition and amount as except described in table 3 in above-described embodiment 5, modulating coloured composition similarly to Example 5, and having carried out various evaluation.
Evaluation result is shown in table 6.
Embodiment 19 and comparative example 3 and 6
Except making the kind of (A) ~ (E) composition and amount as except described in table 3 in above-described embodiment 7, modulating coloured composition similarly to Example 7, and having carried out various evaluation.
Evaluation result is shown in table 6.
Embodiment 26,27,33 and 34 and comparative example 7,8,11 and 12
Except making the kind of (A) ~ (E) composition and amount as except described in table 4 in above-described embodiment 1, modulating coloured composition similarly to Example 1, and having carried out various evaluation.
Evaluation result is shown in table 7.
Embodiment 30 ~ 32,35 and 36 and comparative example 10,13 and 14
Except making the kind of (A) ~ (E) composition and amount as except described in table 4 in above-described embodiment 5, modulating coloured composition similarly to Example 5, and having carried out various evaluation.
Evaluation result is shown in table 7.
Embodiment 28,29 and comparative example 9
Except making the kind of (A) ~ (E) composition and measure as except record in table 4 in above-described embodiment 7, modulate coloured composition similarly to Example 7, and carried out various evaluation.
Evaluation result is shown in table 7.
Table 2
Table 3
Table 4
The implication of the abbreviation of each composition in above-mentioned table 2 ~ 4 is as follows respectively.
((C) free-radical polymerised compound)
C-1:KAYARAD DPHA (trade name, Japanese chemical drug Products, the potpourri of dipentaerythritol acrylate and Dipentaerythritol Pentaacrylate)
((D) optical free radical propellant)
D-1:IRGACURE 369 (trade name, BASF AG's product, 2-benzyl-2-dimethylamino-1-(4-morphlinophenyl) butanone-1)
D-2:ADEKA arc Luz NCI-831 (trade name, O-acyl group oxime compound, ADEKA Products)
((E) compound)
E-1-1: the compound that above-mentioned formula (E-1-1) represents
E-2-1: the compound that above-mentioned formula (E-2-1) represents
E-2-2: the compound that above-mentioned formula (E-2-2) represents
E-3-1: the compound that above-mentioned formula (E-3-1) represents
E-4-1: the compound that above-mentioned formula (E-4-1) represents
E-4-2: the compound that above-mentioned formula (E-4-2) represents
E-4-3: the compound that above-mentioned formula (E-4-3) represents
E-4-4: the compound that above-mentioned formula (E-4-4) represents
E-4-5: the compound that above-mentioned formula (E-4-5) represents
E-5-1: the compound that above-mentioned formula (E-5-1) represents
(other compounds)
R-1: the compound that following formula (R-1) represents
(chemical formula 12)
The compound that the above-mentioned formula (R-1) used in comparative example 1 ~ 3 represents does not belong to (E) compound of the present invention's regulation, but in table 3, conveniently charges in (E) compound one hurdle.
Table 5
Table 6
Table 7

Claims (11)

1. coloured composition, contains:
(A) colorant,
(B) binder resin,
(C) free-radical polymerised compound,
(D) optical free radical generation agent,
(E) there is the compound that group that following formula (E0) represents directly is combined in the structure on aromatic rings,
＊－(CR II 2)x－O－R I(E0)
In formula (E0),
R ithe alkyl of hydrogen atom or carbon number 1 ~ 4,
R iIseparately represent the alkyl of hydrogen atom or carbon number 1 ~ 4,
X is 1 or 2,
" * " represents the associative key be directly combined on aromatic rings.
2. coloured composition according to claim 1, it is characterized in that, described (E) compound is for having the compound of at least one group be selected from 1 valency group that following formula (E0-1) represents and the divalent group that following formula (E0-2) represents
(chemical formula 1)
In formula (E0-1) and (E0-2),
E0 is respectively the group that above-mentioned formula (E0) represents,
Z separately represents hydroxyl or 1 valency organic group,
"+" represents associative key respectively,
A1 is the integer of 1 ~ 5,
B1 is the integer of 0 ~ 4,
But meet the relation of a1+b1=1 ~ 5;
A2 is the integer of 1 ~ 4,
B2 is the integer of 0 ~ 3,
But meet the relation of a2+b2=1 ~ 4.
3. coloured composition according to claim 2, it is characterized in that, Z in described formula (E0-1) and (E0-2) separately represents alkoxy, the alkoxyalkoxy group of carbon number 2 ~ 8, the acyloxy, 2 of carbon number 2 ~ 6 of hydroxyl, carbon number 1 ~ 6,3-glycidoxy or 2,3-dihydroxy propoxyl group.
4. coloured composition according to claim 3, is characterized in that, described (E) compound is at least one compound in the compound that is selected from following formula (E-1) ~ (E-5) and represents respectively,
(chemical formula 2)
(chemical formula 3)
In formula (E-1) ~ (E-5),
E0 is respectively the group that described formula (E0) represents,
Z separately represents the acyloxy of the alkoxyalkoxy group of the alkoxy of hydroxyl, carbon number 1 ~ 6, carbon number 2 ~ 8, carbon number 2 ~ 6,2,3-glycidoxies or 2,3-dihydroxy propoxyl group,
R separately represents alkyl, the acyl group of carbon number 2 ~ 6, the phenyl or naphthyl of hydrogen atom, carbon number 1 ~ 6,
A separately represents singly-bound ,-O-,-S-,-CO-,-COO-,-OCO-,-SO-,-SO 2-,-CR 2-or the group that represents of following formula (T-1), formula-CR 2-in, R and aforementioned synonym,
(chemical formula 4)
In above-mentioned formula (T-1), Z and aforementioned synonym, n is the integer of 0 ~ 4, and "+" represents associative key;
C1, c2, d1 and d2 separately represent the integer of 0 ~ 5, but meet the condition of c1+d1=0 ~ 5 and c2+d2=0 ~ 5, and in c1 and c2 at least 1 is not 0;
E1 ~ e3 and f1 ~ f3 separately represents the integer of 0 ~ 5, but meets the condition of e1+f1=0 ~ 5, e2+f2=0 ~ 5 and e3+f3=0 ~ 5, and in e1 ~ e3 at least 1 is not 0;
G1 ~ g4 and h1 ~ h4 separately represents the integer of 0 ~ 5, but meets the condition of g1+h1=0 ~ 5, g2+h2=0 ~ 5, g3+h3=0 ~ 5 and g4+h4=0 ~ 5, and in g1 ~ g4 at least 1 is not 0;
I1 ~ i3 and j1 ~ j3 separately represents the integer of 0 ~ 5,
I4 and j4 separately represents the integer of 0 ~ 4, but meets the condition of i1+j1=0 ~ 5, i2+j2=0 ~ 5, i3+j3=0 ~ 5 and i4+J4=0 ~ 4, and in i1 ~ i4 at least 1 is not 0;
K1, k2, L1 and L2 separately represent the integer of 0 ~ 5,
K3 and L3 separately represents the integer of 0 ~ 4, but meets the condition of k1+L1=0 ~ 5, k2+L2=0 ~ 5 and k3+L3=0 ~ 4, and in k1 ~ k3 at least 1 is not 0;
M is the integer of 1 ~ 5.
5. the coloured composition according to any one of Claims 1 to 4, is characterized in that, relative to (B) binder resin 100 mass parts, described (E) compound containing proportional be 0.1 ~ 50 mass parts.
6. the coloured composition according to any one of Claims 1 to 4, is characterized in that, described (D) optical free radical produces agent and contains O-acyl group oxime compound.
7. the coloured composition according to any one of Claims 1 to 4, is characterized in that, adds up to benchmark with the solid constituent of coloured composition, described (A) colorant containing proportional be 15 ~ 45 quality %.
8. the coloured composition according to any one of Claims 1 to 4, is characterized in that, described (A) colorant contains dyestuff.
9. color solidification film, is characterized in that, uses the coloured composition according to any one of claim 1 ~ 8 to be formed.
10. color solidification film according to claim 9, is characterized in that, is pixel, black matrix" or black interval part.
11. display elements, is characterized in that, have the color solidification film described in claim 9 or 10.
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