CN104749882A - 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
CN104749882A
CN104749882A CN201410822660.8A CN201410822660A CN104749882A CN 104749882 A CN104749882 A CN 104749882A CN 201410822660 A CN201410822660 A CN 201410822660A CN 104749882 A CN104749882 A CN 104749882A
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methyl
group
acrylate
publication
coloured composition
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CN104749882B (en
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米田英司
依田杏介
间嶋宽
宫下由佳
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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
    • 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
    • C09B11/00—Diaryl- or thriarylmethane dyes
    • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
    • C09B11/10—Amino derivatives of triarylmethanes
    • 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)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials For Photolithography (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Optical Filters (AREA)
  • Liquid Crystal (AREA)

Abstract

A coloring composition capable of forming a coloring cured film with excellent heat resistance, excellent solvent resistance and inhibited migrating property is provided. The coloring composition comprises (A) a coloring agent and (B) a polymerizable compound. The (A) coloring agent comprises polymers of unsaturated monomers comprising unsaturated monomers (a1) shown as a formula (1). In the formula (1), R1 to R6 independently represent hydrogen, C1-C8 alkyl, phenyl or a group with alkene unsaturated groups, R7 to R8 independently represent C1-C8 alkyl or chlorine, R9 to R10 independently represent hydrogen, C1-C8 alkyl or chlorine, l and m independently represent an integer from 0 to 4, at least one of R1 to R6 is a group with alkene unsaturated groups, and the group with alkene unsaturated groups is CH2=CR11-COO-X-group (wherein R11 is hydrogen or methyl, and X is C5-C12 divalent alkyl).

Description

Coloured composition, color solidification film and display element
Technical field
The present invention relates to coloured composition, color solidification film and display element, in more detail, relate to for the formation of the coloured composition of the color solidification film used in transmission-type or reflection-type color liquid crystal display element, solid-state imager, organic EL display element, Electronic Paper etc., the color solidification film using this coloured composition to be formed and the display element with this color solidification film.
Background technology
There will be a known when using colored radiation-sensitive composition to manufacture colored filter, on substrate coating pigment decentralized colored radiation-sensitive composition, carry out drying after, irradiate radioactive ray (below claim " exposure ") with desired pattern form to dry coating and develop, the method obtaining each color pixel thus (such as can see patent documentation 1 ~ 2.)。Also there will be a known (such as can see patent documentation 3 by the method for the optical polymerism composition formation black matrix" being dispersed with carbon black.)。In addition, also there will be a known and use pigment-dispersing type colored resin composition, obtained the method for each color pixel by ink-jetting style (such as can see patent documentation 4).
In order to the high-precision refinement of the high brightness and high color purity or solid-state imager that realize display element, known use dyestuff is effective as colorant.But know, generally speaking, compared with pigment, the thermotolerance of dyestuff, poor solvent resistance, this is the strong dyestuff expecting a kind of thermotolerance of exploitation, excellent solvent resistance just.For this reason, as the dyestuff that thermotolerance etc. is excellent, existing people proposes to use such as triaryl methane compounds (such as can see patent documentation 5,6).
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:PCT applies for No. 2010/123071 Publication
Patent documentation 6: Japanese Unexamined Patent Publication 2012-017425 publication
Summary of the invention
But, even if use the triaryl methane compounds recorded in patent documentation 5 ~ 6, also cannot say it is fully to meet the requirement to thermotolerance, solvent resistance.In addition, the dyestuff in the pixel of colored pattern can to the pixel, diaphragm etc. of other adjacent colors not containing the cured film of colorant carry out colour migration move (below be also called " migration property ".), thus there is the problem that the display characteristic of display element is low, with regard to this problem, there is above-mentioned triaryl methane compounds might not make us situation about being fully satisfied with.Therefore, even if when using triaryl methane compounds as colorant, still strongly expecting to have and a kind ofly can form thermotolerance, the dye compositions of color solidification film that excellent solvent resistance and migration property are inhibited.
Therefore, the object of the present invention is to provide a kind ofly can form thermotolerance, the coloured composition of color solidification film that excellent solvent resistance and migration property are inhibited.In addition, the color solidification film using this coloured composition to be formed is provided provide and there is the display element that this cured film.
Present inventor conducts in-depth research, and found that, by using specific polymkeric substance as colorant, can solve the problem.
That is, the invention provides a kind of coloured composition, this coloured composition contains (A) colorant and (B) polymerizable compound,
Wherein, (A) colorant contains the polymkeric substance (below also referred to as " in line with toner " (colorant of the present invention)) of unsaturated monomer, described unsaturated monomer contains the unsaturated monomer (a1) with the structure that following formula (1) represents
(chemical formula 1)
(in formula (1),
R 1~ R 6represent the alkyl of hydrogen atom, carbon number 1 ~ 8, phenyl independently of each other or there is the group of alkene unsaturated group,
Ar represents aromatic hydrocarbyl,
R 7~ R 8represent alkyl or the chlorine atom of carbon number 1 ~ 8 independently of each other,
R 9~ R 10represent alkyl or the chlorine atom of hydrogen atom, carbon number 1 ~ 8 independently of each other,
L and m represents the integer of 0 ~ 4 independently of each other.
Wherein, R 1~ R 6in at least 1 for having the group of alkene unsaturated group, this group with alkene unsaturated group is CH 2=CR 11-COO-X-group (R 11represent hydrogen atom or methyl, X represents the divalent alkyl of carbon number 5 ~ 12).〕
In addition, the invention provides the color solidification film using above-mentioned coloured composition to be formed and the display element with this color solidification film.Here, " color solidification film " refers in display element, solid-state imager each color pixel, black matrix" (matrix), black interval part (spacer, or title " chock insulator matter ") etc. that use.
Use coloured composition of the present invention, thermotolerance can be formed, color solidification film that excellent solvent resistance and migration property are inhibited.
Therefore, coloured composition of the present invention can be used for making the solid-state imagers such as display element, cmos image sensor such as color liquid crystal display device, organic EL display element, Electronic Paper very well.
Embodiment
The present invention is described in detail below.
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 in line with toner.
First the unsaturated monomer (a1) (being also called for short " unsaturated monomer (a1) " below) with the structure that following formula (1) represents formed in line with toner is described.Unsaturated monomer (a1) has various resonant structure, but in this manual, these resonant structures is regarded as the structure equal with the unsaturated monomer with the structure that following formula (1) represents.
(chemical formula 2)
(in formula (1),
R 1~ R 6represent the alkyl of hydrogen atom, carbon number 1 ~ 8, phenyl independently of each other or there is the group of alkene unsaturated group,
Ar represents aromatic hydrocarbyl,
R 7~ R 8represent alkyl or the chlorine atom of carbon number 1 ~ 8 independently of each other,
R 9~ R 10represent alkyl or the chlorine atom of hydrogen atom, carbon number 1 ~ 8 independently of each other,
L and m represents the integer of 0 ~ 4 independently of each other.
Wherein, R 1~ R 6in at least 1 for having the group of alkene unsaturated group, this group with alkene unsaturated group is CH 2=CR 11-COO-X-group (R 11represent hydrogen atom or methyl, X represents the divalent alkyl of carbon number 5 ~ 12.)。〕
R in above-mentioned formula (1) 1~ R 10in the alkyl of carbon number 1 ~ 8 can be straight chain, also can be side chain.As object lesson, such as, can be methyl, ethyl, n-pro-pyl, isopropyl, normal-butyl, isobutyl, sec-butyl, the tert-butyl group, n-pentyl, sec-amyl, neopentyl, n-hexyl, n-heptyl, n-octyl etc.Wherein, as R 1~ R 6in the alkyl of carbon number 1 ~ 8, be preferably the alkyl of carbon number 1 ~ 4, be especially preferably methyl or ethyl.In addition, as R 7~ R 10in the alkyl of carbon number 1 ~ 8, be preferably the alkyl of carbon number 1 ~ 4, be especially preferably methyl.
At R 1~ R 6in have in the group of alkene unsaturated group, the number of alkene unsaturated group can be 1, also can be more than 2, but preferably has 1 alkene unsaturated group.As alkene unsaturated group, such as, it can be the group with (methyl) acryloyl group, ethenyl aromatic yl, ethyleneoxy, allyl etc.Wherein, consider from reactive angle, be preferably (methyl) acryloyl group.
Unsaturated monomer (a1) is R 1~ R 6in at least 1 group with alkene unsaturated group, this group with alkene unsaturated group is CH 2=CR 11-COO-X-group.
Here, R 11be hydrogen atom or methyl, can suitably select.In addition, X represents the divalent alkyl of carbon number 5 ~ 12.
As the divalent alkyl of the carbon number 5 ~ 12 represented by X, can be the divalent aliphatic alkyl of carbon number 5 ~ 12, divalent ester ring type alkyl, divalent aromatic hydrocarbyl.
As the aliphatic alkyl of carbon number 5 ~ 12, can be alkane two base of carbon number 5 ~ 12, can be straight chain, also can be side chain.As object lesson, such as, can be pentane-1,5-bis-base, hexane-1,6-bis-base, hexane-1,5-bis-base, hexane-1,2-bis-base, heptane-1,7-bis-base, octane-1,8-bis-base, decane-1,10-bis-base, dodecane-1,12-bis-base etc.Wherein, be preferably alkane two base of carbon number 5 ~ 10, be more preferably alkane two base of carbon number 6 ~ 8, be especially preferably hexane-1,6-bis-base, octane-1,8-bis-base.
As the divalent ester ring type alkyl of carbon number 5 ~ 12, it can be the cycloalkylidene of carbon number 5 ~ 12.As object lesson, such as, can be cyclopentylene, cyclohexylidene, sub-ring octyl group etc.Wherein, be preferably the cycloalkylidene of carbon number 5 ~ 8, be more preferably the cycloalkylidene of carbon number 6 ~ 8, be especially preferably cyclohexylidene.Cyclohexylidene has Isosorbide-5-Nitrae-cyclohexylidene, 1,3-cyclohexylidene, 1,2-cyclohexylidene, considers from sterically hindered little angle, is preferably Isosorbide-5-Nitrae-cyclohexylidene.
As the divalent aromatic hydrocarbyl of carbon number 5 ~ 12, it can be the arlydene of carbon number 6 ~ 12.As object lesson, such as, can be phenylene, naphthylene, biphenylene etc.Wherein, be preferably the arlydene of carbon number 6 ~ 10, be more preferably phenylene, naphthylene.In addition, phenylene has ortho position body, a position body and contraposition body, considers from sterically hindered little angle, is preferably contraposition body.In naphthylene, preferred Isosorbide-5-Nitrae-naphthylene.
In above-mentioned X, the divalent aliphatic alkyl of preferred carbon number 5 ~ 12, the divalent ester ring type alkyl of carbon number 5 ~ 12, more preferably the divalent ester ring type alkyl of carbon number 5 ~ 12.
At R 1~ R 6in any one when being the group with alkene unsaturated group, preferred R 1~ R 6in 1 or 2 be CH 2=CR 11-COO-X-group, more preferably R 1~ R 6in 1 be CH 2=CR 11-COO-X-group.
In addition, the CH that has of unsaturated monomer (a1) 2=CR 11-COO-X-group and other groups with alkene unsaturated group also can be aggregated in more than 2, more preferably have 1 CH 2=CR 11-COO-X-group.
As the aromatic hydrocarbyl in Ar, be preferably carbon number 6 ~ 20 so that be 6 ~ 10 aromatic hydrocarbyl.As object lesson, such as, it can be the group removing 2 ~ 4 hydrogen atoms from benzene, naphthalene, biphenyl or anthracene.Wherein, the group removing 2 ~ 4 hydrogen atoms from benzene or naphthalene is preferably.
As l and m, be preferably 0 or 1.
Unsaturated monomer (a1) separately or can mix two or more and use.The object lesson of structure that represents of display type (1) below.
(chemical formula 3)
Being preferably in line with toner can the multipolymer of unsaturated monomer of ethylenically unsaturated monomers (also claiming " unsaturated monomer (a2) " below) of copolymerization containing other beyond unsaturated monomer (a1).As the example of this unsaturated monomer (a2), can be such as there is the ethylenically unsaturated monomers of more than 1 carboxyl, N-substituted maleimide amine, aromatic ethenyl compound, (methyl) acrylate, vinyl ether, polymer molecular chain end on there is the macromonomer etc. of list (methyl) acryloyl group.Unsaturated monomer (a2) separately or can mix two or more and use.
As the above-mentioned ethylenically unsaturated monomers with more than 1 carboxyl, 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.
In addition, as above-mentioned N-substituted maleimide amine, such as, can be N-phenylmaleimide, N-N-cyclohexylmaleimide etc.
In addition, as above-mentioned aromatic ethenyl compound, can be such as styrene, α-methyl styrene, 4-Vinyl phenol, to hydroxy-alpha-methyl styrene, to vinylbenzyl glycidyl ether, acenaphthylene etc.
In addition, as above-mentioned (methyl) acrylate, it can be such as (methyl) alkyl acrylate of (methyl) acrylate methyl esters, (methyl) n-butyl acrylate, (methyl) 2-EHA and so on
(methyl) acrylic acid hydroxy alkyl ester of (methyl) acrylic acid 2-hydroxyl ethyl ester, (methyl) acrylic acid 2-hydroxypropyl acrylate and so on,
(methyl) acrylate of the unsaturated alcohol of (methyl) vinyl acrylate, (methyl) allyl acrylate and so on,
(methyl) benzyl acrylate of (methyl) phenyl acrylate, (methyl) benzyl acrylate and so on,
(methyl) acrylate of the polyvalent alcohol of single (methyl) acrylate of polyglycol (degree of polymerization 2 ~ 10) methyl ether (methyl) acrylate, polypropylene glycol (degree of polymerization 2 ~ 10) methyl ether (methyl) acrylate, polyglycol (degree of polymerization 2 ~ 10), single (methyl) acrylic acid of polypropylene glycol (degree of polymerization 2 ~ 10), glycerine list (methyl) acrylate and so on
(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 and so on (methyl) acrylate with alicyclic hydrocarbon radical,
Fragrant and mellow (methyl) acrylate of ethylene-oxide-modified (methyl) acrylate of (methyl) acrylic acid 4-hydroxy phenyl ester, p-cumylphenol and so on, etc.
As (methyl) acrylate, (methyl) acrylate had containing oxygen saturation heterocyclic radical also can be used.Here, " containing oxygen saturation heterocyclic radical " refers to containing oxygen atom as the heteroatomic saturated heterocyclyl forming heterocycle, and the atomicity preferably forming ring is the cyclic ether group of 3 ~ 7.As cyclic ether group, can be Oxyranyle (oxiranyl), oxetanylmethoxy (oxetanyl), 3,4-epoxycyclohexyl, tetrahydrofuran base etc., wherein, consider from reactive angle, be preferably Oxyranyle, oxetanylmethoxy, 3,4-epoxycyclohexyls.
As (methyl) acrylate had containing oxygen saturation heterocyclic radical, can be such as (methyl) glycidyl acrylate, (methyl) acrylate with Oxyranyle of (methyl) acrylic acid 2-hydroxyethyl glycidol ether, (methyl) acrylic acid 2-hydroxypropyl glycidol ether, (methyl) acrylic acid 3-hydroxypropyl glycidol ether, (methyl) acrylic acid 4-hydroxyl butyl glycidyl ether, polyethylene glycol-propylene glycol (methyl) glycidyl ether and so on
(methyl) acrylate with 3,4-epoxycyclohexyl of (methyl) acrylic acid 3,4-epoxycyclohexyl-methyl ester and so on,
(methyl) acrylate with oxetanylmethoxy of 3-((methyl) acryloyloxymethyl) oxetanes, 3-((methyl) acryloyloxymethyl)-3-Ethyloxetane and so on,
(methyl) acrylate with tetrahydrofuran base of THFMA and so on, etc.
In addition, as above-mentioned vinyl ether, such as, can be vinyl acetate, cyclohexyl vinyl ether, isobornyl vinyl ether, three ring (5.2.1.0 2,6) decane-8-base vinyl ether, pentacyclopentadecandimethanol base vinyl ether, 3-(vinyloxy methyl)-3-Ethyloxetane etc.
In addition; having the macromonomer of list (methyl) acryloyl group as the above-mentioned end at polymer molecular chain, such as, can be the macromonomer at the end of polymer molecular chain with list (methyl) acryloyl group of polystyrene, poly-(methyl) methyl acrylate, poly-(methyl) n-butylacrylate, polysiloxane and so on.
Wherein, consider from thermotolerance, solvent resistance, migration property suppression, dispersed angle, in line with in toner, can the ethylenically unsaturated monomers (a2) of copolymerization as other, preferably containing (methyl) acrylate, more preferably containing being selected from (methyl) acrylate and at least a kind in (methyl) benzyl acrylate of having containing oxygen saturation heterocyclic radical.The thermotolerance in line with toner can be improved in this way, thus preferably.Have in (methyl) acrylate containing oxygen saturation heterocyclic radical, preferably there is (methyl) acrylate of at least a kind of group be selected from Oxyranyle, oxetanylmethoxy and 3,4-epoxycyclohexyl.In (methyl) benzyl acrylate, preferably (methyl) phenyl acrylate.
When having unsaturated monomer (a2) in line with toner, consider from thermotolerance, solvent resistance, migration property suppression, dispersed angle, the copolymerization ratios of unsaturated monomer (a2) is preferably with under type.
Namely, in line with the ratio p of the unsaturated monomer (a1) in all structural units of toner and the ratio r of unsaturated monomer (a2) with molar ratio computing, be preferably p/r=1/99 ~ 30/70, be more preferably p/r=2/98 ~ 25/75, be especially preferably p/r=3/97 ~ 20/80.
In addition, when use be selected to have containing at least a kind in (methyl) acrylate of oxygen saturation heterocyclic radical and (methyl) benzyl acrylate as unsaturated monomer (a2), consider from the angle of thermotolerance, solvent resistance, having in unsaturated monomer (a2) is preferably 5 ~ 45 % by mole containing (methyl) acrylate of oxygen saturation heterocyclic radical and the copolymerization ratios (s) of (methyl) benzyl acrylate, be more preferably 10 ~ 40 % by mole, be especially preferably 15 ~ 30%.
Can as required and containing negative ion in line with toner, with generally in electric neutrality.
As this anionoid, such as, can be halide ion, boron anion, phosphate anion, carboxylate anion, sulfate anion, organic sulfonic acid anion, nitrogen negative ion, methide anion etc.
As above-mentioned halide ion, can be fluoride ion, chloride ion, bromide ion, iodide ion etc.
In addition, as boron anion, such as, can be BF 4 -deng Inorganic Boron negative ion;
(CF 3) 4b -, (CF 3) 3bF -, (CF 3) 2bF 2 -, (CF 3) BF 3 -, (C 2f 5) 4b -, (C 2f 5) 3bF -, (C 2f 5) BF 3 -, (C 2f 5) 2bF 2 -, (CF 3) (C 2f 5) 2bF -, (C 6f 5) 4b -, ((CF 3) 2c 6h 3) 4b -, (CF 3c 6h 4) 4b -, (C 6f 5) 2bF 2 -, (C 6f 5) BF 3 -, (C 6h 3f 2) 4b -, B (CN) 4 -, B (CN) F 3 -, B (CN) 2f 2 -, B (CN) 3f -, (CF 3) 3b (CN) -, (CF 3) 2b (CN) 2 -, (C 2f 5) 3b (CN) -, (C 2f 5) 2b (CN) 2 -, (n-C 3f 7) 3b (CN) -, (n-C 4f 9) 3b (CN) -, (n-C 4f 9) 2b (CN) 2 -, (n-C 6f 13) 3b (CN) -, (CHF 2) 3b (CN) -, (CHF 2) 2b (CN) 2 -, (CH 2cF 3) 3b (CN) -, (CH 2cF 3) 2b (CN) 2 -, (CH 2c 2f 5) 3b (CN) -, (CH 2c 2f 5) 2b (CN) 2 -, (CH 2cH 2c 3f 7) 2b (CN) 2 -, (n-C 3f 7cH 2) 2b (CN) 2 -, (C 6h 5) 3b (CN) -, tetraphenylborate negative ion, four (single fluorophenyl) borate anion, four (difluorophenyl) borate anion, four (trifluorophenyl) borate anion, four (tetrafluoro phenyl) borate anion, four (pentafluorophenyl group) borate anion, four (trifluoromethyl phenyl) borate anion, four (tolyl) borate anion, four (xylyl) borate anion, (triphenyl, pentafluorophenyl group) borate anion, (three (pentafluorophenyl groups), phenyl) borate anion, the organoboron anion such as 13 hydrogen-7,8-bis-carbon 11-borates root negative ion (tridecahydride-7,8-dicarbaundecaborate anion) in addition, can also be Japanese Unexamined Patent Publication 10-195119 publications, Japanese Unexamined Patent Publication 2010-094807 publication, Japanese Unexamined Patent Publication 2006-243594 publication, Japanese Unexamined Patent Publication 2002-341533 publication, the boron anion recorded in Japanese Unexamined Patent Publication 8-015521 publication etc.
In addition, as phosphate anion, such as, can be HPO 4 2-, PO 4 3-, PF 6 -deng inorganic phosphate negative ion;
(C 2f 5) 2pF 4 -, (C 2f 5) 3pF 3 -, ((CF 3) 2cF) 2pF 4 -, ((CF 3) 2cF) 3pF 3, (n-C 3f 7) 2pF 4 -, (n-C 3f 7) 3pF 3 -, (n-C 4f 9) 3pF 3 -, (C 2f 5) (CF 3) 2pF 3 -, ((CF 3) 2cFCF 2) 2pF 4 -, ((CF 3) 2cFCF 2) 3pF 3 -, (n-C 4f 9) 2pF 4 -, (n-C 4f 9) 3pF 3 -, (C 2f 4h) (CF 3) 2pF 3 -, (C 2f 3h 2) 3pF 3 -, (C 2f 5) (CF 3) 2pF 3 -, octylphosphonic acid negative ion, dodecylphosphoric acid negative ion, octadecyl phosphate anion, phosphenylic acid negative ion, the organic phosphoric acid negative ion such as nonyl phenyl phosphate anion.
In addition, as carboxylate anion, such as, can be CH 3cOO -, C 2h 5cOO -, C 6h 5cOO -deng, can be the carboxylate anion recorded in Japanese Unexamined Patent Publication 2009-265641 publication, Japanese Unexamined Patent Publication 2008-096680 publication etc. in addition.
In addition, as sulfate anion, such as, can be sulfate anion, sulfite anion.
As organic sulfonic acid anion, such as, can be the alkyl sulfonic acid negative ion such as methane-sulforic acid negative ion, ethyl sulfonic acid negative ion, trifluoromethanesulfonic acid negative ion, nine fluorine fourth sulfonic acid anions;
Benzene sulfonate anion, benzenedisulfonic acid negative ion, p-toluenesulfonic acid negative ion, to aryl sulfonic acid negative ion such as trifluoromethane sulfonic acid negative ion, phenyl-pentafluoride sulfonic acid anion, naphthalene sulfonic acids negative ion, naphthalenedisulfonic acid negative ion; 2-(methyl) acryloxy-1,1,2,2-tetrafluoro ethyl sulfonic acid negative ion, 2-(4-ethenylphenyl oxygen base)-1,1,2,2-tetrafluoro ethyl sulfonic acid negative ion and the organic sulfonic acid anion recorded in PCT application No. 2011/037195 Publication, Jap.P. No. 3736221 instructions, Japanese Unexamined Patent Publication 2011-070172 publication etc.
In addition, as nitrogen negative ion, such as, can be ((CN) 2n) -, ((FSO 2) 2n) -, ((FSO 2) N (CF 3sO 2)) -, ((CF 3sO 2) 2n) -, ((FSO 2) N (CF 3cF 2sO 2)) -, ((FSO 2) N{ (CF 3) 2cFSO 2) -, ((FSO 2) N (CF 3cF 2cF 2sO 2)) -, ((FSO 2) N (CF 3cF 2cF 2cF 2sO 2)) -, ((FSO 2) N{ (CF 3) 2cFCF 2sO 2) -, ((FSO 2) N{CF 3cF 2(CF 3) CFSO 2) -, ((FSO 2) N{ (CF 3) 3cSO 2) -deng, and the nitrogen negative ion recorded in Japanese Unexamined Patent Publication 2011-133844 publication, Japanese Unexamined Patent Publication 2011-116803 publication, Japanese Unexamined Patent Publication 2010-090341 publication.
In addition, as methide anion, such as, can be (CF 3sO 2) 3c -, (CF 3cF 2sO 2) 3c -, ((CF 3) 2cFSO 2) 3c -, (CF 3cF 2cF 2sO 2) 3c -, (CF 3cF 2cF 2cF 2sO 2) 3c -, ((CF 3) 2cFCF 2sO 2) 3c -, (CF 3cF 2(CF 3) CFSO 2) 3c -, ((CF 3) 3cSO 2) 3c -, (FSO 2) 3c -deng and at Japanese Unexamined Patent Publication 2011-145540 publication, United States Patent (USP) the 5th, the methide anion recorded in 554, No. 664 instructionss, Japanese Unexamined Patent Publication 2005-309408 publication, Japanese Unexamined Patent Publication 2004-085657 publication, Japanese Unexamined Patent Application Publication 2010-505787 publications etc.
The weight-average molecular weight (Mw) of the polystyrene conversion recorded in line with toner gel permeation chromatography (being called for short GPC below) (stripping solvent: tetrahydrofuran) is generally 1,000 ~ 100,000, be preferably 3,000 ~ 50,000.In this way, the suppression of thermotolerance, solvent resistance, migration property, film covering characteristics, electrical characteristics, pattern form, resolution can be made to become good.
In addition, the weight-average molecular weight in line with toner (Mw) 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.Mn mentioned here is the number-average molecular weight of the polystyrene conversion recorded with GPC (stripping solvent: tetrahydrofuran).
Other colorants that coloured composition of the present invention also can mix beyond in line with toner use.As other colorants, without particular restriction, can suitably select color, material according to purposes.As other colorants, can be in line with toner beyond pigment, dyestuff, other colorants can use alone or in combination of two kinds or more.Wherein, consider from the angle 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, can be at Colour Index (C.I.; The Society of Dyers and Colourists corporation issues) in be categorized as the compound of pigment, that is, the compound of following attached dye index (C.I.) number.
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, paratonere 264;
C.I. the viridine green such as pigment Green 7, C.I. pigment green 36, C.I. naphthol green 58;
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 12 9, C.I. pigment yellow 13 8, 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, can be the mordant pigment recorded in Japanese Unexamined Patent Publication 2001-081348 publication, Japanese Unexamined Patent Publication 2010-026334 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.
Wherein, preferably containing at least a kind that is selected from blue pigment and violet pigment, more preferably containing being selected from C.I. pigment blue 15: 6 and C.I. pigment Violet 23 at least a kind.Thereby, it is possible to easily form thermotolerance and excellent solvent resistance and the color solidification film that is inhibited of migration property, especially blue pixel.
In addition, as dyestuff, preferred triarylmethane dye, anthraquinone dye, azo dyes etc.More specifically, can be the organic dyestuff recorded in 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.
In the present invention, other pigment mixed arbitrarily can be carried out refining rear use by the combination of recrystallization method, reprecipitation method, solvent cleaning method, sublimed method, vaccum heating method or these methods.In addition, its particle surface also can be carried out modified use with resin by these pigment as requested.As the resin to pigment particles modifying surface, such as, can be the Vehicle resins or commercially available various pigment dispersion resins recorded in Japanese Unexamined Patent Publication 2001-108817 publication.As the resin-coating method of carbon blacksurface, such as, can adopt the method recorded in Japanese Unexamined Patent Publication 9-71733 publication, Japanese Unexamined Patent Publication 9-95625 publication, Japanese Unexamined Patent Publication 9-124969 publication etc.In addition, organic pigment uses after primary particle being carried out miniaturization by so-called salt mill method.As the method for salt mill, such as, can adopt method disclosed in Japanese Unexamined Patent Publication 8-179111 publication.
In addition, in the present invention, while other colorants using mixing arbitrarily, also known spreading agent and dispersing aid can be added.As known spreading agent, can be such as polyurethanes spreading agent, polyethyleneimine: amine spreading agent, polyoxyethylene alkyl ether class spreading agent, polyoxyethylene alkyl phenyl ether class spreading agent, polyethylene glycol di class spreading agent, fatty acid esters of sorbitan class spreading agent, polyesters spreading agent, acrylic dispersants etc., in addition, as dispersing aid, it can be pigment derivative etc.
Above-mentioned spreading agent can obtain from commercial channels, such as, can be listed below respectively: as Disperbyk-2000, Disperbyk-2001, BYK-LPN 6919, the BYK-LPN 21116, BYK-LPN 22102 (above is Bi Ke chemistry (BYK) Products) etc. of acrylic dispersants; As Disperbyk-161, Disperbyk-162, Disperbyk-165, Disperbyk-167, Disperbyk-170, Disperbyk-182 (being Bi Ke chemistry (BYK) Products above), Solsperse 76500 (Lubrizol Corp.'s product) etc. of polyurethanes spreading agent; As the Solsperse-24000 (Lubrizol Corp.'s product) etc. of polyethyleneimine: amine spreading agent; As Ajisper-PB821, Ajisper-PB822, Ajisper-PB880, Ajisper-PB881 (being Ajinomoto Fine-Techno Products above) etc. of polyesters spreading agent; And BYK-LPN21324 (Bi Ke chemistry (BYK) Products).
In addition, as pigment derivative, specifically, can be the sulfonic acid etc. of copper phthalocyanine, diketopyrrolopyrrolecocrystals, quinophthalone.
In the present invention, other colorants separately or can mix two or more and use.
Relative to the total content of colorant, containing of other colorants is proportional preferably at below 70 quality %, more preferably at below 50 quality %.To its lower limit without particular restriction, at more than 0.01 quality %.
From forming thermotolerance, solvent resistance, migration property suppresses and the black matrix" of brightness is high, excitation is excellent pixel or light-proofness excellence, the angle of black interval part are considered, (A) colorant in the solid constituent of coloured composition usually account for 5 ~ 70 quality % containing proportional, be preferably 10 ~ 60 quality %.Here, solid constituent refers to the composition beyond solvent described later.
-(B) polymerizable compound-
In the present invention, polymerizable compound refers to the compound with more than 2 polymerizable groups.As polymerizable groups, such as, can be alkene unsaturated group, Oxyranyle, oxetanylmethoxy, N-alkoxy methyl amino etc.In the present invention, preferably use the compound with more than 2 (methyl) acryloyl groups or the compound with more than 2 N-alkoxy methyl amino as polymerizable compound.
As the object lesson of compound with more than 2 (methyl) acryloyl groups, multifunctional (methyl) acrylate that can be 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.
Here, as aliphatic polyhydroxy compound, can be such as the divalent aliphatic polyhydroxy compound of ethylene glycol, propylene glycol, polyglycol, polypropylene glycol and so on, aliphatic polyhydroxy compounds more than 3 valencys of glycerine, trimethylolpropane, pentaerythrite, dipentaerythritol and so on.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 acid anhydrides, it can be 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.
In addition, as caprolactone modification multifunctional (methyl) acrylate, such as, can be the middle compound recorded in paragraph (0015) ~ (0018) of Japanese Unexamined Patent Publication 11-44955 publication.As above-mentioned alkylene oxide modification multifunctional (methyl) acrylate, can be such as by bisphenol-A two (methyl) acrylate of at least a kind of modification be selected from oxirane and epoxypropane, by isocyanuric acid three (methyl) acrylate of at least a kind of modification be selected from oxirane and epoxypropane, by trimethylolpropane tris (methyl) acrylate of at least a kind of modification be selected from oxirane and epoxypropane, by pentaerythrite three (methyl) acrylate of at least a kind of modification be selected from oxirane and epoxypropane, by pentaerythrite four (methyl) acrylate of at least a kind of modification be selected from oxirane and epoxypropane, by dipentaerythritol five (methyl) acrylate of at least a kind of modification be selected from oxirane and epoxypropane, by dipentaerythritol six (methyl) acrylate etc. of at least a kind of modification be selected from oxirane and epoxypropane.
In addition, as the compound with more than 2 N-alkoxy methyl amino, such as, can be the compound etc. with melamine structure, benzoguanamine structure or urea structure.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, and this concept comprises melamine, benzoguanamine or their condensation product.As the object lesson of compound 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.
In these polymerizable compounds, multifunctional (methyl) acrylate that aliphatic polyhydroxy compound preferably more than 3 valencys and (methyl) acrylic acid react and obtains, caprolactone modification multifunctional (methyl) acrylate, 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 '-four (alkoxy methyl) benzoguanamine.From thermotolerance, solvent resistance, migration property suppresses good, and the intensity of dyed layer is high, the surface smoothness of dyed layer is excellent, and not easily scumming on the substrate in unexposed portion and on light shield layer, the angle that film remains etc. is considered, especially the trimethylolpropane triacrylate in multifunctional (methyl) acrylate that the aliphatic polyhydroxy compound preferably more than 3 valencys and (methyl) acrylic acid react and obtains, pentaerythritol triacrylate, Dipentaerythritol Pentaacrylate, dipentaerythritol acrylate, there is the compound that pentaerythritol triacrylate in multifunctional (methyl) acrylate of carboxyl and succinic anhydride react and obtain, the compound that Dipentaerythritol Pentaacrylate and succinic anhydride react and obtain.
In the present invention, (B) polymerizable compound separately or can mix two or more and uses.
Relative to (A) colorant 100 mass parts, the content of (B) polymerizable compound in the present invention is preferably 10 ~ 1,000 mass parts, is more preferably 20 ~ 700 mass parts, is especially preferably 100 ~ 500 mass parts.In this way, thermotolerance, solvent resistance, migration property suppress to become good, and curability, alkali-developable improve further, can suppress to occur on the substrate in unexposed portion or on light shield layer that dirty version, film are residual etc. with high level.-(C) binder resin-
As (C) binder resin in the present invention, without particular restriction, but preferably there is the resin of the acidic functionality such as carboxyl, phenolic hydroxyl group.Wherein, preferably have the polymkeric substance (below also referred to as " carbonyl bearing polymer ") of carboxyl, can be such as the ethylenically unsaturated monomers (below also referred to as " unsaturated monomer (c1) ") with more than 1 carboxyl can the multipolymer of ethylenically unsaturated monomers (below also referred to as " unsaturated monomer (c2) ") of copolymerization with other.
As unsaturated monomer (c1), 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 (c1) separately or can mix two or more and use.
In addition; as unsaturated monomer (c2), can be such as the above-mentioned part about unsaturated monomer (a2) pass the imperial examinations at the provincial level exemplify the ethylenically unsaturated monomers with more than 1 carboxyl, N-substituted maleimide amine, aromatic ethenyl compound, (methyl) acrylate, vinyl ether, there is at polymer molecule chain end the macromonomer etc. of list (methyl) acryloyl group.As object lesson, it can be material same as described above.
Unsaturated monomer (c2) separately or can mix two or more and use.
In the multipolymer of unsaturated monomer (c1) with unsaturated monomer (c2), the copolymerization ratios of the unsaturated monomer (c1) in this multipolymer is preferably 5 ~ 50 quality %, is more preferably 10 ~ 40 quality %.By making unsaturated monomer (c1) copolymerization within the scope of this, the coloured composition of alkali-developable and excellent storage stability can be obtained.
As the object lesson of unsaturated monomer (c1) with the multipolymer of unsaturated monomer (c2), such as, it can be 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.
In the multipolymer of unsaturated monomer (c1) with unsaturated monomer (c2), as preferred mode, can containing having containing the multipolymer (below also referred to as " specific copolymer ") of oxygen saturation heterocyclic radical as unsaturated monomer (c2) (methyl) acrylate.
In addition; in the present invention; as 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 on side chain there is the polymerism unsaturated links such as (methyl) acryloyl group carbonyl bearing polymer as binder resin.
As the object lesson of carbonyl bearing polymer on side chain with polymerism unsaturated links such as (methyl) acryloyl groups, can be such as react with the polymerizable unsaturated compound with Oxyranyle containing the multipolymer of the monomer of unsaturated carboxylic acid and obtain multipolymer,
Containing unsaturated carboxylic acid and have multipolymer that the multipolymer of monomer of polymerizable unsaturated compound of Oxyranyle and unsaturated carboxylic acid react and obtain,
Containing unsaturated carboxylic acid and the polymkeric substance that there is the multipolymer of monomer of polymerizable unsaturated compound of hydroxyl and unsaturated isocyanate compound and be obtained by reacting.
The weight-average molecular weight (Mw) of the polystyrene conversion that the binder resin gel permeation chromatography (being called for short GPC below) (stripping solvent: tetrahydrofuran) in the present invention records is generally 1,000 ~ 100,000, be preferably 3,000 ~ 50,000.In this way, the residual film ratio of overlay film, pattern form, thermotolerance, electrical characteristics, resolution improve further, and can with the generation of dry foreign matter during high level suppression coating.
In addition, the weight-average molecular weight (Mw) of the binder resin 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.Mn mentioned here refers to the number-average molecular weight of the polystyrene conversion recorded with GPC (stripping solvent: tetrahydrofuran).
Binder resin in the present invention manufactures by known method, such as, control structure, Mw, Mw/Mn of binder resin by method disclosed in Japanese Unexamined Patent Publication 2003-222717 publication, Japanese Unexamined Patent Publication 2006-259680 publication, PCT application No. 2007/029871 Publication etc.
In the present invention, (C) binder resin separately or can mix two or more and uses.
In the present invention, relative to (A) colorant 100 mass parts, the content of (C) binder resin is generally 10 ~ 1,000 mass parts, is preferably 20 ~ 500 mass parts.In this way, alkali-developable, the storage stability of coloured composition, colorimetric properties can be improved further.
-Photoepolymerizationinitiater initiater-
Photoepolymerizationinitiater initiater can be added in coloured composition of the present invention.Coloured composition can be given thus with radiation-sensitive.The Photoepolymerizationinitiater initiater used in the present invention is the compound producing spike, and this spike can make (B) polymerizable compound start polymerization by the exposure under the radioactive ray such as visible ray, ultraviolet, far ultraviolet, electron ray, X ray.
As this Photoepolymerizationinitiater initiater, such as, can be thioxanthone compounds, acetophenone compound, united imidazole, triaizine compounds, O-acyl group oxime compound, salt compound, benzoin compound, benzophenone cpd, α-dione compounds, multinuclear naphtoquinone compounds, diazo-compounds, acid imide sulfonate compound etc.
In the present invention, Photoepolymerizationinitiater initiater separately or can mix 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 preferred Photoepolymerizationinitiater initiater of the present invention, as the object lesson of thioxanthone compounds, can be thioxanthones, CTX, 2-methyl thioxanthones, ITX, ITX, 2,4-bis-clopenthixal ketone, 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2,4-diisopropylthioxanthone etc.
In addition, as the object lesson of acetophenone compound, can be 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.
In addition, as the object lesson of united imidazole, can be 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.
In addition, when using bisglyoxaline as Photoepolymerizationinitiater initiater, consider from the angle that can improve sensitivity, preferably and use hydrogen donor." hydrogen donor " mentioned here refers to can to the compound of the free radical supply hydrogen atom produced by united imidazole by exposure.As hydrogen donor, such as, can be the mercaptan hydrogen donor, 4 such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, the amine hydrogen donors such as 4 '-bis-(dimethylamino) benzophenone, 4,4 '-bis-(diethylamino) benzophenone.In the present invention, these hydrogen donors separately or can mix two or more and use, but consider from the angle that can improve luminous sensitivity further, and preferably combine more than a kind mercaptan hydrogen donor and more than a kind amine hydrogen donor use.
In addition, as the object lesson of triaizine compounds, can be 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, two (the trichloromethyl)-s-triazine of 6-, 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 triaizine compounds of halomethyl.
In addition, as the object lesson of O-acyl group oxime compound, can be 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, NCI-831, NCI-930 (above is ADEKA Products), DFI-020, DFI-091 (above is Daito Chemix Products) etc. also can be used.
In the present invention, when using the Photoepolymerizationinitiater initiater beyond the united imidazoles such as acetophenone compound, can be used together sensitizer.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, 2,5-two (4-diethylamino benzal) cyclohexanone, 7-diethylamino-3-(4-diethylamino benzoyl) cumarin, 4-(diethylamino) chalcone etc.
In the present invention, relative to (B) polymerizable compound 100 mass parts, the content of Photoepolymerizationinitiater initiater is preferably 0.01 ~ 120 mass parts, is especially preferably 1 ~ 100 mass parts.In this way, curability and film covering characteristics can be improved further.
-solvent-
Coloured composition of the present invention contains other compositions of above-mentioned (A) and (B) composition and interpolation arbitrarily, but usually adds solvent and be modulated into liquid composition.
As above-mentioned solvent, form (A) and (B) composition of coloured composition, other compositions and do not react with these compositions, there is appropriate volatile solvent as long as can disperse or dissolve, just can suitable choice for use.
In this solvent, can be 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, pigment-dispersing, coating is angularly considered, preferably uses (many) 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 the present invention, solvent separately or can mix two or more and uses.
To the content of solvent without particular restriction, but the total concentration of each composition preferably beyond the desolventizing of coloured composition is 5 ~ 50 quality %, is more preferably 10 ~ 40 quality %.In this way, coloured composition dispersiveness, the colorant dispersion had good stability and coating can be obtained, having good stability.
-adjuvant-
Coloured composition of the present invention also can contain various adjuvant as required.
As adjuvant, such as, can be: the filling agent such as glass, aluminium oxide, the macromolecular compounds such as polyvinyl alcohol (PVA), poly-(fluoroalkyl) class, the surfactant such as fluorine surfactant, silicone 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 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)-5-chlorobenzotriazole, alkoxy benzophenone, the anti-agglutinant 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, the curing accelerators such as methacrylic acid 2-(0-(1 '-methyl propylene is amino) carboxyamino) ethyl ester, etc.In addition, as curing accelerator, the curing accelerator recorded in paragraph (0162) ~ (0169) of Japanese Unexamined Patent Publication 2012-088457 publication can be adopted.
Coloured composition of the present invention can adopt suitable method to modulate, and as its modulator approach, such as, can be method disclosed in Japanese Unexamined Patent Publication 2008-58642 publication, Japanese Unexamined Patent Publication 2010-132874 publication etc.When using dyestuff and pigment as colorant, the method as disclosed in Japanese Unexamined Patent Publication 2010-132874 publication can be adopted, namely, mix with the dispersible pigment dispersion etc. modulated separately after dyestuff being passed into the 1st filter, by the dye solution by the 1st filter, obtain coloured composition, again this coloured composition is passed into the 2nd filter, modulate thus.In addition, also can adopt with the following method, namely, after dyestuff, above-mentioned (B) composition and other component dissolves of using as required are passed into the 1st filter in solvent and by gained solution, solution by the 1st filter is mixed with the dispersible pigment dispersion modulated separately, obtain coloured composition, then this coloured composition is led in people the 2nd filter, modulate thus.In addition, also can adopt with the following method, namely, after dye solution being passed into the 1st filter, mix by the dye solution of the 1st filter and above-mentioned (B) composition and other compositions of using as required, dissolve, gained solution is passed into the 2nd filter, again the solution by the 2nd filter is mixed with the dispersible pigment dispersion modulated separately, obtain coloured composition, this coloured composition is passed into the 3rd filter, modulate thus.
color solidification film and manufacture method thereof
Color solidification film of the present invention coloured composition of the present invention is formed, and specifically, refers to each color pixel, black matrix", black interval part etc. that use in colored filter.
Below color solidification film used in colored filter and forming method thereof is described.
As the method manufacturing colored filter, the first, can following methods be enumerated.First, form light shield layer (black matrix") on a surface of a substrate as required, the part forming pixel is divided.Then, after being coated with the aqueous constituent of such as blue radiation-sensitive coloured composition of the present invention on the substrate, carry out prebake conditions, solvent evaporated, form film.Then, after via photomask this film being exposed, use alkaline developer to develop, dissolve the unexposed portion of removing film.Then, formed by rear baking with the pel array of the blue pixel patterns (color solidification film) of the sequence of regulation configuration.
Then, use each radiation-sensitive coloring resin composition of green or redness, carry out the coating of each radiation-sensitive coloured composition, prebake conditions, exposure, development and rear baking as described above, form green pixel array and red pixel array successively on the same substrate.Obtain the colored filter being configured with indigo plant, green, red trichromatic pel array on substrate thus.But in the present invention, the order forming each color pixel is not limited to said sequence.
In addition, black matrix" is formed by utilizing photoetching process to form desired pattern the metallic films such as the chromium formed in the mode of film with sputtering method, vapour deposition method, also can use the radiation-sensitive coloured composition being dispersed with black pigment, be formed in the same manner as forming the situation of above-mentioned pixel.
As the substrate used when forming colored filter, such as, can be glass, silicone, polycarbonate, polyester, aromatic polyamide, polyamidoimide, polyimide etc.
In addition, also can as requested in advance to the pre-treatment that these substrates are suitable for, described pre-treatment can be such as the chemical treatments, Cement Composite Treated by Plasma, ion plating, sputtering, gas-phase reaction method, vacuum evaporation etc. of carrying out with silane coupling agent etc.
When radiation-sensitive coloured composition is applied on substrate, the rubbing method that spraying process, rolling method, method of spin coating (spin-coating method), slot coating processes (slot coated method), stick coating method etc. are suitable can be adopted, especially preferably adopt spin-coating method or slot coating processes.
Prebake conditions is undertaken by combination drying under reduced pressure and heat drying usually.Drying under reduced pressure usually proceeds to pressure and reaches 50 ~ 200Pa.In addition, the condition of heat drying is generally and carries out 1 ~ 10 minute at 70 ~ 110 DEG C.
Coating thickness, with dried film thickness gauge, is generally 0.6 ~ 8 μm, is preferably 1.2 ~ 5 μm.
As the radioactive ray light source used when forming at least a kind of being selected from pixel and black matrix", can be 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, argon laser, YAG laser, XeCl excimers laser, N_2 laser.As exposure light source, also ultraviolet LED can be used.Optimal wavelength is at the radioactive ray of 190 ~ 450nm scope.
The exposure of radioactive ray is generally preferably 10 ~ 10,000J/m 2.
In addition, as above-mentioned alkaline developer, preference is as the aqueous solution of sodium carbonate, sodium bicarbonate, NaOH, potassium hydroxide, tetramethylammonium hydroxide, choline, 1,8-diazabicyclo-(5.4.0)-7-undecylene, 1,5-diazabicyclo-(4.3.0)-5-nonene etc.
Also the such as water-miscible organic solvent such as methyl alcohol, ethanol, surfactant etc. can be added in right amount in alkaline developer.In addition, usually wash after alkali development.
As development treatment method, spray development method, spray development method, immersion development method can be used, soak and put formula (covering liquid) development method etc.Development conditions preferably carries out 5 ~ 300 seconds at normal temperatures.
The condition of rear baking is generally carries out about 10 ~ 60 minutes at 180 ~ 280 DEG C.
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 manufacturing colored filter, the method obtaining each color pixel disclosed in Japanese Unexamined Patent Publication 7-318723 publication, Japanese Unexamined Patent Publication 2000-310706 publication etc. with ink-jetting style can be adopted.In the method, the next door having shade function concurrently is formed first on the surface of the substrate.Then, in the next door formed, spray the liquid composition of such as blue thermosetting coloured composition of the present invention with ink discharge device, carry out prebake conditions afterwards, evaporating solvent.Then, after as required to the exposure of this film, carry out rear baking and make it solidify, form blue pattern of pixels.
Then, use each thermosetting coloured composition of green or redness, form green pattern of pixels and red pattern of pixels as described above on the same substrate successively.Obtain the colored filter being configured with the trichromatic pattern of pixels of blue, green and red on substrate thus.But in the present invention, the order forming each color pixel is not limited to said sequence.
In addition, next door not only has shade function, and also play the effect making to be ejected into assorted thermosetting coloured composition in zoning not colour mixture, therefore, compared with the black matrix" used in above-mentioned first method, thickness is thick.So next door is formed with black radiation-ray sensitive composition usually.
Formed colored filter time use substrate, radioactive ray light source, in addition also have prebake conditions, rear baking method identical with above-mentioned first method with condition.Like this, the thickness of pixel formed by ink-jetting style and the height in next door are same degree.
After forming diaphragm as required in the pattern of pixels formed like this, form nesa coating by sputtering method.Also after formation nesa coating, distance piece can be formed further, make colored filter thus.Distance piece is formed with radiation-ray sensitive composition usually, but also can make the distance piece (black interval part) with light-proofness.In this case, use the colored radiation-sensitive composition being dispersed with black colorant, but coloured composition of the present invention also can well for the formation of this black interval part.
Coloured composition of the present invention all can use well when forming the arbitrary color solidification film such as each color pixel, black matrix", black interval part used in above-mentioned colored filter.
Colored filter containing the color solidification film of the present invention formed by this method has high brightness and colouring power, thus exceedingly useful to color liquid crystal display device, colour pick-up tube element, color sensor, organic EL display element, Electronic Paper etc.In addition, as long as display element described later has more than at least a kind color solidification film using coloured composition of the present invention to be formed.
display element
Display element of the present invention has color solidification film of the present invention.As display element, can be colour liquid crystal display device, organic EL display element, Electronic Paper etc.
The color liquid crystal display device with 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 colored filter on the substrate different from the driving substrate being configured with thin film transistor (TFT) (TFT), driving substrate clips liquid crystal layer toward each other with the substrate being formed with colored filter.And then also can adopt following structure: the substrate being formed with colored filter on the surface of driving substrate being configured with thin film transistor (TFT) (TFT) and the substrate being formed with ITO (indium oxide doped with tin) electrode clip liquid crystal layer toward each other.The structure of the latter has can improve aperture opening ratio extraordinarily, can be become clear, the advantage of the liquid crystal display cells of fine.In addition, when adopting the structure of the latter, black matrix" and black interval part can be formed in the substrate side being formed with colored filter and the either side be formed with in the substrate side of ITO.
The color liquid crystal display device with color solidification film of the present invention is except cold cathode fluorescent tube (CCFL:coldcathode fluorescent lamp), and can have with White LED is the back light unit of light source.As White LED, can be such as display predetermined colors in combination LED, green LED and blue led, the White LED of white light is obtained by colour mixture, combined blue LED, red LED and green-emitting phosphor, the White LED of white light is obtained by colour mixture, combined blue LED, red light-emitting phosphor and green-emitting phosphor body, the White LED of white light is obtained by colour mixture, the White LED of white light is obtained by the colour mixture of blue led and YAG fluorophor, combined blue LED, orange luminescence fluorophor and green-emitting phosphor body, the White LED of white light is obtained by colour mixture, combination ultraviolet LED, red light-emitting phosphor, green-emitting phosphor body and blue-light-emitting fluorescent material, the White LED etc. of white light is obtained by colour mixture.
The color liquid crystal display device with color solidification film of the present invention can adopt TN (twisted-nematic) type, STN (supertwist is to the row) liquid crystal mode that type, IPS (coplanar switch) type, VA (vertical orientated) type, OCB (optical compensation birefringence) type etc. are suitable.
In addition, the organic EL display element with color solidification film of the present invention can adopt suitable structure, such as, can be structure disclosed in Japanese Unexamined Patent Publication 11-307242 publication.
In addition, the Electronic Paper with color solidification film of the present invention can adopt suitable structure, such as, can be structure disclosed in Japanese Unexamined Patent Publication 2007-41169 publication.
(embodiment)
Further embodiments of the present invention are specifically described below by enumerating embodiment.But the present invention is not limited to following embodiment.
< is in line with the synthesis > of toner
Synthesis example 1
(synthesis of the unsaturated monomer (a1) that formula (1) represents)
To stirrer being housed and carrying out in advance adding three (dibenzalacetone) two palladium (0) 3.36g (3.67mmol), (±)-2 in the three-necked bottle of the 1L of nitrogen displacement, 2 '-bis-(diphenyl phosphine)-1,1 '-dinaphthalene 4.58g (7.36mmol) and undertaken degassed 1 by nitrogen bubble in advance, 2-dimethoxy-ethane 450mL, stirs 1 hour under nitrogen flowing, at 80 DEG C.Then, potpourri is cooled to less than 40 DEG C, sodium tert-butoxide 25.0g (0.260mol), 4-aminocyclohexanol 23.0g (0.200mol), 1-bromonaphthalene 38.0g (0.184mol) is added successively, stirred at reflux 3 hours when not making air enter in system.Afterwards, by reaction mixture cool to room temperature, with diatomite filtration, and clean insolubles with ethyl acetate, by gained solution Rotary Evaporators reduced pressure concentration.Refined residue obtained by silica gel column chromatography, obtain the maltosemalt sugar shape solid of 33.0g (0.137mol, yield 74%).Using this compound as (A1).
(chemical formula 4)
To being equipped with stirrer and carrying out in advance adding above-claimed cpd (A1) 12.0g (0.0497mol), triethylamine 7.55g (0.0746mol), DMAP 6.07g (0.0497mol), ethyl acetate 250mL in the three-necked bottle of the 500mL of nitrogen displacement, be cooled to interior temperature 5 DEG C.In this potpourri, dripping methacrylic chloride 6.24g (0.0259mol) when making interior temperature be no more than 10 DEG C, then, making interior temperature rise to room temperature, stirring 4 hours under nitrogen flowing, at same temperature.Afterwards, with water 300mL, saturated aqueous common salt 300mL successively cleaning reaction potpourri, after anhydrous sodium sulfate drying organic layer, 40g is evaporated to Rotary Evaporators.Then, add toluene 200g, be evaporated to 40g with Rotary Evaporators, then add toluene 85g.At room temperature in gained solution, add 4 successively, 4 '-bis-(diethylamino) benzophenone 20.5g (0.0633mol), 4-metoxyphenol 0.100g, phosphoryl chloride phosphorus oxychloride 8.05g (0.0518mol), stir 2 hours under nitrogen flowing, at 100 DEG C.Afterwards, reaction mixture is cooled to room temperature, removes most of toluene with Rotary Evaporators decompression distillation, be dissolved in chloroform 500mL by residue obtained, wash with water 500mL.With Rotary Evaporators, reduced pressure concentration is carried out to organic layer, in residue obtained, add acetone, make total weight be 400g.The solution of gained is here added drop-wise in diisopropyl ether 3200g, leaching gained solid.By this solid drying under reduced pressure 12 hours at 50 DEG C, obtain the coloring solid of 18.0g (0.0276mol, yield 56%).Using this compound as (A2).
(chemical formula 5)
Above-claimed cpd (A2) 9.00g (13.8mmol), two (fluoroform sulphonyl) imine lithium 5.94g (20.7mmol) is added in the 100mL conical flask that stirrer is housed, add ethyl acetate 90mL, ion exchange water 90mL again, stirred at ambient temperature about 2 hours.Then be separated removing water layer, organic layer ion exchange water 100mL is cleaned 3 times.After organic layer is under reduced pressure concentrated, by residue drying under reduced pressure 12 hours at 50 DEG C, obtain the compound 11.4g (12.7mmol, yield 92%) that following formula (A3) represents thus.Using this compound as (A3).
(chemical formula 6)
(synthesis of polymkeric substance (1))
Stirrer will be housed and backflow cooling tube and the abundant nitrogen displacement of the 100mL three-necked bottle of thermometer are installed, adding cyclohexanone 15.0g, be heated to interior temperature 80 ± 2 DEG C under nitrogen flowing.Mixing cpd (A3) 4.50g (5.02mmol), methyl methacrylate 6.00g (59.9mmol), methacrylic acid 4.50g (52.3mmol), polymerization initiator V-65 (medicine Products pure with light) 2.18g (8.79mmol), cyclohexanone 45.0g, be modulated into solution, in keeping, temperature is 80 ± 2 DEG C, spends within 2 hours, drop in three-necked bottle this solution pump.After dropping terminates, continue stirring 1 hour at the same temperature again.Then, 0.728g (2.93mmol) 2 will be made, 2 '-azo two (2,4-methyl pentane nitrile) (medicine Products pure with light, trade name V-65) solution that is dissolved in gained in cyclohexanone 1.13g once adds in reaction mixture, stir 30 minutes at the same temperature, continue to stir 30 minutes at 95 DEG C.Reactant liquor is cooled to room temperature, then is added dropwise in a large amount of hexane, obtain coloring solid, by this coloring solid drying under reduced pressure at 50 DEG C, obtain the polymkeric substance 13.9g (yield 93%) that following structural formula represents.The Mw of resulting polymers (1) is 5,100.Using this polymkeric substance as colorant (A-1).
(chemical formula 7)
Synthesis example 2
(synthesis of polymkeric substance (2))
Stirrer will be housed and backflow cooling tube and the abundant nitrogen displacement of the 100mL three-necked bottle of thermometer are installed, adding cyclohexanone 15.0g, be heated to interior temperature 70 ± 2 DEG C under nitrogen flowing.Mixing cpd (A3) 4.50g (5.02mmol), methyl methacrylate 3.00g (30.0mmol), glycidyl methacrylate 3.00g (21.1mmol), methacrylic acid 4.50g (52.3mmol), polymerization initiator V-65 (medicine Products pure with light) 2.02g (8.13mmol), cyclohexanone 45.0g, be modulated into solution, in keeping, temperature is 70 ± 2 DEG C, spends within 2 hours, drop in three-necked bottle this solution pump.After dropping terminates, continue stirring 1 hour at the same temperature again.Then, 0.728g (2.71mmol) 2 will be made, 2 '-azo two (2,4-methyl pentane nitrile) (medicine Products pure with light, trade name V-65) solution that is dissolved in gained in cyclohexanone 1.16g once adds in reaction mixture, stirs 3 hours at the same temperature.Reactant liquor is cooled to room temperature, then is added dropwise in a large amount of hexane, obtain coloring solid, by this coloring solid drying under reduced pressure at 50 DEG C, obtain the polymkeric substance 14.1g (yield 94%) that following structural formula represents.The Mw of resulting polymers (2) is 5,300.Using this polymkeric substance as colorant (A-2).
(chemical formula 8)
Synthesis example 3 ~ 11
Except in synthesis example 2 by except the kind of unsaturated monomer (a1) and unsaturated monomer (a2) and quantitative change are more shown in table 1, synthesized polymkeric substance (3) ~ (11) in the same manner as synthesis example 2.Using resulting polymers (3) ~ (11) as colorant (A-6) ~ (A-14).In addition, the amount of unsaturated monomer (a1) and the unsaturated monomer (a2) used is recorded in table 2 with material amount, and by the copolymerization ratios in line with the unsaturated monomer (a1) in toner with " p ", represent with " s " containing (methyl) acrylate of oxygen saturation heterocyclic radical and the copolymerization ratios of (methyl) benzyl acrylate with having in " r " and unsaturated monomer (a2) in line with the copolymerization ratios of the unsaturated monomer (a2) in toner.
Table 1
Table 2
In table 1 ~ 2, each composition is as follows.
(A3): above-claimed cpd (A3)
MMA: methyl methacrylate
GMA: glycidyl methacrylate
OXMA:3-(methacryloxymethyl)-3-Ethyloxetane
M100: methacrylic acid 3,4-epoxycyclohexyl ester (trade name CYCLOMER M100, DaicelChemical Products)
MAA: methacrylic acid
EHMA: 2-Ethylhexyl Methacrylate
PhMA: phenyl methacrylate
PMI:N-phenyl maleimide
VA: vinyl acetate
Relatively synthesis example 1
The C.I. Blue 7 of 5.00g (9.72mmol), two (fluoroform sulphonyl) imine lithium 4.19g (14.6mmol) is added in the 100mL conical flask that stirrer is housed, add chloroform 50mL, ion exchange water 25mL again, stirred at ambient temperature about 2 hours.Then, be separated removing water layer, clean organic layer 2 times with ion exchange water.After organic layer is under reduced pressure concentrated, by residue drying under reduced pressure 12 hours at 50 DEG C, obtain the compound 5.88g (7.78mmol, yield 80%) that following formula represents thus.Using gained compound as colorant (A-3).
(chemical formula 9)
Relatively synthesis example 2
The ClO of the compound that method synthesis following formula (A4) recorded in the embodiment with Jap.P. No. 3736221 instructions represents 4 -salt.Then, the ClO of compound except representing by following formula (A4) in the synthesis of above-mentioned polymkeric substance (1) 4 -salt replaces, beyond compound (A3), synthesizing, obtain polymkeric substance in the same manner as polymkeric substance (1).Using this polymkeric substance as colorant (A-5).
(chemical formula 10)
The synthesis > of < binder resin
Synthesis example 12
In the flask with cooling tube and stirrer, add propylene glycol methyl ether acetate 100 mass parts, carry out nitrogen displacement.Be heated to 80 DEG C, 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 is dripped at the same temperature with 1 hour, 2 '-azo two (2,4-methyl pentane nitrile) mixed solution of 6 mass parts, keep this temperature, be polymerized 2 hours.Then, by the temperature to 100 of reaction solution DEG C, polymerization 1 hour, obtains binder resin solution (solid component concentration 33 quality %) thus further.The Mw of gained binder resin is 12,200, Mn is 6,500.Using this binder resin as " binder resin (C1) ".The modulation > of < colourant solution
Modulation example 1
Colorant (A-1) 10 mass parts of above-mentioned gained is dissolved in propylene glycol monomethyl ether 90 mass parts, modulates colourant solution (A-1).
Modulation example 2
Colorant (A-2) 10 mass parts of above-mentioned gained is dissolved in propylene glycol monomethyl ether 90 mass parts, modulates colourant solution (A-2).
Modulation example 3
Colorant (A-3) 5 mass parts of above-mentioned gained is dissolved in propylene glycol monomethyl ether 95 mass parts, modulates colourant solution (A-3).
Modulation example 4
The C.I. Blue 7 of 5 mass parts is dissolved in propylene glycol monomethyl ether 95 mass parts, modulates colourant solution (A-4).
Modulation example 5 ~ 14
Except replacing except colorant (A-1) with colorant (A-5) ~ (A-14) in modulation example 1, modulate colourant solution (A-5) ~ (A-14) in the same manner as modulation example 1.
The modulation > of < dispersible pigment dispersion
Modulation example 15
Be used as the C.I. pigment blue 15 of 15 mass parts of colorant: 6, as BYK-LPN21116 (Bi Ke chemistry (BYK) Products) 12.5 mass parts (solid component concentration 40 quality %) of spreading agent, propylene glycol methyl ether acetate 72.5 mass parts as solvent, process with ball mill, modulate dispersible pigment dispersion (a-1).Modulation example 16
Be used as the C.I. naphthol green 58 of 15 mass parts of colorant, as BYK-LPN6919 (Bi Ke chemistry (BYK) Products) 8.3 mass parts (solid component concentration 60 quality %) of spreading agent, propylene glycol methyl ether acetate 76.7 mass parts as solvent, process with ball mill, modulate dispersible pigment dispersion (a-2).Modulation example 17
Be used as the C.I. pigment yellow 13 8 of 15 mass parts of colorant, as BYK-LPN21116 (Bi Ke chemistry (BYK) Products) 12.5 mass parts (solid component concentration 40 quality %) of spreading agent, propylene glycol methyl ether acetate 72.5 mass parts as solvent, process with ball mill, modulate dispersible pigment dispersion (a-3).Embodiment 1
Will as the dispersible pigment dispersion of (A) colorant (a-1) 30.5 mass parts, colourant solution (A-1) 23.0 mass parts, as binder resin (C1) solution (solid component concentration 33 quality %) 26.3 mass parts of (C) binder resin, as the dipentaerythritol acrylate of (B) polymerizable compound and potpourri (the Japanese chemical drug Products of Dipentaerythritol Pentaacrylate, trade name KAYARAD DPHA) 9.9 mass parts, as 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl) butane-1-ketone (the trade name Irgacure369 of Photoepolymerizationinitiater initiater, Ciba Specialty Chemicals's product) 1.8 mass parts and NCI-930 (ADEKA Products) 0.1 mass parts, as fluorine class surfactant Megafac F-554 (DIC Products) 0.05 mass parts and mix as the propylene glycol methyl ether acetate of solvent, modulate the blue colored composition (B-1) of solid component concentration 20 quality %.
evaluation of Heat Tolerance
Be formed with the SiO preventing sodion stripping blue colored composition (B-1) is applied to surface with spin coater 2after on the soda-lime glass substrate of film, carry out 2 minutes prebake conditions with the hot plates of 90 DEG C, form the film of thickness 2.5 μm.
Then, after this substrate cool to room temperature, via photomask, film is irradiated to the radioactive ray comprising each wavelength of 365nm, 405nm and 436nm with high-pressure sodium lamp, with 400J/m 2exposure expose.Afterwards, to these substrates with 1kgf/cm 2the developer solution be made up of the potassium hydroxide aqueous solution of 0.04 quality % of the development pressure injection 23 DEG C of (nozzle footpath 1mm), carries out spray development in 90 seconds.Then, clean this substrate with ultrapure water, after air-dry, carry out further toasting after 30 minutes in the cleaning oven of 200 DEG C, on substrate, form dot pattern thus.
For gained dot pattern, use the MCPD2000 that color analyzer (great mound electronics corporation produces) determine chromaticity coordinate value (x, y) in CIE color development system and values (Y) with illuminant-C, 2 degree of visuals field.
Then, aforesaid substrate being added at 230 DEG C baking after 90 minutes, measure chromaticity coordinate value (x, y) and values (Y), to look change, and the ⊿ E before and after additional baking *ab evaluates.Its result ， is Jiang ⊿ E *the average evaluation that ab value is less than 3.0 is "○", and more than 3.0, be less than the average evaluation of 5.0 for " △ ", the average evaluation of more than 5.0 is "×".Evaluation result is shown in table 3.⊿ E *ab value is less, illustrates that thermotolerance is better.
solvent resistance is evaluated
Be formed with the SiO preventing sodion stripping blue colored composition (B-1) is applied to surface with spin coater 2after on the soda-lime glass substrate of film, carry out 2 minutes prebake conditions with the hot plates of 90 DEG C, form the film of thickness 2.5 μm.
Then, after this substrate cool to room temperature, via photomask, film is irradiated to the radioactive ray comprising each wavelength of 365nm, 405nm and 436nm with high-pressure sodium lamp, with 400J/m 2exposure expose.Afterwards, to these substrates with 1kgf/cm 2the developer solution be made up of the potassium hydroxide aqueous solution of 0.04 quality % of the development pressure injection 23 DEG C of (nozzle footpath 1mm), carries out spray development in 90 seconds.Then, clean this substrate with ultrapure water, after air-dry, carry out further toasting after 30 minutes in the cleaning oven of 230 DEG C, on substrate, form dot pattern thus.Then, aforesaid substrate is flooded 40 minutes in the propylene glycol methyl ether acetate of 80 DEG C.
Measure the chromaticity coordinate value (x, y) before and after dipping and values (Y) respectively, to the look change before and after dipping and ⊿ E *ab evaluates.Its result ， is Jiang ⊿ E *the average evaluation that ab value is less than 3.0 is "○", and more than 3.0, be less than the average evaluation of 5.0 for " △ ", the average evaluation more than 5.0 is "×".Evaluation result is shown in table 3.⊿ E *ab value is less, illustrates that solvent resistance is better.
migration property is evaluated
The green coloring composition modulated by aftermentioned method (G-1) is being coated on the SiO being formed with on the surface and preventing sodion stripping with spin coater 2after on the soda-lime glass substrate of film, carry out 2 minutes prebake conditions with the hot plates of 90 DEG C, form the film of thickness 2.4 μm.
Then, after this substrate is cooled to room temperature, use high-pressure sodium lamp when not via irradiating the radioactive ray comprising each wavelength of 365nm, 405nm and 436nm when photomask to film, with 400J/m 2exposure carry out whole exposure.Afterwards, to these substrates with 1kgf/cm 2the developer solution be made up of the potassium hydroxide aqueous solution of 0.04 quality % of the development pressure injection 23 DEG C of (nozzle footpath 1mm), carries out spray development in 90 seconds.Then, clean this substrate with ultrapure water, after air-dry, carry out further toasting after 30 minutes in the cleaning oven of 230 DEG C, on substrate, form green cured film (T-1) thus.
After blue colored composition (B-1) being applied to green cured film (T-1) with spin coater and being upper, carry out 2 minutes prebake conditions with 90 DEG C of hot plates, form the film of thickness 2.5 μm.Then, after this substrate is cooled to room temperature, to this substrate with 1kgf/cm 2the developer solution be made up of the potassium hydroxide aqueous solution of 0.04 quality % of the development pressure injection 23 DEG C of (nozzle footpath 1mm), carries out spray development in 90 seconds.Then, clean this substrate with ultrapure water, carry out air-dry.Be called from being coated with in green cured film (T-1) blue colored composition (B-1) (operation-1) to the operation between air-dry.
Before and after (operation-1), measure the values (Y) of green cured film (T-1) respectively, the values change before and after (operation-1) and ⊿ Y are evaluated.The average evaluation that ⊿ Y value is less than 0.2 by its result ， is "○", by more than 0.2, be less than the average evaluation of 0.7 for " △ ", be "×" by the average evaluation more than 0.7.Evaluation result is shown in table 3.⊿ Y value is less, illustrates that migration property is more suppressed.
The modulator approach of the green coloring composition (G-1) that migration property uses in evaluating is as follows.
Will as the dispersible pigment dispersion of (A) colorant (a-2) 30.5 mass parts, dispersible pigment dispersion (a-3) 25.0 mass parts, as binder resin (C1) solution (solid component concentration 33 quality %) 26.3 mass parts of (C) binder resin, as the dipentaerythritol acrylate of (B) polymerizable compound and potpourri (the Japanese chemical drug Products of Dipentaerythritol Pentaacrylate, trade name KAYARAD DPHA) 9.9 mass parts, as 2-benzyl-2 dimethylamino-1-(4-morpholino phenyl) butane-1-ketone (the trade name Irgacure369 of Photoepolymerizationinitiater initiater, Ciba Specialty Chemicals's product) 1.8 mass parts and NCI-930 (ADEKA Products) 0.1 mass parts, as fluorine class surfactant Megafac F-554 (DIC Products) 0.05 mass parts and mix as the propylene glycol methyl ether acetate of solvent, modulate the green coloring composition (G-1) of solid component concentration 20 quality %.
Embodiment 2 ~ 6, comparative example 1 ~ 3
Replace except using colourant solution (A-2) ~ (A-9) in embodiment 1, except colourant solution (A-1), modulating blue colored composition (B-2) ~ (B-9) similarly to Example 1.And except blue colored composition (B-1), carried out thermotolerance, solvent resistance and migration property evaluation except replacing with blue colored composition (B-2) ~ (B-9) similarly to Example 1.Evaluation result is shown in table 3.
Embodiment 7
Will as the colourant solution of (A) colorant (A-10) 50.0 mass parts, as binder resin (C1) solution (solid component concentration 33 quality %) 14.4 mass parts of (C) binder resin, as the dipentaerythritol acrylate of (B) polymerizable compound and potpourri (the Japanese chemical drug Products of Dipentaerythritol Pentaacrylate, trade name KAYARAD DPHA) 8.2 mass parts, as NCI-930 (ADEKA Products) 1.3 mass parts of Photoepolymerizationinitiater initiater, 2, 2 '-bis-(2-chlorphenyl)-4, 4 ', 5, 5 '-tetraphenyl-1, 2 '-bisglyoxaline 0.2 mass parts, 2, 4-diethyl thioxanthone 0.2 mass parts and 2-mercaptobenzothiazole 0.1 mass parts, as Megafac F-554 (DIC Products) 0.04 mass parts of fluorine class surfactant and the propylene glycol methyl ether acetate as solvent, modulate the blue colored composition (B-10) of solid component concentration 20 quality %.
Then, except using blue colored composition (B-10) to replace, except blue colored composition (B-1), having carried out thermotolerance, solvent resistance and migration property evaluation similarly to Example 1 in embodiment 1.Evaluation result is shown in table 3.
Embodiment 8 ~ 11
Except replacing, except colourant solution (A-10), modulating blue colored composition (B-11) ~ (B-14) similarly to Example 7 with colourant solution (A-11) ~ (A-14) in embodiment 7.And except using blue colored composition (B-11) ~ (B-14) to replace, except blue colored composition (B-10), having carried out thermotolerance, solvent resistance and migration property evaluation similarly to Example 7.Evaluation result is shown in table 3.
Table 3
Colourant solution Blue colored composition Thermotolerance Solvent resistance Migration property
Embodiment 1 A-1 B-1 ○ ○ ○
Embodiment 2 A-2 B-2 ○ ○ ○
Embodiment 3 A-6 B-6 ○ Δ ○
Embodiment 4 A-7 B-7 Δ ○ ○
Embodiment 5 A-8 B-8 ○ ○ ○
Embodiment 6 A-9 B-9 ○ ○ ○
Embodiment 7 A-10 B-10 ○ ○ ○
Embodiment 8 A-11 B-11 ○ ○ ○
Embodiment 9 A-12 B-12 ○ ○ ○
Embodiment 10 A-13 B-13 ○ ○ ○
Embodiment 11 A-14 B-14 ○ ○ ○
Comparative example 1 A-3 B-3 ○ × Δ
Comparative example 2 A-4 B-4 × × Δ
Comparative example 3 A-5 B-5 Δ Δ Δ

Claims (8)

1. coloured composition, it contains (A) colorant and (B) polymerizable compound,
Wherein, (A) colorant contains the polymkeric substance of unsaturated monomer, and described unsaturated monomer contains the unsaturated monomer (a1) with structure shown in following formula (1),
In formula (1),
R 1~ R 6represent the alkyl of hydrogen atom, carbon number 1 ~ 8, phenyl independently of each other or there is the group of alkene unsaturated group,
Ar represents aromatic hydrocarbyl,
R 7~ R 8represent alkyl or the chlorine atom of carbon number 1 ~ 8 independently of each other,
R 9~ R 10represent alkyl or the chlorine atom of hydrogen atom, carbon number 1 ~ 8 independently of each other,
L and m represents the integer of 0 ~ 4 independently of each other,
R 1~ R 6in at least 1 for having the group of alkene unsaturated group, this group with alkene unsaturated group is CH 2=CR 11-COO-X-group, wherein, R 11represent hydrogen atom or methyl, X represents the divalent alkyl of carbon number 5 ~ 12.
2. coloured composition according to claim 1, is characterized in that, described polymkeric substance is also can the multipolymer of unsaturated monomer of ethylenically unsaturated monomers (a2) of copolymerization containing other.
3. coloured composition according to claim 2, it is characterized in that, containing being selected from, have can the ethylenically unsaturated monomers (a2) of copolymerization as other containing at least a kind in (methyl) acrylate of oxygen saturation heterocyclic radical and (methyl) benzyl acrylate.
4. coloured composition according to claim 3, it is characterized in that, containing there is (methyl) acrylate of at least a kind of group be selected from Oxyranyle, oxetanylmethoxy and 3,4-epoxycyclohexyl as (methyl) acrylate had containing oxygen saturation heterocyclic radical.
5. the coloured composition according to any one of Claims 1 to 4, is characterized in that, also containing at least a kind that is selected from blue pigment and violet pigment.
6. the coloured composition according to any one of Claims 1 to 4, is characterized in that, also containing (C) binder resin.
7. color solidification film, it is formed with the coloured composition according to any one of claim 1 ~ 6.
8. display element, it has color solidification film according to claim 7.
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