CN110023350A - (methyl) acrylic acid series polymeric compounds, (methyl) acrylic block copolymer, pigment dispersion, photosensitive coloring composition, colored filter, printing ink composition, compound block copolymer, pigment dispersing agent and smears - Google Patents

(methyl) acrylic acid series polymeric compounds, (methyl) acrylic block copolymer, pigment dispersion, photosensitive coloring composition, colored filter, printing ink composition, compound block copolymer, pigment dispersing agent and smears Download PDF

Info

Publication number
CN110023350A
CN110023350A CN201780073427.6A CN201780073427A CN110023350A CN 110023350 A CN110023350 A CN 110023350A CN 201780073427 A CN201780073427 A CN 201780073427A CN 110023350 A CN110023350 A CN 110023350A
Authority
CN
China
Prior art keywords
general formula
methyl
acrylic acid
polymeric compounds
acid series
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201780073427.6A
Other languages
Chinese (zh)
Other versions
CN110023350B (en
Inventor
大庭一敏
白鸟进
宫本彩子
尼沙德·佩鲁尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Artience Co Ltd
Original Assignee
Toyo Ink SC Holdings Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toyo Ink SC Holdings Co Ltd filed Critical Toyo Ink SC Holdings Co Ltd
Publication of CN110023350A publication Critical patent/CN110023350A/en
Application granted granted Critical
Publication of CN110023350B publication Critical patent/CN110023350B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/12—Esters of phenols or saturated alcohols
    • C08F222/24—Esters containing sulfur
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/006—Preparation of organic pigments
    • C09B67/0069—Non aqueous dispersions of pigments containing only a solvent and a dispersing agent
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D17/00—Pigment pastes, e.g. for mixing in paints
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • 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
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Optics & Photonics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Structural Engineering (AREA)
  • Architecture (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Materials For Photolithography (AREA)
  • Optical Filters (AREA)
  • Polymerisation Methods In General (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)

Abstract

Novel (methyl) acrylic block copolymer and its manufacturing method are provided as the gimmick that can carry out industrial block copolymer using the general radical polymerization simplicity other than active free radical polymerization and inexpensively can be synthesized.A kind of (methyl) acrylic block copolymer (C), it is that single amount body unsaturated to ethylene is polymerized in the presence of (methyl) acrylic acid series polymeric compounds (A3), wherein described (methyl) acrylic acid series polymeric compounds (A3) are that generation is carboxy-modified at (methyl) acrylic acid series polymeric compounds (A2) made of anhydride group by two in (methyl) acrylic acid series polymeric compounds (A1), and make the anhydride group, with the compound of more than one mercapto or in the molecule there is more than one hydroxyl to react with the compound of more than one mercapto with more than one amino in the molecule, (methyl) acrylic acid series polymeric compounds (A3) have mercapto in single terminal region, (methyl) acrylic acid series polymeric compounds (A1) are that there are two carboxyl and one in tool in the molecule Single amount body unsaturated to ethylene is polymerized in the presence of the compound of above mercapto, and there are two carboxyls in single terminal region tool for (methyl) acrylic acid series polymeric compounds (A1).

Description

(methyl) acrylic acid series polymeric compounds, (methyl) acrylic block copolymer, pigment point Granular media, photosensitive coloring composition, colored filter, printing ink composition, compound block Copolymer, pigment dispersing agent and smears
Technical field
The present invention relates to a kind of (methyl) acrylic block copolymer and as (methyl) acrylic acid series of wherein mesosome Polymer and use these compound block copolymer, pigment dispersing agent, surface modifier, smears and then containing described The pigment dispersion of copolymer or intermediate, colored filter photosensitive coloring composition, photosensitive coloring composition, colour Optical filter, printing ink composition.
Background technique
Bond has (methyl) the acrylic block copolymer of different types of polymer blocks usually by different Monomer is continuously polymerize and is manufactured, and has developed various polymerizations up to now.In recent years, energetically development and utilization are lived The manufacturing method of the block copolymer (block copolymer) of free love base polymerization has developed the various utilizations system Make method, controllable structure or molecular weight distribution polymerization.
Living radical polymerization is energetically developed from or so nineteen ninety, especially in image recording material or figure As being miniaturize in order to prevent to the cohesion of the pigment of nanometer level and keeping fine state in display display applications, it is known that The pigment dispersing agent for the block polymer (polymer) that effective use is fabricated by active free radical polymerization is as dispersion The especially excellent material of stability (patent document 1).In addition, gathering as used in the most apex field for manufacturing nanotechnology etc. Fit method, also attracts attention.
Living radical polymerization has various gimmicks, as representative polymerization, it is known to use nitroxide system Polymerization/N-Methyl pyrrolidone (N-Methyl Pyrrolidone, NMP) method of catalyst has used transition metal complex The atom freedom of movement base polymerization of series catalysts/atom transfer radical polymerization (Atom Transfer Radical Polymerization, ATRP) method, use invertibity addition-cracking chain transfer polymerization of dithioesters series catalysts/reversible Addition fracture chain tra nsfer (Reversible Addition-Fragmentation Transfer, RAFT) method, used it is organic The polymerization of tellurium series catalysts/tellurides mediation polymerization (Telluride-mediated polymerization, TERP) method, Iodine transfer polymerization/reversible chain tra nsfer catalytic polymerization (Reversible chain of iodine based compound has been used in the catalyst Transfer catalyzed polymerization, RTCP) method etc..
However, needing to be directed into condensate with catalyst combination and by special protecting group in nitroxide series catalysts At in long-chain, having the shortcomings that the protecting group price is very high.In addition, polymerization reaction needs hot conditions (100 DEG C or more), The control of industrial aspect is extremely difficult.In addition, just there is the stink person from sulfur compound in dithioesters series catalysts Project is more for viewpoint with a large amount of toxicity.Further, it may have following disadvantage: condensate generated has from sulphur Coloring.
On the other hand, as transition metal series catalysts, for example, using make ligand in Cu, Ni, Re, Rh, Ru Deng complex compound made of in the compound for center metal, about the polymerization for having used organic tellurium based compound in the catalyst, Also metal tellurium compound is used, about the polymerization for having used iodine compound in the catalyst, also using organic iodines such as iodate alkyl Compound.
However, using the transition-metal catalyst or organic tellurium series catalysts, iodine compound catalyst, It has the drawback that and is not easy to completely remove or be difficult to go in industrial aspect in a large amount of catalyst own product after the reaction Except catalyst (patent document 2).In addition, having the drawback that when discarding unwanted catalyst in terms of meeting generation environment Problem.
Existing technical literature
Patent document
Patent document 1: Japanese Patent No. 5734821
Patent document 2: Japanese Patent Laid-Open 2011-202169 bulletin
Summary of the invention
Problem to be solved by the invention
The invention is intended to solve described problem point, and being designed to provide can be using leading to other than active free radical polymerization Radical polymerization is easy and cheap and is easy to carry out industrial novel (methyl) acrylic block copolymerization Object mesosome condensate and then has used these pigment dispersing agent, colored filter with photosensitive with its manufacturing method and wherein It property coloured composition and used the polymeric compound block copolymer of the intermediate, changed by the surface of resin treatment Good dose, smears etc..
Technical means to solve problem
The inventors of the present invention are artificial to be solved the problems, such as described all and effort research has been repeated, and the present invention is as a result completed. That is, according to the present invention, provide described below will have (methyl) acrylic acid series polymeric compounds of anhydride group be used in single terminal region Polymeric novel (methyl) the acrylic block copolymer of intermediate and polymerization, thus can to solve the problem.
That is, being by (methyl) acrylic acid series polymeric compounds the present invention relates to a kind of (methyl) acrylic acid series polymeric compounds (A2) (A1) possessed by two it is carboxy-modified formed at anhydride group, and (methyl) acrylic acid series polymeric compounds (A2) are in single end region Domain has anhydride group, and (methyl) acrylic acid series polymeric compounds (A1) are that there are two carboxyl and more than one sulphur in tool in the molecule Single amount body unsaturated to ethylene is polymerized in the presence of the compound of alcohol radical, and (methyl) acrylic polymeric There are two carboxyls in single terminal region tool for object (A1).
About an embodiment of (methyl) acrylic acid series polymeric compounds (A2), in intramolecular tool, there are two carboxyls Compound with more than one mercapto is compound (D) represented by the following general formula (1).
[changing 1]
General formula (1)
(in general formula (1), R1For methylene or ethylidene)
Moreover, it relates to which a kind of (methyl) acrylic acid series polymeric compounds (A2), are to make (methyl) acrylic polymeric More than one hydroxyl in object (A1'), with
Acid chloride group in tricarboxylic acid anhydride acyl chlorides (E) or the reaction of an anhydride group in the intramolecular of tetracarboxylic anhydride (F) and At, and (methyl) acrylic acid series polymeric compounds (A2) have more than one anhydride group in single terminal region, wherein (the first Base) acrylic acid series polymeric compounds (A1') be in the molecule with more than one hydroxyl and more than one mercapto chemical combination Single amount body unsaturated to ethylene is polymerized in the presence of object, and (methyl) acrylic acid series polymeric compounds (A1') exist Single terminal region has more than one hydroxyl.
About an embodiment of (methyl) acrylic acid series polymeric compounds (A2), there is more than one in the intramolecular Hydroxyl and more than one mercapto compound be the following general formula (2) represented by compound (G),
The tricarboxylic acid anhydride acyl chlorides (E) is compound (H1) represented by following chemical formula (3),
The tetracarboxylic anhydride (F) is compound (H2) represented by the following general formula (4).
[changing 2]
General formula (2)
(in general formula (2), R2For that can have the alkyl of heteroatomic divalent~tetravalence, n1Integer for 1~3)
[changing 3]
Chemical formula (3)
[changing 4]
General formula (4)
(in general formula (4), k1It is 1 or 2)
Moreover, it relates to which a kind of (methyl) acrylic acid series polymeric compounds (A3), are to make (methyl) of the invention Anhydride group in acrylic acid series polymeric compounds (A2) and
In the molecule the compound with more than one amino and more than one mercapto or
In the molecule there is more than one hydroxyl to react with the compound of more than one mercapto, and described (methyl) acrylic acid series polymeric compounds (A3) have mercapto in single terminal region.
About an embodiment of (methyl) acrylic acid series polymeric compounds (A3), there is more than one in the intramolecular Amino and more than one mercapto compound be the following general formula (5) represented by compound (I1),
Having the compound of more than one hydroxyl and more than one mercapto in the intramolecular is the following general formula (6) Represented compound (I2).
[changing 5]
General formula (5)
[changing 6]
General formula (6)
(in general formula (5) and general formula (6),
R3For hydrogen atom, alkyl or aryl,
R4For that can have the alkyl of heteroatomic divalent~tetravalence, n2Integer for 1~3)
Moreover, it relates to which a kind of (methyl) acrylic acid series polymeric compounds (A3), are in (methyl) acrylic polymeric In object (A1'),
Make the acrylic acid series polymeric compounds (A1') more than one hydroxyl possessed by single terminal region and
Have more than one isocyanate group and the compound of more than one (methyl) acryloyl group anti-in the molecule It answers,
And then makes (methyl) acryloyl group and there is more than one amino and more than one mercaptan in the molecule The compound of base carries out Michael addition reaction and forms, and (methyl) acrylic acid series polymeric compounds (A3) have in single terminal region There is mercapto, wherein described (methyl) acrylic acid series polymeric compounds (A1') are in the molecule with more than one hydroxyl and one Single amount body unsaturated to ethylene is polymerized in the presence of the compound of a above mercapto, and (methyl) third Olefin(e) acid based polymer (A1') has more than one hydroxyl in single terminal region.
Moreover, it relates to which a kind of (methyl) acrylic block copolymer (C), is in (the first of the invention Base) in the presence of acrylic acid series polymeric compounds (A3), single amount body unsaturated to ethylene is polymerized.
Moreover, it relates to which a kind of (methyl) acrylic acid series polymeric compounds (A2), are indicated by the following general formula (7).
[changing 7]
General formula (7)
(in general formula (7), (A) is (methyl) acrylic acid series polymeric compounds residue,
R5For the bilvalent radical being directly bonded or in the group as composed by alkylidene, arlydene and epoxy alkyl,
L1To be directly bonded or-O-C (=O)-,
X1For tetravalence base shown in the following general formula (8), general formula (9) or general formula (10),
Y1For hydrogen atom or-COOH)
[changing 8]
General formula (8)
(in general formula (8), R6For methine, ethylidine (ethylidyne group) or 1,1,2- second, three base (1,1,2- ethanetriyl group))
[changing 9]
General formula (9)
(in general formula (9), k2It is 1 or 2)
[changing 10]
General formula (10)
(in general formula (10), Q1For be directly bonded or the bilvalent radical of carbon number 1~20)
Moreover, it relates to which a kind of (methyl) acrylic acid series polymeric compounds (A3), are indicated by the following general formula (11).
[changing 11]
General formula (11)
(in general formula (11), (A) is (methyl) acrylic acid series polymeric compounds residue,
R7For the bilvalent radical being directly bonded or in the group as composed by alkylidene, arlydene and alkylene oxide,
L2To be directly bonded or-O-C (=O)-,
X2For tetravalence base shown in the following general formula (12), general formula (13), general formula (14) or general formula (15),
Y2For hydrogen atom or-COOH, Y3And Y4In any one be base shown in the following general formula (16) or general formula (17), Y3And Y4 The other of be hydrogen atom or COOR15, R15For hydrogen atom, alkyl, aryl or halogen atom)
[changing 12]
General formula (12)
(in general formula (12), R8For three base of methine, ethylidine or 1,1,2- second)
[changing 13]
General formula (13)
(in general formula (13), k3It is 1 or 2)
[changing 14]
General formula (14)
(in general formula (14), Q2For be directly bonded or the bilvalent radical of carbon number 1~20)
[changing 15]
General formula (15)
(in general formula (15), R9For alkylidene)
[changing 16]
General formula (16)
(in general formula (16), M1For-NR11Or-O-, R11For hydrogen atom, alkyl or arlydene,
R10For the bilvalent radical in the group as composed by alkylidene, arlydene and alkylene oxide)
[changing 17]
General formula (17)
(in general formula (17), R12、R13Separately for selected from the group as composed by alkylidene, arlydene and alkylene oxide In bilvalent radical,
R14For hydrogen atom, alkyl, aryl or halogen atom)
Moreover, it relates to which a kind of (methyl) acrylic block copolymer (C), is by the following general formula (18) table Show.
[changing 18]
General formula (18)
(in general formula (18), (A) is (methyl) acrylic acid series polymeric compounds residue,
R16For the bilvalent radical being directly bonded or in the group as composed by alkylidene, arlydene and alkylene oxide,
L3To be directly bonded or-O-C (=O)-,
X3For tetravalence base shown in the following general formula (19), general formula (20), general formula (21) or general formula (22),
Y5For hydrogen atom or-COOH,
Y6And Y7In any one be base shown in the following general formula (23) or general formula (24), Y6And Y7The other of for hydrogen it is former Son or COOR24, R24For hydrogen atom, alkyl, aryl or halogen atom)
[changing 19]
General formula (19)
(in general formula (19), R17For methine, ethylidine or 1,1,2- second, three base)
[changing 20]
General formula (20)
(in general formula (20), k4It is 1 or 2)
[changing 21]
General formula (21)
(in general formula (21), Q3For be directly bonded or the bilvalent radical of carbon number 1~20)
[changing 22]
General formula (22)
(in general formula (22), R18For alkylidene)
[changing 23]
General formula (23)
(in general formula (23), M2For-NR20Or-O-, R20For hydrogen atom or alkyl,
R19For the bilvalent radical in the group as composed by alkylidene, arlydene and alkylene oxide,
It (B) is (methyl) acrylic acid series polymeric compounds residue)
[changing 24]
General formula (24)
(in general formula (24), R21、R22Separately for selected from the group as composed by alkylidene, arlydene and alkylene oxide In bilvalent radical,
R23For hydrogen atom, alkyl, aryl or halogen atom,
It (B) is (methyl) acrylic acid series polymeric compounds residue)
Moreover, it relates to a kind of pigment dispersion, containing pigment, pigment dispersing agent and organic solvent, and it is described Pigment dispersing agent is the block copolymer (C) of the invention.
Moreover, it relates to a kind of photosensitive coloring composition, containing the pigment dispersion of the invention, and institute Photosensitive coloring composition is stated for colored filter.
Moreover, it relates to which a kind of photosensitive coloring composition, contains pigment, pigment dispersing agent, alkali-soluble tree Rouge, multi-functional single amount body and optical free radical initiator, and the photosensitive coloring composition is used for colored filter, the alkali Soluble resin is the block copolymer (C) of the invention.
Moreover, it relates to which a kind of colored filter, has by the photosensitive coloring composition shape of the invention At filter segments (Filter segment).
Moreover, it relates to a kind of printing ink composition, contain pigment, pigment dispersing agent, adhesive resin and organic Solvent, and pigment dispersing agent or adhesive resin are the block copolymer (C) of the invention.
Moreover, it relates to a kind of compound block copolymer, it uses described of the invention in single terminal region tool There are (methyl) acrylic acid series polymeric compounds (A2) of anhydride group as precursor.
Moreover, it relates to a kind of pigment dispersing agent, of the invention there is acid in single terminal region it uses described (methyl) acrylic acid series polymeric compounds (A2) of anhydride group.
Moreover, it relates to a kind of surface modifier or smears, it uses described of the invention in single end region Domain has (methyl) acrylic acid series polymeric compounds (A2) of anhydride group.
The effect of invention
According to the present invention, it is possible to provide can it is easy using the general radical polymerization other than active free radical polymerization and It is cheap and be easy to carry out industrial novel (methyl) acrylic block copolymer and its manufacturing method and wherein Mesosome condensate is used in turn described in these pigment dispersing agent, colored filter photosensitive coloring composition and use The polymeric compound block copolymer of intermediate, by surface modifier, smears of resin treatment etc..
Specific embodiment
The present invention be single terminal region have anhydride group novel (methyl) acrylic acid series polymeric compounds (A2), use (first Base) acrylic acid series polymeric compounds (A2) and obtain in single terminal region (methyl) acrylic acid series polymeric compounds with mercapto (A3) and (methyl) acrylic acid series polymeric compounds (A3) is used and (methyl) the acrylic block copolymer (C) of acquisition.Separately Outside, be related to it is a kind of obtained using other methods in single terminal region (methyl) acrylic acid series polymeric compounds with mercapto (A3) and (methyl) acrylic acid series polymeric compounds (A3) is used and (methyl) the acrylic block copolymer (C) of acquisition.
In single terminal region there is the manufacturing method of (methyl) acrylic acid series polymeric compounds (A2) of anhydride group to include the following steps (1-1) or step (1-2).These steps generate (methyl) acrylic acid series polymeric compounds including the use of the chain transfer reaction of mercapto (A1) or the step of (methyl) acrylic acid series polymeric compounds (A1').
(1-1): in the presence of the compound of carboxyl and more than one mercapto there are two having in the molecule, to ethylene Property unsaturated single amount body polymerize, and obtain that there are two (methyl) acrylic acid series polymeric compounds of carboxyl in single terminal region tool (A1), then will be described two carboxy-modified at anhydride group, and obtain (methyl) acrylic acid that there is anhydride group in single terminal region The step of based polymer (A2)
(1-2): in the presence of the compound in the molecule with more than one hydroxyl and more than one mercapto, Single amount body unsaturated to ethylene polymerize, and obtains (methyl) propylene for having more than one hydroxyl in single terminal region Sour based polymer (A1') then makes acid chloride group or tetrabasic carboxylic acid in one above hydroxyl and tricarboxylic acid anhydride acyl chlorides (E) Anhydride group reaction in the intramolecular of acid anhydride (F), and obtain the (first that there is more than one anhydride group in single terminal region Base) acrylic acid series polymeric compounds (A2) the step of
In addition, in the case where the manufacturing method of single terminal region (methyl) acrylic acid series polymeric compounds (A3) with mercapto includes State step (2-1) or step (2-2).
(2-1): obtaining single terminal region (methyl) acrylic acid series polymeric compounds (A3) with mercapto the step of, described (methyl) acrylic acid series polymeric compounds (A3) are the acid made through the step (1-1) or step (1-2) resulting polymer (A2) Anhydride group and the in the molecule compound with more than one amino and more than one mercapto or
In the molecule there is more than one hydroxyl to react with the compound of more than one mercapto.
(2-2): obtaining single terminal region (methyl) acrylic acid series polymeric compounds (A3) with mercapto the step of, described (methyl) acrylic acid series polymeric compounds (A3) are that Yu Dan terminal region is poly- with more than one hydroxyl (methyl) acrylic acid series It closes in object (A1'),
Make the acrylic acid series polymeric compounds (A1') more than one hydroxyl possessed by single terminal region and
Have more than one isocyanate group and the compound of more than one (methyl) acryloyl group anti-in the molecule It answers,
And then makes (methyl) acryloyl group and there is more than one amino and more than one mercaptan in the molecule The compound of base carries out Michael addition reaction and forms, wherein described (methyl) acrylic acid series polymeric compounds (A1') are in molecule In the presence of the interior compound with more than one hydroxyl and more than one mercapto single amount body unsaturated to ethylene into Row is polymerized.
In addition, the manufacturing method of (methyl) acrylic block copolymer (C) includes the following steps (3).The step is It utilizes the chain transfer reaction of the mercapto in (methyl) acrylic acid series polymeric compounds (A3) and generates polymer.
(3): in the presence of through the step (2-1) or step (2-2) resulting polymer (A3) not to ethylene The step of single amount body of saturation is polymerize
(methyl) acrylic block copolymer (C) of the invention and the block copolymerization for having used active free radical polymerization etc. Object is compared, and the difficult catalyst removal step relative to metallic catalyst or organoiodine compound etc. is not needed.In addition, sulphur The problem of stink Deng caused by, coloring, is also few, and then can also carry out and general free radical under the synthesis condition of oxygen concentration etc. Advantage is also high in terms of paradigmatic system polymerization under the same conditions and color, production equipment, obtains using general polymerization (methyl) acrylic block copolymer.
(methyl) acrylic acid series polymeric compounds (A1) or (methyl) acrylic acid series polymeric compounds (A1') or (methyl) acrylic acid Based polymer (B) may include a kind of unsaturated single amount body of ethylene, also may include the unsaturated single amount body of a variety of ethylene.
About the step to obtain copolymer of the invention (A2), copolymer (A3) and copolymer (C), closed It is shown below and is illustrated at the concrete example of method.
But it is not limited to these concrete example.
Following concrete examples (I) are to obtain (methyl) acrylic acid by the step (1-1), step (2-1) and step (3) The concrete example of based block copolymer (C).
[concrete example (I)]
< step (1-1): there is the synthesis > of (methyl) acrylic acid series polymeric compounds (A2) of anhydride group in single terminal region
In having in the molecule, there are two changes represented by compound, the i.e. general formula (1) of carboxyl and more than one mercapto In the presence of closing object (D), amount body unsaturated single to ethylene polymerize, and obtains that there are two carboxyls in single terminal region tool (methyl) acrylic acid series polymeric compounds (A1) (following proposal (1)).
[changing 25]
General formula (1) (compound (D))
(in general formula (1), R1For methylene or ethylidene)
[changing 26]
Scheme (1)
(in scheme (1), (A) is (methyl) acrylic acid series that single amount body unsaturated to arbitrary ethylene has carried out polymerization Converging portion, and be (methyl) acrylic acid series polymeric compounds (A1) residue.R1It is identical as the general formula (1))
Two in the polymer (A1) are carboxy-modified at anhydride group, and obtaining has anhydride group in single terminal region (methyl) acrylic acid series polymeric compounds (A2) (following proposal (2)).
[changing 27]
Scheme (2)
(each symbol in scheme (2) is identical as scheme (1))
As long as having in the molecule there are two the compound of carboxyl and more than one mercapto is to play as chain-transferring agent Function person is then not particularly limited.General formula (1) compound represented (D) can preferably be enumerated.Change as shown in general formula (1) Close object (D), such as 2- mercapto succinic acid, 2- sulfydryl glutaric acid can be enumerated etc..Preferably 2- mercapto succinic acid.
In addition, as the other examples for having the compound there are two carboxyl and more than one mercapto in the molecule, it can 2,2- di-2-ethylhexylphosphine oxide (thioglycolic acid), 2,3-dimercaptosuccinic acid, 4,5- dimercapto phthalic acid etc. are enumerated, but and unlimited Due to these.
Have in the molecule and can be used alone one kind, or combination there are two the compound of carboxyl and more than one mercapto Using two or more.
Hereinafter, being shown as the scheme (1-1) of the preferred concrete example of scheme (1), scheme (2), scheme (2-1).But It is not limited to these.
[changing 28]
Scheme (1-1)
[changing 29]
Scheme (2-1)
(each symbol in scheme (1-1), scheme (2-1) is identical as scheme (1))
As the method for being cyclized terminal carboxyl group as the scheme (2), such as acetic anhydride or 2 can be used, 6- is bis- The intramolecular condensations catalyst such as [(2,2,6,6- tetramethyl -1- piperidyl) methyl] phenylboric acid, and carry out intramolecular dehydration contracting It closes and obtains acid anhydrides.In addition, can also be following method: carrying out intramolecular dehydration under high temperature heating conditions without using catalyst Condensation.
Wherein, for producing the viewpoint of aspect or cost etc., the series of acetic anhydride is more preferably used in the catalyst. In addition, being not limited to these methods.
< step (2-1): in the synthesis > of single terminal region (methyl) acrylic acid series polymeric compounds (A3) with mercapto
Make the anhydride group of the polymer (A2) and there is more than one amino and more than one mercaptan in the molecule Compound (I1) represented by the compound of base, i.e. the following general formula (5) or in the molecule have more than one hydroxyl and one Compound (I2) reaction represented by compound, i.e. the following general formula (6) of a above mercapto, and obtain in single terminal region (methyl) acrylic acid series polymeric compounds (A3) (following proposal (3)) with mercapto.
[changing 30]
General formula (5) (compound (I1))
[changing 31]
General formula (6) (compound (I2))
(in general formula (5) and general formula (6),
R3For hydrogen atom, alkyl or aryl,
R4For that can have the alkyl of heteroatomic divalent~tetravalence, n2Integer for 1~3)
As R4In hetero atom, O (oxygen), N (nitrogen), S (sulphur) etc. can be enumerated, wherein preferably O.As divalent~tetravalence Alkyl, aliphatic alkyl, aromatic hydrocarbyl and these combination can be enumerated.As R4, wherein being preferably selected from alkylidene, Asia Person in aryl and epoxy alkyl.More preferably alkylidene.
[changing 32]
Scheme (3)
(each symbol in scheme (3) is identical as each symbol in the general formula (1), general formula (5) and general formula (6))
Hereinafter, being shown as the scheme (3-1) of the preferred concrete example of scheme (3).But it is not limited to these.
[changing 33]
Scheme (3-1)
(each symbol in scheme (3-1) is identical as scheme (3))
It as compound (I1) represented shown in general formula (5), such as can enumerate: 2- aminoothyl mercaptan, 3- aminopropan The amino alkanes thio-alcohols such as base -1- mercaptan, 1- aminopropyl -2- mercaptan, 4- amino -1- butanethiol；2- aminothiophenol, 3- ammonia Aminobenzenes thio-alcohols such as base benzenethiol, 4- aminothiophenol etc., preferably amino alkane mercaptan.These can be used alone, can also In any combination and with two or more.In addition, being not limited to these.
As compound (I2) represented shown in general formula (6), such as can enumerate: 2 mercapto ethanol, 2- sulfydryls hexanol, 2- [2- (2- sulfydryl ethyoxyl) ethylenebis dithiocarbamate] ethyl alcohol, 2- (2- sulfydryl ethyoxyl) ethyl alcohol, 2- (2- mercaptoethyl is thio) ethyl alcohol, 8- sulfydryl -3,6- dioxaoctane -1- alcohol, 11- sulfydryl -3,6,9- trioxaundecane -1- alcohol, tetra- oxa- of 3,6,9,12- - The 14- sulfydryl tetradecane -1- alcohol, five oxa- heptadecane -1- alcohol of 17- sulfydryl -3,6,9,12,15-, 2- (mercapto methyl) -3- sulfydryl - The mercaptan such as 1- propyl alcohol (thioalcohol) class.These can be used alone, can also be in any combination and with two or more.In addition, It is not limited to these.
The ratio of compound (I1), the amino of compound (I2) or hydroxyl (mol) is preferably relative to (methyl) acrylic acid The anhydride group (mol) of based copolymer (A2) and be 0.3~1.5 range.In turn, more preferably 0.8~1.2.
It is reacted as the anhydride group made in (methyl) acrylic acid series polymeric compounds (A2) with compound (I1), compound (I2) Method can be enumerated after mixing within the temperature range of 15 DEG C~70 DEG C and carry out 1 hour or so the method being stirred to react, but and unlimited Due to these.
< step (3): the synthesis > of (methyl) acrylic block copolymer (C)
In the presence of (methyl) acrylic acid series polymeric compounds (A3), single amount body unsaturated to ethylene is polymerize (following Scheme (4) or scheme (5)).
[changing 34]
Scheme (4)
Hereinafter, being shown as the scheme (4-1) of the preferred concrete example of scheme (4).But it is not limited to these.
[changing 35]
Scheme (4-1)
[changing 36]
Scheme (5)
Hereinafter, being shown as the scheme (5-1) of the preferred concrete example of scheme (5).But it is not limited to these.
[changing 37]
Scheme (5-1)
((B) in scheme (4), scheme (4-1), scheme (5) and scheme (5-1) is to be appointed to by step (3) The unsaturated single amount body of the ethylene of meaning has carried out (methyl) the acrylic polymeric portion of polymerization.Other each symbols are as described above)
By the concrete example (I), (methyl) acrylic block copolymer (C) can get.
Secondly, being illustrated to following concrete examples (II).Concrete example (II) is by the step (1-2), step (2-1) And step (3) and obtain the concrete example of (methyl) acrylic block copolymer (C).
[concrete example (II)]
< step (1-2): there is (methyl) acrylic acid series polymeric compounds (A2) > of anhydride group in single terminal region
Obtain (methyl) acrylic acid series polymeric compounds (A1') that there is more than one hydroxyl in single terminal region, (first Base) acrylic acid series polymeric compounds (A1') be in the molecule with more than one hydroxyl and more than one mercapto chemical combination In the presence of compound (G) represented by object, i.e. the following general formula (2), amount body unsaturated single to ethylene be polymerized (under State scheme (6)).
[changing 38]
General formula (2) (compound (G))
(in general formula (2), R2For that can have the alkyl of heteroatomic divalent~tetravalence, n1Integer for 1~3)
R2In divalent~tetravalence alkyl can be set as and the R in the general formula (6)4Identical person.
[changing 39]
Scheme (6)
(in scheme (6), (A) is (methyl) acrylic acid series that single amount body unsaturated to arbitrary ethylene has carried out polymerization Converging portion, and be (methyl) acrylic acid series polymeric compounds (A1') residue.R2It is identical as the general formula (2))
Hereinafter, being shown as the scheme (6-1) of the preferred concrete example of scheme (6).But it is not limited to these.
[changing 40]
Scheme (6-1)
((A) in scheme (6-1) is identical as scheme (6))
(methyl) acrylic acid series polymeric compounds (A2) that there is more than one anhydride group in single terminal region are obtained, it is described (methyl) acrylic acid series polymeric compounds (A2) are the more than one hydroxyls and tricarboxylic acid anhydride acyl chlorides made in the polymer (A1') (E) anhydride group reaction in the intramolecular of acid chloride group or tetracarboxylic anhydride (F) in forms (following proposal (7) or scheme (8))。
[changing 41]
Scheme (7)
(in scheme (7), the integer that P is 1~3, other each symbols are identical as the scheme (6))
Hereinafter, being shown as the scheme (7-1) of the preferred concrete example of scheme (7).But it is not limited to these.
[changing 42]
Scheme (7-1)
(each symbol in scheme (7-1) is identical as the scheme (7))
[changing 43]
Scheme (8)
(each symbol in scheme (8) is identical as the scheme (7))
Hereinafter, being shown as the scheme (8-1) of the preferred concrete example of scheme (8).But it is not limited to these.
[changing 44]
Scheme (8-1)
(each symbol in scheme (8-1) is identical as the scheme (8))
Tricarboxylic acid anhydride acyl chlorides (E), tetracarboxylic anhydride (F) preferably with one in equimolar number and polymer (A1') with On hydroxyl reaction, more specifically, using tricarboxylic acid anhydride acyl chlorides (E), it is generally desirable to only with an acid chloride group Reaction, using tetracarboxylic anhydride (F), it is generally desirable to only react an anhydride group in two anhydride groups.
As long as the compound in the molecule with more than one hydroxyl and more than one mercapto is as chain-transferring agent It functions, is then not particularly limited.Preferably general formula (2) compound represented (G).
It as general formula (2) compound represented (G), such as can enumerate: 2 mercapto ethanol, 2- sulfydryls hexanol, 6- sulfydryl -1- Hexanol, 3- sulfydryl -1- propyl alcohol, 7- sulfydryl -1-heptanol, thioglycerol, 1,3- dimercapto -2- propyl alcohol, dimercapto pentaerythrite, three Sulfydryl pentaerythrite etc., but it is not limited to these.
It as the other examples of compound (G), can enumerate: 2- (2- sulfydryl ethyoxyl) ethyl alcohol, 2- [2- (2- sulfydryl ethoxy Base) ethylenebis dithiocarbamate] ethyl alcohol, 8- sulfydryl -3,6- dioxaoctane -1- alcohol, 11- sulfydryl -3,6,9- trioxaundecane -1- alcohol, Five oxa- heptadecane -1- alcohol of 17- sulfydryl -3,6,9,12,15-, 2- (mercapto methyl) -3- sulfydryl -1- propyl alcohol, dimercaprol, 2, 2- dimethyl -3- sulfydryl -1- propyl alcohol, bis- (the mercapto methyl) -1- propyl alcohol of 2,2-, 8- sulfydryl -1- octanol, 10- sulfydryl -1- decyl alcohol, 11- sulfydryl -1- undecyl alcohol etc., but it is not limited to these.There is more than one hydroxyl and more than one sulphur in the molecule The compound of alcohol radical can be used alone one kind, or be applied in combination two or more.
As the example of tricarboxylic acid anhydride acyl chlorides (E), can enumerate: trimellitic anhydride acyl chlorides, 4- (chlorocarbonyl) hexamethylene -1, 2- dicarboxylic anhydride, N, N'-1,4- phenylene bis- [octahydro -1,3- dioxo -5- isobenzofuran formamides], 5- [4- (chloroformyl Base) benzoyl] isobenzofuran -1,3- diketone, 3,4- diphenyl -5- (chloroformyl) phthalic anhydride, 1,3- dioxy Generation -6- (chloroformyl) isobenzofuran -5- benzyl carboxylate, 1,3- dioxo -1,3- dihydroisobenzofuran -4- carboxylic acid chloride Deng, but it is not limited to these.Tricarboxylic acid anhydride acyl chlorides (E) can be used alone one kind, or be applied in combination two or more.
It as the example of tetracarboxylic anhydride (F), can enumerate: pyromellitic dianhydride, 1H, 3H- naphtho- [2,3-c:6,7-c'] two Furans -1,3,6,8- tetrone, the Asia 2,3,6,7- biphenyltetracarboxyacid acid 2,3:6,7- dianhydride, 3,4,8,9- pyrene tetrabasic carboxylic acid 3,4:8,9- bis- Acid anhydride, 5,5'- bis- [isobenzofuran] -1,1', 3,3'- tetrone, 2,3,6,7- anthracene tetrabasic carboxylic acid 2,3:6,7- dianhydride, 4- methyl-1 H, Two furans -1,3,5,7- tetrone of 3H- benzo [1,2-c:4,5-c'], 1,4,5,8- naphthalene tetracarboxylic acid 1,8:4,5- dianhydride, 5,5'- (1,4- phenylene) bis- (isobenzofuran -1,3- diketone), 5,5'- (2,6- naphthalene-diyl) bis- (isobenzofuran -1,3- diketone), 5,5'- (2,7- naphthalene-diyl) bis- (isobenzofuran -1,3- diketone), 5,5'- (xenyl -4,4'- diyl) bis- (different benzo furans Mutter -1,3- diketone), the bis- (isobenzofuran -1,3- of 5,5'- (1,1':4', 1 "-terphenyl (terbenzene) -4,4 "-diyl) Diketone), two furans -1,3,6,8- tetrone of benzo [1,2-c:3,4-c'], 5,5'- di-2-ethylhexylphosphine oxide (isobenzofuran -1,3- two Ketone), 5,5'- (5- phenyl -1,3- phenylene) bis- (isobenzofuran -1,3- diketone), 4- phenyl -1H, 3H- benzo [1,2-c: 4,5-c'] two furans -1,3,5,7- tetrones, 1,2,5,6- naphthalene tetracarboxylic acids 1,2:5,6- dianhydride etc., but it is not limited to these.Four Carboxylic acid anhydrides (F) can be used alone one kind, or be applied in combination two or more.
< step (2-1): in the synthesis > of single terminal region (methyl) acrylic acid series polymeric compounds (A3) with mercapto
Make the anhydride group of the polymer (A2) and there is more than one amino and more than one mercaptan in the molecule Compound (I1) represented by the compound of base, the i.e. described general formula (5) or in the molecule have more than one hydroxyl and one Compound (I2) reaction represented by the compound of a above mercapto, the i.e. described general formula (6), and acquisition is in single terminal region (methyl) acrylic acid series polymeric compounds (A3) (following proposal (9) or scheme (10)) with mercapto.
[changing 45]
Scheme (9)
[changing 46]
Scheme (10)
(each symbol in scheme (9) and scheme (10) and the scheme (7), general formula (5) and general formula (6) it is identical)
Hereinafter, being shown as the scheme (9-1) of the preferred concrete example of scheme (9), scheme (10), scheme (10-1).But It is to be not limited to these.
[changing 47]
Scheme (9-1)
[changing 48]
Scheme (10-1)
(each symbol in scheme (9-1) and scheme (10-1) is identical as the scheme (9), scheme (10))
< step (3): the synthesis > of (methyl) acrylic block copolymer (C)
Single amount body unsaturated to ethylene is polymerize (following sides in the presence of (methyl) acrylic acid series polymeric compounds (A3) Case (11) or following proposal (12)).
[changing 49]
Scheme (11)
[changing 50]
Scheme (12)
(in scheme (11) and scheme (12), (B) is unsaturated to the arbitrary ethylene obtained by step (3) Single amount body has carried out (methyl) the acrylic polymeric portion of polymerization.Other each symbols are as described above)
By the concrete example (II), (methyl) acrylic block copolymer (C) can get.
Secondly, being illustrated to following concrete examples (III).Concrete example (III) is to obtain (first by (2-2) and (3) Base) acrylic block copolymer (C) concrete example.Furthermore the step of obtaining (methyl) acrylic acid series polymeric compounds (A1') is institute State step (1-2) like that, thus herein illustrate to omit.
[concrete example (III)]
< step (2-2): in single terminal region (methyl) acrylic acid series polymeric compounds (A3) > with mercapto
In in (methyl) acrylic acid series polymeric compounds (A1') that single terminal region has more than one hydroxyl, make One above hydroxyl and there is more than one isocyanate group and more than one (methyl) acryloyl in the molecule The compound of base reacts, and then makes (methyl) acryloyl group and have more than one amino and more than one in the molecule Mercapto compound carry out Michael addition reaction, and obtain in single terminal region (methyl) acrylic acid with mercapto Based polymer (A3) (following proposal (13)).
[changing 51]
Scheme (13)
(in scheme (13), R25For hydrogen atom or methyl, R26For that can have the alkyl of heteroatomic divalent~tetravalence, W 1 ~3 integer, other each symbols are as described above).
R26In divalent~tetravalence alkyl can be set as and the R in the general formula (6)4For identical person.Furthermore there is isocyanide The compound of perester radical and more than one (methyl) acryloyl group has R26Alkyl valence mumber -1 (methyl) acryloyl Base.
Hereinafter, being shown as the scheme (13-1) of the preferred concrete example of scheme (13).But it is not limited to these.
[changing 52]
Scheme (13-1)
(each symbol in scheme (13-1) is identical as scheme (13))
Method can be listed below: as synthesis condition, make (methyl) that there is more than one hydroxyl in single terminal region More than one hydroxyl in acrylic acid series polymeric compounds (A1') and there is more than one isocyanate group and one in the molecule After the compound of above (methyl) acryloyl group mixes within the temperature range of 70 DEG C~100 DEG C, carry out 1 hour or so stirring Reaction has more than one amino and more than one sulphur at 100 DEG C to (methyl) acryloyl group and in the molecule The compound of alcohol radical carries out 5 hours heating stirrings, and carries out Michael addition reaction.But it is not limited to these methods.
< step (3): the synthesis > of (methyl) acrylic block copolymer (C)
In the presence of (methyl) acrylic acid series polymeric compounds (A3), single amount body unsaturated to ethylene is polymerize (following Scheme (14)).
[changing 53]
Scheme (14)
(in scheme (14), (B) is that the single amount body unsaturated to arbitrary ethylene obtained by step (3) carries out (methyl) the acrylic polymeric portion of polymerization.Other each symbols are as described above)
There is (methyl) propylene of anhydride group in single terminal region by what the concrete example (I), concrete example (II) obtained The preferred structure of sour based polymer (A2) can be indicated using the following general formula (7).
[changing 54]
General formula (7)
(in general formula (7), (A) is (methyl) acrylic acid series polymeric compounds residue,
R5For the bilvalent radical being directly bonded or in the group as composed by alkylidene, arlydene and epoxy alkyl,
L1To be directly bonded or-O-C (=O)-,
X1For tetravalence base shown in the following general formula (8), general formula (9) or general formula (10),
Y1For hydrogen atom or-COOH)
[changing 55]
General formula (8)
(in general formula (8), R6For methine, ethylidine or 1,1,2- second, three base)
[changing 56]
General formula (9)
(in general formula (9), k2It is 1 or 2)
[changing 57]
General formula (10)
(in general formula (10), Q1For be directly bonded or the bilvalent radical of carbon number 1~20)
Preferably X1For tetravalence base shown in general formula (9), k2It is 1.
There is mercaptan in single terminal region by what the concrete example (I), concrete example (II), concrete example (III) obtained The preferred structure of (methyl) acrylic acid series polymeric compounds (A3) of base can be indicated using the following general formula (11).
[changing 58]
General formula (11)
(in general formula (11), (A) is (methyl) acrylic acid series polymeric compounds residue,
R7For the bilvalent radical being directly bonded or in the group as composed by alkylidene, arlydene and alkylene oxide,
L2To be directly bonded or-O-C (=O)-,
X2For tetravalence base shown in the following general formula (12), general formula (13), general formula (14) or general formula (15),
Y2For hydrogen atom or-COOH, Y3And Y4In any one be base shown in the following general formula (16) or general formula (17), Y3And Y4 The other of be hydrogen atom or COOR15, R15For hydrogen atom, alkyl, aryl or halogen atom)
[changing 59]
General formula (12)
(in general formula (12), R8For three base of methine, ethylidine or 1,1,2- second)
General formula (13)
[changing 60]
General formula (13)
(in general formula (13), k3It is 1 or 2)
[changing 61]
General formula (14)
(in general formula (14), Q2For be directly bonded or the bilvalent radical of carbon number 1~20)
[changing 62]
General formula (15)
(in general formula (15), R9For alkylidene)
[changing 63]
General formula (16)
(in general formula (16), M1For-NR11Or-O-, R11For hydrogen atom, alkyl or arlydene,
R10For the bilvalent radical in the group as composed by alkylidene, arlydene and alkylene oxide)
[changing 64]
General formula (17)
(in general formula (17), R12、R13Separately for selected from the group as composed by alkylidene, arlydene and alkylene oxide In bilvalent radical,
R14For hydrogen atom, alkyl, aryl or halogen atom)
(methyl) acrylic block obtained by the concrete example (I), concrete example (II), concrete example (III) is total The preferred structure of polymers (C) can utilize the hydrogen atom by the mercapto of single terminal region of general formula (11) to be transformed to polymer (B) the following general formula (18) indicates.
[changing 65]
General formula (18)
(in general formula (18), (A) is (methyl) acrylic acid series polymeric compounds residue,
R16For the bilvalent radical being directly bonded or in the group as composed by alkylidene, arlydene and alkylene oxide,
L3To be directly bonded or-O-C (=O)-,
X3For tetravalence base shown in the following general formula (19), general formula (20), general formula (21) or general formula (22),
Y5For hydrogen atom or-COOH,
Y6And Y7In any one be base shown in the following general formula (23) or general formula (24), Y6And Y7The other of for hydrogen it is former Son or COOR24, R24For hydrogen atom, alkyl, aryl or halogen atom)
[changing 66]
General formula (19)
(in general formula (19), R17For methine, ethylidine or 1,1,2- second, three base)
[changing 67]
General formula (20)
(in general formula (20), k4It is 1 or 2)
[changing 68]
General formula (21)
(in general formula (21), Q3For be directly bonded or the bilvalent radical of carbon number 1~20)
[changing 69]
General formula (22)
(in general formula (22), R18For alkylidene)
[changing 70]
General formula (23)
(in general formula (23), M2For-NR20Or-O-, R20For hydrogen atom or alkyl,
R19For the bilvalent radical in the group as composed by alkylidene, arlydene and alkylene oxide,
It (B) is (methyl) acrylic acid series polymeric compounds residue)
[changing 71]
General formula (24)
(in general formula (24), R21、R22Separately for selected from the group as composed by alkylidene, arlydene and alkylene oxide In bilvalent radical,
R23For hydrogen atom, alkyl, aryl or halogen atom,
It (B) is (methyl) acrylic acid series polymeric compounds residue)
The unsaturated single amount body > of < ethylene
As the unsaturated single amount body of ethylene, such as can enumerate: (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) n-propyl, (methyl) isopropyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) 2-EHA, (methyl) cyclohexyl acrylate, (methyl) stearyl acrylate, (methyl) lauryl (methyl) alkyl-acrylates such as ester, (methyl) acrylic acid 3-methyl cyclohexanol ester, (methyl) isobornyl acrylate；
(methyl) phenyl acrylate, (methyl) benzyl acrylate, (methyl) phenoxyethyl acrylate, phenoxy group diethyl two Alcohol (methyl) acrylate etc. aromatic series (methyl) esters of acrylic acid；
Hetero ring types (methyl) acrylate such as (methyl) tetrahydrofurfuryl acrylate, oxetanes (methyl) acrylate Class；
The poly- alkane of alkoxies such as methoxyl group polypropylene glycol (methyl) acrylate, ethyoxyl polyethylene glycol (methyl) acrylate Glycol (methyl) esters of acrylic acid；
(methyl) acrylamide, N, N- dimethyl (methyl) acrylamide, N, N- diethyl (methyl) acrylamide, N- are different N substituted type (methyl) acrylic amides such as propyl (methyl) acrylamide, diacetone (methyl) acrylamide, acryloyl morpholine
(methyl) acrylic acid N, N- dimethylamino ethyl ester, (methyl) acrylic acid N, N- diethylamino ethyl ester etc. contain amino (methyl) esters of acrylic acid；
And the nitriles such as (methyl) acrylonitrile.
Furthermore in the present embodiment, so-called (methyl) acrylate respectively indicates methacrylate and acrylate, So-called (methyl) acrylamide respectively indicates Methacrylamide and acrylamide.
In addition, as that can be enumerated: styrene, α-methylstyrene with single amount body of the acrylic acid list amount body Equal phenylethylenes；The second such as ethyl vinyl ether, n-propyl vinethene, isopropyl-ethylene ether, n-butyl vinyl ether, isobutylvinyl ether Alkene ethers；The fatty acid ethylenes esters such as vinyl acetate, vinyl propionate.
< polymerization condition >
To (methyl) acrylic acid series polymeric compounds (A1) or (methyl) acrylic acid series polymeric compounds (A1'), (methyl) acrylic acid series The method that polymer (B) is polymerize is not particularly limited, and existing method is polymerize before.In addition, can also appoint Simultaneously use polymerization initiator in meaning ground.But it is not limited to these.To obtain the ethylene of (methyl) acrylic acid series polymeric compounds (B) Property unsaturated single amount body be preferably different compositions from polymer (A1) or polymer (A1').
(methyl) acrylic acid series polymeric compounds (A1) or (methyl) acrylic acid series polymeric compounds (A1'), (methyl) acrylic acid series are poly- The weight average molecular weight for closing object (B) is preferably 1000~500000, and more preferably 2000~50000, and then preferably 2000 ~12000, particularly preferably 3000~8000.
[utilization of polymer (C)]
(methyl) acrylic block copolymer (C) of the invention can be used as pigment dispersing agent, alkali soluble resin, bonding Agent resin and utilize, it is solvable especially to can be used as the pigment dispersing agent for being suitable for colored filter photosensitive coloring composition, alkali Property resin and utilize.In addition, can be used as the pigment dispersing agent for being suitable for printing ink composition, adhesive resin and utilize.
< pigment dispersing agent >
(methyl) acrylic block copolymer (C) can be suitable as pigment dispersing agent.
Pigment dispersing agent include be adsorbed in the colorants such as pigment property colorant compatibility position and with Toner carrier has the solvent compatibility position of compatibility, and plays and be adsorbed in colorant and make colorant in color carrier Dispersion stability effect.In the case where using (methyl) acrylic block copolymer (C) as pigment dispersing agent, example Such as in the manufacturing method, as long as synthesis has following (methyl) acrylic acid series polymeric compounds (A1) or (methyl) acrylic acid series poly- (methyl) the acrylic block copolymer (C) of object (A1') and following (methyl) acrylic acid series polymeric compounds (B) are closed, it is described (methyl) acrylic acid series polymeric compounds (A1) or (methyl) acrylic acid series polymeric compounds (A1') include the second affinity to colorant The unsaturated single amount body of alkene, (methyl) acrylic acid series polymeric compounds (B) include the ethylene insatiable hunger affinity to solvent Body is measured with single.
As pigment dispersing agent, can also be suitble to using with acidic substituent person with any in alkali subtituent person Kind, but in the case where being used as colored filter coloured composition, the dispersion stabilization of alkaline dispersing agent is excellent and preferred.Alkali The amine value of property dispersing agent if 10mgKOH/g or more and 99mgKOH/g hereinafter, then dissolubility becomes well in developer solution, It can develop before the deadline in development step, it in addition will not non-pixel portion remaining pigmentary resin group on substrate The undissolved object of object is closed, therefore preferably.More preferably 50mgKOH/g~90mgKOH/g.
In addition, about (methyl) acrylic block copolymer (C) of the invention, since pigment adsorption base is arranged to high-density Column, thus it is strong to the absorption of pigment, in addition without crosslinking, it is thus ensured that high dispersion stabilization.On the other hand, point of random Powder is thickened because of crosslinking sometimes due to being randomly configured with pigment adsorption base.
Relative to 100 parts by weight of pigment, the content of (methyl) acrylic block copolymer (C) be preferably 1 parts by weight~ 70 parts by weight, and then preferably 10 parts by weight~60 parts by weight.It is in the blending amount of (methyl) acrylic block copolymer (C) In the case where more than 1 parts by weight, it is easy to get the effect of pigment-dispersing.In addition, if 70 parts by weight hereinafter, then using institute When stating coloured composition and making the pattern of pixels of colored filter by photoetching process, alkali-developable becomes good.
(methyl) acrylic block copolymer (C) of the invention not only can ensure that high pigment dispersion stability, but also Pigment dispersing agent especially as colored filter purposes, it can be achieved that before difficult polymolecularity and solvent resistance and deposit.
In addition, not only more easily being set using general than the block copolymer synthesized by active free radical polymerization It is standby to be produced, and used in the resist purposes, it also confirmed that the tremendous ground of alkali-developable is good.Recognize Be for reason: molecular weight distribution specific activity free radical polymerization product design broader, and can maintain block type structure, therefore aobvious Shadow speed improves tremendously because of the influence of low molecular weight compositions.Moreover it is often difficult to be closed using active free radical polymerization 2.0 or more wide block type structure is distributed as at molecular weight, (methyl) acrylic block copolymer (C) of the invention can As new block dispersant.
< has the unsaturated single amount body > of the ethylene of heat cross-linking photocrosslinking reaction functional group
(methyl) acrylic block copolymer (C) of the invention can also in (methyl) acrylic acid series polymeric compounds (A1) or Contain the functional group with heat cross-linking or photocrosslinking reaction in (methyl) acrylic acid series polymeric compounds (B) residue.Be preferably selected from by The different thiocyanic acid ester group of furyl, active methylene group, active methylene, blocked isocyanate ester group, block, oxetanyl, At least one of group composed by tert-butyl, acrylate-based and methacrylate.
Described in being imported in (methyl) acrylic acid series copolymer (A) or (methyl) acrylic acid series copolymer (B) residue Dispersion stabilization or pigment dispersing agent can be improved relative to aobvious as pigment dispersing agent in heat cross-linking photocrosslinking reaction functional group The dissolubility of shadow liquid, and further increase chemical-resistant.
It is polymerize by using the unsaturated single amount body of the ethylene with the functional group, functional group can be imported.
As the unsaturated single amount body of the ethylene with furyl, such as methacrylic acid chaff ester can be enumerated etc..But and It is not limited to these.
It as the unsaturated single amount body of the ethylene of active methylene or active methylene, such as can enumerate: (methyl) Acrylic acid 2- (1,3 dioxo butoxy) ethyl ester, (methyl) acrylic acid 2- (1,3 dioxo butoxy) propyl ester, (methyl) propylene Sour 3- (1,3 dioxo butoxy) propyl ester, (methyl) acrylic acid 2- (1,3 dioxo butoxy) butyl ester, (methyl) acrylic acid 3- (1,3 dioxo butoxy) butyl ester, (methyl) acrylic acid 4- (1,3 dioxo butoxy) butyl ester etc..But it is not limited to this A bit.
So-called blocked isocyanate ester group or the different thiocyanic acid ester group of block refer to isocyanate group or different thiocyanic acid ester group The protecting group that is detached from and using heating and the structure for carrying out block, block is detached from high temperature, and generates isocyanates Base or different thiocyanic acid ester group.
These and hydroxyl etc. carry out cross-linking reaction, therefore are preferably used in combination with hydroxyl etc..In addition, if every with pigment dispersing agent One molecule is averagely counted blocked isocyanate ester group being set as a, and hydroxyl is set as b, then preferably a × b is 2 or more, more excellent It is selected as 5 or more.
Body is measured as with the unsaturated list of the ethylene of isocyanate group or different thiocyanic acid ester group, such as can be enumerated: (first Base) propenoyl isocyanate, (methyl) acrylic acid 2- isocyanatoethyl methacrylate, 2- (methyl) acryloyloxyethoxy ethyl be different Cyanate, 1,1- (bis- (methyl) acryloyloxymethyls) ethyl isocyanate, (methyl) acryloyl group phenyl isocyanate Deng (methyl) esters of acrylic acid containing isocyanate group；Alpha, alpha-dimethyl -4- isopropenyl benzyl isocyanates etc. is containing different Styrene derived species of cyanic acid ester group etc..But it is not limited to these.
It as the unsaturated single amount body of the ethylene with oxetanyl, such as can enumerate: oxetanes (methyl) The unsaturated single amount body of the ethylene such as acrylate, (3- Ethyloxetane -3- base) methacrylate.But it is and unlimited Due to these.
As the unsaturated single amount body of the ethylene with tert-butyl, such as Tert-butyl Methacrylate, acrylic acid can be enumerated Tert-butyl ester etc..But it is not limited to these.
As acrylate-based and methacrylate method is imported, method etc. can be listed below: by making to have There are the unsaturated single amount body of the ethylene of hydroxyl and a part of the unsaturated single amount body of ethylene to be copolymerized and obtained with hydroxyl (methyl) acrylic acid series polymeric compounds (A1) or (methyl) acrylic acid series polymeric compounds (B) after, make the hydroxyl whole or one Point with there is isocyanate group or different thiocyanic acid ester group (methyl) acrylate in isocyanate group or different thiocyanic acid Ester group reaction.But it is not limited to these.
By using these heat cross-linking photocrosslinking reaction functional group, pigment dispersing agent of the invention is to comprising described It can get after pigment dispersing agent and coloured composition the progress thermmohardening photo-hardening of heat cross-linking photocrosslinking reaction functional group excellent Different chemical-resistant, solvent resistance, heat resistance, alkali resistance.Its reason is: passing through heat cross-linking photocrosslinking reaction functional group (respectively furyl, active methylene group or active methylene, blocked isocyanate ester group, oxetanyl, tert-butyl, propylene Perester radical and methacrylate) burn-back and be crosslinked.
Heat cross-linking photocrosslinking reaction functional group is preferably in composition (methyl) acrylic acid series copolymer (A1) or (methyl) 5 moles of %~90 mole % are used in total 100 moles of % of the unsaturated single amount body of the ethylene of acrylic acid series copolymer (B), Particularly preferably use 20 moles of %~60 mole %.If less than 5 moles of %, the effect being crosslinked is few, if more than 90 moles %, Then polymer can cause cross-linking reaction in synthesis and gelation occurs sometimes.
< colorant >
It, can be from existing various pigment before and dyestuff as workable colorant in coloured composition of the invention Arbitrarily select.These pigment dyes can be used alone, or is optionally used in mixed way with arbitrary ratio two or more.
About the content of colorant, on the basis of all nonvolatile components of coloured composition (100 weight %), just obtain For the viewpoint of sufficient colorrendering quality, preferably 10 weight % or more, more preferably 15 weight % or more, most preferably 20 Weight % or more.In addition, for the viewpoint of the stability of coloured composition, preferred colorant content be 90 weight % with Under, more preferably 80 weight % are hereinafter, most preferably 70 weight % or less.
< organic pigment >
As colorant, the concrete example for the pigment that can be used when forming the pixel of colored filter is shown.
It as red pigment, such as can enumerate: color index (Color Index, C.I.) paratonere (Pigment Red) 1, C.I. paratonere 2, C.I. pigment red 3, C.I. pigment red 4, C.I. paratonere 5, C.I. paratonere 6, C.I. paratonere 7, C.I. pigment Red 8, C.I. Pigment Red 9, C.I. paratonere 12, C.I. paratonere 14, C.I. paratonere 15, C.I. paratonere 16, C.I. paratonere 17, C.I. pigment red 21, C.I. paratonere 22, C.I. paratonere 23, C.I. pigment red 31, C.I. paratonere 32, C.I. pigment red 37, C.I. pigment red 38, C.I. pigment red 41, C.I. pigment red 47, C.I. pigment red 48, C.I. pigment Red 48:1, C.I. pigment red 4 8:2, C.I. pigment red 4 8:3, C.I. pigment red 4 8:4, C.I. pigment red 49, C.I. paratonere 49:1, C.I. pigment red 4 9:2, C.I. paratonere 50:1, C.I. paratonere 52:1, C.I. paratonere 52:2, C.I. paratonere 53, C.I. paratonere 53:1, C.I. paratonere 53:2, C.I. paratonere 53:3, C.I. paratonere 57, C.I. paratonere 57:1, C.I. paratonere 57:2, C.I. paratonere 58:4, C.I. paratonere 60, C.I. paratonere 63, C.I. paratonere 63:1, C.I. face Expect red 63:2, C.I. paratonere 64, C.I. paratonere 64:1, C.I. paratonere 68, C.I. paratonere 69, C.I. pigment red 81, C.I. pigment red 81: 1, C.I. pigment red 81: 2, C.I. pigment red 81: 3, C.I. pigment red 81: 4, C.I. pigment Red 83, C.I. Pigment Red 88, C.I. Pigment Red 9 0:1, C.I. paratonere 101, C.I. paratonere 101:1, C.I. paratonere 104, C.I. pigment Red 108, C.I. paratonere 108:1, C.I. paratonere 109, C.I. pigment red 112, C.I. paratonere 113, C.I. paratonere 114, C.I. pigment red 122, C.I. pigment red 123, C.I. paratonere 144, C.I. pigment red 146, C.I. paratonere 147, C.I. pigment red 149, C.I. paratonere 151, C.I. paratonere 166, C.I. paratonere 168, C.I. paratonere 169, C.I. face Expect red 170, C.I. paratonere 172, C.I. paratonere 173, C.I. paratonere 174, C.I. paratonere 175, C.I. paratonere 176, C.I. paratonere 177, C.I. paratonere 178, C.I. pigment red179, C.I. paratonere 181, C.I. paratonere 184, C.I. paratonere 185, C.I. paratonere 187, C.I. paratonere 188, C.I. paratonere 190, C.I. paratonere 193, C.I. face Expect red 194, C.I. paratonere 200, C.I. paratonere 202, C.I. paratonere 206, C.I. Pigment Red 207, C.I. paratonere 208, C.I. paratonere 209, C.I. pigment red 21 0, C.I. pigment red 21 4, C.I. pigment red 21 6, C.I. paratonere 220, C.I. paratonere 221, C.I. paratonere 224, C.I. paratonere 230, C.I. paratonere 231, C.I. paratonere 232, C.I. face Expect red 233, C.I. paratonere 235, C.I. paratonere 236, C.I. paratonere 237, C.I. paratonere 238, C.I. paratonere 239, C.I. paratonere 242, C.I. paratonere 243, C.I. paratonere 245, C.I. paratonere 247, C.I. paratonere 249, C.I. paratonere 250, C.I. paratonere 251, C.I. paratonere 253, C.I. paratonere 254, C.I. paratonere 255, C.I. face Expect red 256, C.I. paratonere 257, C.I. paratonere 258, C.I. paratonere 259, C.I. paratonere 260, C.I. paratonere 262, C.I. paratonere 263, C.I. paratonere 264, C.I. paratonere 265, C.I. paratonere 266, C.I. paratonere 267, C.I. paratonere 268, C.I. paratonere 269, C.I. paratonere 270, C.I. paratonere 271, C.I. paratonere 272, C.I. face Expect red 273, C.I. paratonere 274, C.I. paratonere 275, C.I. paratonere 276 etc..
In these, for obtaining viewpoint of the high contrast than, high brightness, preferably C.I. pigment red 4 8:1, C.I. face Expect red 122, C.I. paratonere 168, C.I. paratonere 177, C.I. paratonere 202, C.I. paratonere 206, C.I. paratonere 207, C.I. paratonere 209, C.I. paratonere 224, C.I. paratonere 242 or C.I. paratonere 254, and then preferably C.I. face Expect red 177, C.I. paratonere 209, C.I. paratonere 224, C.I. paratonere 242 or C.I. paratonere 254.
It as blue pigment, such as can enumerate: C.I. pigment blue 1, C.I. pigment blue 1: 2, C.I. pigment blue 9, C.I. face Material basket 14, C.I. pigment blue 15, C.I. pigment blue 15: 1, C.I. pigment blue 15: 2, C.I. pigment blue 15: 3, C.I. pigment blue 15:4, C.I. pigment blue 15: 6, C.I. pigment blue 16, C.I. pigment blue 17, C.I. pigment blue 19, C.I. pigment blue 25, C.I. Pigment blue 27, C.I. pigment blue 28, C.I. pigment blue 29, C.I. pigment blue 33, C.I. pigment blue 35, C.I. pigment blue 36, C.I. pigment blue 56, C.I. pigment blue 56:1, C.I. pigment blue 60, C.I. pigment Blue-61, C.I. pigment Blue-61: 1, C.I. pigment Blue 62, C.I. pigment blue 63, C.I. pigment blue 66, C.I. pigment blue 67, C.I. pigment blue 68, C.I. pigment blue 71, C.I. face Material basket 72, C.I. pigment blue 73, C.I. pigment blue 74, C.I. pigment blue 75, C.I. pigment blue 76, C.I. pigment blue 78, C.I. Pigment blue 79 etc..In these, for obtaining viewpoint of the high contrast than, high brightness, preferably C.I. pigment blue 15, C.I. face Material basket 15:1, C.I. pigment blue 15: 2, C.I. pigment blue 15: 3, C.I. pigment blue 15: 4 or C.I. pigment blue 15: 6, Jin Eryou It is selected as C.I. pigment blue 15: 6.In addition, it is possible to use Japanese Patent Laid-Open 2004-333817 bulletin, Japanese Patent No. Aluminium phthalocyanine color recorded in No. 4893859 bulletins etc. etc., is not particularly limited to these.
It as viridine green, such as can enumerate: C.I. naphthol green 1, C.I. naphthol green 2, C.I. naphthol green 4, C.I. pigment Green 7, C.I. naphthol green 8, C.I. naphthol green 10, C.I. naphthol green 13, C.I. naphthol green 14, C.I. naphthol green 15, C.I. pigment Green 17, C.I. naphthol green 18, C.I. naphthol green 19, C.I. naphthol green 26, C.I. pigment green 36, C.I. naphthol green 45, C.I. face Expect green 48, C.I. naphthol green 50, C.I. naphthol green 51, C.I. naphthol green 54, C.I. naphthol green 55 or C.I. naphthol green 58.These In, for obtaining viewpoint of the high contrast than, high brightness, preferably C.I. pigment Green 7, C.I. pigment green 36 or C.I. pigment Green 58.In addition, it is possible to use Japanese Patent Laid-Open 2008-19383 bulletin, Japanese Patent Laid-Open 2007-320986 bulletin, The ZnPc pigment etc. recorded in Japanese Patent Laid-Open 2004-70342 bulletin etc., is not particularly limited to these.
In these blue pigments or viridine green, especially zinc halide phthalocyanine color or aluminium phthalocyanine color, which can get, utilizes other Viridine green and none obtained high spectral transmission, wide color reproduction region, if but these pigment and the face that uses before Material is compared, with the slightly worse problem of heat resistance, solvent resistance.But even if being the coloured composition for having used these pigment, It can be dispersed by using (methyl) the acrylic block copolymer (C) as present invention and to obtain stability good Good and coloured composition with excellent heat resistance, solvent resistance.
In addition, in green coloring composition and yellow uitramarine can be used.As can yellow uitramarine, can enumerate: C.I. pigment yellow 1, C.I. pigment yellow 2, C.I. pigment yellow 3, C.I. pigment yellow 4, C.I. pigment yellow 5, C.I. pigment yellow 6, C.I. Pigment yellow 10, C.I. pigment Yellow 12, C.I. pigment yellow 13, C.I. pigment Yellow 14, C.I. pigment yellow 15, C.I. pigment yellow 16, C.I. pigment yellow 17, C.I. pigment yellow 18, C.I. pigment yellow 24, C.I. pigment yellow 31, C.I. pigment yellow 32, C.I. pigment yellow 34, C.I. pigment yellow 35, C.I. pigment yellow 35:1, C.I. pigment yellow 36, C.I. pigment yellow 36:1, C.I. pigment yellow 37, C.I. Pigment yellow 37:1, C.I. pigment yellow 40, C.I. pigment yellow 42, C.I. pigment yellow 43, C.I. pigment yellow 53, C.I. pigment yellow 55, C.I. pigment yellow 60, C.I. pigment yellow 61, C.I. pigment yellow 62, C.I. pigment yellow 63, C.I. pigment yellow 65, C.I. pigment yellow 73, C.I. pigment yellow 74, C.I. pigment yellow 77, C.I. pigment yellow 81, C.I. pigment yellow 83, C.I. pigment yellow 93, C.I. pigment Yellow 94, C.I. pigment yellow 95, C.I. pigment yellow 97, C.I. pigment yellow 98, C.I. pigment yellow 100, C.I. pigment yellow 101, C.I. Pigment yellow 104, C.I. pigment yellow 106, C.I. pigment yellow 108, C.I. pigment yellow 109, C.I. pigment yellow 110, C.I. pigment yellow 113, C.I. pigment yellow 114, C.I. pigment yellow 115, C.I. pigment yellow 116, C.I. pigment yellow 117, C.I. pigment yellow 118, C.I. pigment yellow 119, C.I. pigment Yellow 12 0, C.I. pigment Yellow 12 3, C.I. pigment Yellow 12 6, C.I. pigment Yellow 12 7, C.I. face Expect yellow 128, C.I. pigment Yellow 12 9, C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 147, C.I. pigment yellow 150, C.I. pigment yellow 151, C.I. pigment yellow 152, C.I. pigment yellow 153, C.I. pigment yellow 154, C.I. pigment yellow 155, C.I. pigment yellow 156, C.I. pigment yellow 161, C.I. pigment yellow 162, C.I. pigment yellow 164, C.I. pigment yellow 166, C.I. face Expect yellow 167, C.I. pigment yellow 168, C.I. pigment yellow 169, C.I. pigment yellow 17 0, C.I. pigment yellow 17 1, C.I. pigment yellow 172, C.I. pigment yellow 17 3, C.I. pigment yellow 17 4, C.I. pigment yellow 17 5, C.I. pigment yellow 17 6, C.I. pigment yellow 17 7, C.I. pigment yellow 17 9, C.I. pigment yellow 180, C.I. pigment yellow 181, C.I. pigment yellow 182, C.I. pigment yellow 185, C.I. face Expect yellow 187, C.I. pigment yellow 188, C.I. pigment yellow 193, C.I. pigment yellow 194, C.I. pigment yellow 198, C.I. pigment yellow 199, C.I. pigment yellow 213, C.I. pigment yellow 214, C.I. pigment yellow 218, C.I. pigment yellow 219, C.I. pigment yellow 220, C.I. pigment yellow 221 etc..Wherein, it is preferable to use selected from C.I. pigment yellow 13 8, C.I. pigment yellow 13 9, C.I. pigment yellow 150, C.I. one or more of pigment yellow 185.
That is, preferably containing zinc halide phthalocyanine color and aluminium phthalocyanine face as the colorant for being used as green coloring composition The excellent person of color characteristics can be made and further containing yellow uitramarine at least any one in material.
As the ratio of particularly preferred pigment, such as the case where having used zinc halide phthalocyanine color and yellow uitramarine Under, on the basis of the total weight of pigment composition, zinc halide phthalocyanine color is the 50 weight % of weight %~100, and yellow uitramarine is 0 weight The weight % of %~50 is measured, more preferably on the basis of the total weight of pigment composition, zinc halide phthalocyanine color is 50 weight %~90 Weight %, yellow uitramarine are 5 weight of weight %~45 %.
In addition, in the case where having used aluminium phthalocyanine color and yellow uitramarine, on the basis of the total weight of pigment composition, aluminium Phthalocyanine color is the 5 weight % of weight %~70, and yellow uitramarine is the 30 weight % of weight %~95, more preferably with pigment composition On the basis of total weight, aluminium phthalocyanine color is the 15 weight % of weight %~60, and yellow uitramarine is 40 weight of weight %~85 %.
When further finding out broader color reproduction region, and with zinc halide phthalocyanine color and aluminium phthalocyanine color and Huang This three kinds of color pigment.As the ratio of preferred pigment, on the basis of the total weight of pigment composition, zinc halide phthalocyanine color is 50 The weight % of weight %~100, aluminium phthalocyanine color are the 0 weight % of weight %~50, and yellow uitramarine is 0 weight of weight %~50 %.
More preferably on the basis of the total weight of pigment composition, zinc halide phthalocyanine color is the 50 weight % of weight %~90, Aluminium phthalocyanine color is the 5 weight % of weight %~45, and yellow uitramarine is 5 weight of weight %~45 %.The structure of the pigment can be passed through Chroma areas is set to broaden extensively at ratio.
It as violet pigment, such as can enumerate: C.I. pigment violet 1, C.I. pigment violet 1: 1, C.I. pigment violet 2, C.I. face Expect purple 2:2, C.I. pigment violet 3, C.I. pigment violet 3: 1, C.I. pigment violet 3: 3, C.I. pigment violet 5, C.I. pigment violet 5:1, C.I. pigment violet 14, C.I. pigment violet 15, C.I. pigment violet 16, C.I. pigment violet 19, C.I. pigment Violet 23, C.I. pigment violet 25, C.I. pigment violet 27, C.I. pigment violet 29, C.I. pigment violet 31, C.I. pigment violet 32, C.I. pigment violet 37, C.I. pigment Purple 39, C.I. pigment violet 42, C.I. pigment violet 44, C.I. pigment violet 47, C.I. pigment violet 49, C.I. pigment violet 50 etc..These In, for obtaining viewpoint of the high contrast than, high brightness, preferably C.I. pigment violet 19 or C.I. pigment Violet 23, Jin Eryou It is selected as C.I. pigment Violet 23.
< dyestuff >
In order to mix colours in pigment dispersing agent, dyestuff can be contained in the range of declining heat resistance.
Commonly known as there is no particular restriction by dyestuff person, as dyestuff, wherein triphenyl methane based dye, triphen can be used Methylmethane system mordant pigment, diphenyl methane based dye, diphenylmethane mordant pigment, quinoline based dye, quinoline system pigment, Thiazine based dye, thiazole based dye, xanthene based dye, xanthene system mordant pigment, diketopyrrolopyrrolecocrystals system pigment etc..
In these, it is preferable to use the xanthene system pigment as xanthene based dye, xanthene system mordant pigment；As quinoline system The quinoline system pigment of dyestuff, quinoline system pigment；As triphenyl methane based dye, the triphenyl of triphenyl methane system mordant pigment Methaneseries pigment；Diketopyrrolopyrrolecocrystals system pigment as diketopyrrolopyrrolecocrystals system pigment.Especially in visible light It has been used in region in the case where carrying out the luminous pigment of fluorescent, the excellent effect of the colored filter of high contrast ratio is made.
< pigment derivative >
Pigment dispersion of the invention can also include in turn pigment derivative, by using pigment derivative, prevent from dispersing The effect of pigment afterwards re-united is big, and brightness and viscosity stability become well, therefore preferably.It, can as pigment derivative It enumerates in organic pigment, anthraquinone, acridone or triazine and has imported alkali subtituent, acidic substituent or can have a substituent group Compound obtained by phthalimide methyl.
About the content of pigment derivative, for the viewpoint that dispersibility improves, relative to 100 parts by weight of pigment, preferably More than 0.5 parts by weight, and then more than preferably 1 parts by weight, more than most preferably 3 parts by weight.In addition, with regard to heat resistance, fast light Property viewpoint for, preferably 40 parts by weight hereinafter, in turn be preferably 35 parts by weight below.
In pigment derivative, using the acid derivant of organic pigment or its metal salt, i.e. pigment derivative this Situation, due to excellent in stability, preferably.The acid derivant of organic pigment or its metal salt further promote pigment and face Expect the pigment adsorption of dispersing agent, and improve the dispersibility of pigment, therefore prevents the effect of the pigment after dispersion re-united big.Cause This, the face made of having used using the acid derivant of organic pigment or its metal salt and having dispersed pigment in pigment carrier In the case where expecting dispersion coloured composition, the colored filter of excellent in stability can get.In turn, by with as (methyl) The pigment dispersing agent of acrylic block copolymer (C) uses simultaneously, and dispersibility further increases, (methyl) acrylic acid series Block copolymer (C) includes: (methyl) acrylic acid series polymeric compounds (A1) with said solvophilic and the function with nitrogen atom (methyl) acrylic acid series polymeric compounds (B) of base.Think that its reason is: the acidity by being configured at the derivative near pigment takes The soda acid base phase interaction of the alkali subtituent of Dai Jiyu dispersing agent and the pigment adsorption for promoting dispersing agent.
It is the following general formula (25) compound represented as the structure of the acid derivant of organic pigment or its metal salt.
General formula (25)
V-Zd
(wherein, in general formula (25), V: organic pigment residue, Z: acidic substituent, d: hydrogen atom or metal ion)
It as the organic pigment for the organic pigment residue for constituting V, such as can enumerate: diketopyrrolopyrrolecocrystals system pigment； The azo pigments such as azo, bisazo, polyazo；Copper phthalocyanine, halogenated copper phthalocyanine, ZnPc, halogenation ZnPc, metal-free phthalocyanine Equal phthualocyanine pigments；Amino anthraquinones, diamino bi-anthraquinone, anthracene pyrimidine, yellow scholar's ketone (flavanthrone), anthanthrone, yin are red The anthraquione pigmentss such as intellectual circle, pyranthrone, violanthrone；Quinacridone pigment；Dioxazine pigment；Purple cyclic ketones (perinone) system Pigment；It is pigment；Thioindigo system pigment；Isoindoline system pigment；Isoindolinone pigment；Restoring (threne) is face Material；Quinophthalone system pigment；Dioxazine pigment；Metal complex system pigment etc..
The acid derivant of organic pigment or its metal salt can be independent, also may include acid derivant and metal salt this two Person, can also be respectively using two or more or be used in mixed way with other pigment derivatives.
< organic solvent >
Organic solvent is used to be coated and be easy in such a way that the dry film thickness of pigment dispersion becomes 0.2 μm~5 μm Form filter segments.It as organic solvent, is not particularly limited, those existing can will be used alone before or optionally with any Ratio be used in mixed way it is two or more.
About the content of organic solvent, pigment dispersing agent is just adjusted to viscosity appropriate and can be formed as the equal of target For the filter segments of even film thickness, preferably relative to 100 parts by weight of pigment with 800 parts by weight~4000 parts by weight amount It uses.
< alkali soluble resin >
In the present invention, the alkali soluble resin that can further add is Alkali-developable resin, has carboxylic in its structure The acidic groups such as base, it is soluble that using alkaline aqueous solution, acidic group, which is neutralized and for water, and can be developed.
As alkali soluble resin, can be used has the photoresist of photonasty base or the non-senses such as unsaturated bond base Photosensitiveness resin.It as the concrete example of photoresist, can enumerate: photonasty thermoprene system resin, photonasty phenol resin, sense Photosensitiveness polyacrylate system resin, photonasty polyamide resin, photosensitive polyimide system resin and unsaturated polyester system tree Rouge, polyester acrylate system resin, polycyclic oxygroup acrylic ester resin, polyacrylic acid ammonia carbamate system resin, polyethers third Olefin(e) acid ester system resin, polyalcohol acrylate system resin etc..It as the concrete example of non-photosensitive resin, can enumerate: cellulose second Acid esters system resin, nitrocellulose prime system resin, polystyrene (total) polymers, polyvinyl butyral system resin, alkyd amino system resin, Polyester based resin, amino resins modified poly ester system resin, polyurethanes system resin, acrylic polyol carbamate system Resin, soluble polyamide system resin, soluble polyimide system resin, soluble polyamide imide series resin, solubility Polyesterimide system resin, hydroxy ethyl cellulose, styrene-maleic acid ester based copolymer, (methyl) acrylic ester (total) Polymers etc..These alkali soluble resins, which can be used alone, one kind or to be applied in combination two or more.Furthermore pigment colorant combines The content of alkali soluble resin in object is preferably 5 mass parts~300 mass parts relative to 100 mass parts of pigment, in turn Preferably 10 mass parts~100 mass parts.
In addition, it is possible to use (methyl) acrylic acid series copolymer (C) of the invention is used as alkali soluble resin.
By photosensitive composite or sense that (methyl) acrylic acid series copolymer (C) of the invention is used as to alkali soluble resin Photosensitiveness coloured composition and the pattern form that obtains is good, developing powder is also fast, is suitable for colored filter purposes.
Think that its reason is: (methyl) acrylic acid series copolymer by using block structure in alkali soluble resin (C), though reason is indefinite, presenceization is locally biased to by position of developing, the resists performance such as developability improves.In addition, Compared to the block of the narrow molecular weight distribution synthesized using the active free radical polymerization for being combined with identical composition, molecular weight etc. For type alkali soluble resin, that there are developing performances is further for (methyl) acrylic acid series copolymer (C) newly developed in the present invention The tendency of goodization.Speculate that reason is: due to speculating molecular weight distribution than the block type alkali using active free radical polymerization synthesis Soluble resin is broad, and can carry out polymeric synthesis, therefore low molecular weight in the state of certainly maintaining block structure Ingredient effectively plays a role for developability raising.
< Photoepolymerizationinitiater initiater >
In photosensitive coloring composition of the invention, in order to harden the composition by ultraviolet light irradiation, and Filter segments are formed by photoetching process, Photoepolymerizationinitiater initiater can be added and combined with solvent development type or alkali developable photosensitive color It is prepared by the form of object.
As Photoepolymerizationinitiater initiater, acetophenone based compound, styrax based compound, benzophenone series chemical combination can be used Object, thioxanthones based compound, thioxanthones based compound, triazine based compound, oxime ester based compound, phosphine based compound, quinone system Close object, borate based compound, carbazole based compound, imidazole compound or titanocenes based compound etc..These photopolymerization are drawn Hair agent can be used alone a kind of or is optionally used in mixed way with arbitrary ratio two or more.
In these, as Photoepolymerizationinitiater initiater, preferably comprising selected from by acetophenone based compound, phosphine based compound, miaow At least one of group composed by azole compounds and oxime ester based compound Photoepolymerizationinitiater initiater.It is poly- by the inclusion of these light Initiator is closed, the pattern form and linearity of filter segments become better.
The content of Photoepolymerizationinitiater initiater is preferably 5 parts by weight~200 parts by weight relative to 100 parts by weight of pigment, just For the viewpoint of photo-hardening and developability, more preferably 10 parts by weight~150 parts by weight.
< photopolymerizable compound >
Comprising carrying out hardening spanning tree by ultraviolet light or heat etc. in the photopolymerizable compound being used in the present invention The monomer or oligomer of rouge.It as photopolymerizable compound, such as can enumerate: (methyl) methyl acrylate, (methyl) acrylic acid Ethyl ester, (methyl) ethyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) third Olefin(e) acid cyclohexyl, (methyl) P-carboxy ethyl acrylates, polyethylene glycol two (methyl) acrylate, 1,6-HD two (methyl) Acrylate, triethylene glycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, trimethylolpropane tris (first Base) acrylate, pentaerythrite three (methyl) acrylate, 1,6 hexanediol diglycidylether two (methyl) acrylate, Bisphenol A diglycidyl ether two (methyl) acrylate, neopentylglycol diglycidyl ether two (methyl) acrylate, two seasons penta Tetrol six (methyl) acrylate, (methyl) tricyclodecyl acrylate, ester acrylate, methylolated melamine (methyl) Various acrylate and the methacrylates such as acrylate, (methyl) acrylic acid epoxy ester, propenoic methyl carbamate, (first Base) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythrite triethylene ether, (methyl) acrylamide, N- hydroxymethyl (methyl) acrylamide, N- vinyl formamide, acrylonitrile etc..These can individually make With or be used in mixed way two or more.These photopolymerizable compounds can be used alone a kind of or optionally with arbitrary ratio It is used in mixed way two or more.
The content of optical polymerism list amount body is preferably 10 parts by weight~300 parts by weight relative to 100 parts by weight of pigment, For the viewpoint of photo-hardening and developability, more preferably 10 parts by weight~200 parts by weight.
< other compositions >
Other dispersing agents, sensitizer, multi-functional thiol, ultraviolet light can be contained in photosensitive coloring composition of the invention Absorbent, polymerization inhibitor, storage stabilizer.In addition, can be coupled containing silane to improve the adhesion with transparent substrate etc. Agent etc. touches enhancer or has the function of the amine compound restored to the molten oxygen deposited.
The preparation method > of < photosensitive coloring composition
Photosensitive coloring composition of the invention can manufacture as follows, that is, use three-roll mill, twin-roll mill, sand The various dispersal devices such as grinding machine, kneader, grater imperceptibly disperse pigment in adhesive tree together with pigment dispersing agent In the color carrier and/or solvent of rouge etc., thus the dispersion that makes paints, and light is mixed in the pigment dispersion Polymerization initiator, photonasty adhesive resin, photopolymerizable compound, sensitizer optionally, multi-functional thiol, ultraviolet light are inhaled Receive agent, polymerization inhibitor, storage stabilizer, solvent, other compositions and manufactured.In addition, including two or more pigment Photosensitive coloring composition can mix imperceptibly disperses each pigment dispersion in color carrier and/or solvent respectively Person, and then Photoepolymerizationinitiater initiater or photopolymerizable compound etc. is mixed and is manufactured.
< colored filter >
Secondly, being illustrated to colored filter of the invention.Colored filter of the invention has on substrate by this The colored filter of invention is formed by filter segments with coloured composition, such as can have black matrix" and Red lightscreening plate Section, green filter segment, blue filter segment.The filter segments can also be and then have magenta filter section, cyan filter Mating plate section and Yellow filter segment person.
As the substrate of transparent substrate etc., glass plate or polycarbonate can be used, polymethyl methacrylate, gather to benzene The resin plates such as dioctyl phthalate second diester.In addition, can also be for the liquid crystal drive after panelization and on the surface of glass plate or resin plate Form the transparent electrode comprising indium oxide, tin oxide etc..
As the forming method using photolithographic assorted filter segments, applied by injection coating, rotary coating, slit The coating methods such as cloth, print roll coating, the photonasty that will be prepared as solvent development type or alkali developable coloring anticorrosive additive material Coloured composition is coated on transparent substrate in such a way that dry film thickness becomes 0.2 μm~10 μm, and is dried.Thereafter, thoroughly It crosses the mask with defined pattern and carries out ultraviolet exposure.
Thereafter, it can be impregnated in solvent or alkaline developer, or by injection etc. come spray development liquid and by unhardened portion It removes and forms required pattern, to form filter segments.In turn, in order to promote the filter segments formed by development Polymerization, can also optionally implement to heat.According to photoetching process, precision can be formed compared with the higher filter segments of print process.
In development, as alkaline developer, the aqueous solution of sodium carbonate, sodium hydroxide etc. can be used, it is possible to use dimethyl The organic bases such as benzyl amine, triethanolamine.In addition, defoaming agent or surfactant can also be added in developer solution.At development Reason method, can be using spray development method, spray developing method, dipping (dip) development method, sheathed immersion (puddle) development method Deng.
, can also be after dry by photosensitive coloring composition coating furthermore in order to improve ultraviolet exposure sensitivity, it will Water-soluble or alkali soluble resin is coated with drying such as polyvinyl alcohol or water soluble acrylic resin, is foring anti-block After the film that caused polymerization hinders, ultraviolet exposure is carried out.
Colored filter of the invention can be manufactured other than the method by electrodeposition process, transfer printing etc..
< adhesive resin >
So-called resin refers to adding in various pigment, ceramics, non-woven fabrics, fiber, leather, paper, ink, coating, metal etc. Can be used as excipient, solid, sticking agent and user in work, also comprising acrylic resin, polyester resin, polyamide, The alcohol such as polyurethane resin, cellulose soluble resin, water-soluble resin etc..But it is not limited to these.
< printing ink composition >
So-called printing ink composition of the invention refers to comprising to print ink as the base gravure ink of representative, flexible ink, net Printing ink, plate ink, ultraviolet light (ultraviolet, UV) constrictive type ink, metallic printing ink, conductive ink, other The composition of functional ink.But it is not limited to these.
< polymer (A2) utilizes >
(methyl) acrylic acid series polymeric compounds (A2) of the invention are used as compound block and are total to using the reactivity of anhydride group The precursor of polymers.For example, being chemically reacted by the reactive functional group with other resins, hold with the Composite of various resins Easily, it can get compound block copolymer.
As the specific gimmick to obtain compound block copolymer, for example, can by with have in main chain or side chain can It is easy acrylic resin, the carbamate resins, polyester tree of the functional group chemically reacted with anhydride groups such as hydroxyl or amino The resins such as rouge, polyamide are mixed and are chemically reacted, and are easy to get compound block resin.
Compound block copolymer can enumerate diblock copolymer, triblock copolymer, segmented copolymer, graft copolymer Deng, but it is not limited to these.
In addition, reactivity and the conduct of anhydride group can also be used in described (methyl) acrylic acid series polymeric compounds (A2) of the invention Various surface modifiers or smears and utilize.For example, can be by (methyl) acrylic acid series polymeric compounds (A2) of the invention and pigment Or the hydroxyl or amino isoreactivity functional group's Composite of dyestuff, and as the surface modifier (pigment point using chemical bonded refractory Powder) and utilize, or can also by reacting and carrying out Composite with the functional group of the substrate surfaces such as packaging material or encapsulation, and It is utilized as new functionalized smears such as barrier performance or abrasion resistence etc. is assigned.But it is not limited to these gimmicks.
< has used the pigment dispersing agent of (methyl) acrylic acid series polymeric compounds (A2) for having anhydride group in single terminal region >
The pigment dispersing agent that described (methyl) acrylic acid series polymeric compounds (A2) of the invention are utilized is carried out specifically It is bright.For example, if azo pigments, then in the knot of the pigment such as paratonere (Pigment Red) 57.1 or pigment red 48, pigment red 49 In structure there is hydroxyl can make by being chemically reacted with the anhydride group of (methyl) acrylic acid series polymeric compounds (A2) of the invention It is utilized for surface modifier (pigment dispersing agent).In addition, not only printing ink application, but also in colored filter resist Used in can also realize same situation in organic pigment.As use be utilized it is of the invention single terminal region have acid The advantages of pigment dispersing agent of (methyl) acrylic acid series polymeric compounds (A2) of anhydride group, with regard to the simplification of the dispersion steps of resin treatment Or can also be without using the viewpoint of pigment derivative etc. for, it is believed that serviceability is also high in high brightness etc..In addition to this, with Cellulose nano-fibrous or colloidal silica is also to have hydroxyl in silicide of representative etc., is consistent with the content.But and It is not limited to these.
< has used the surface modifier of (methyl) acrylic acid series polymeric compounds (A2) for having anhydride group in single terminal region Or smears >
The surface modifier or smears that described (methyl) acrylic acid series polymeric compounds (A2) of the invention are utilized are carried out Detailed description.Specifically, the surface grafting gimmick as macromolecular chain, it can be used as to be utilized and " be grafted to (Grafting-to) surface modifier or smears of method " and utilize.For example, passing through the table in glass with hydroxyl etc. etc. Face applies (methyl) acrylic acid series polymeric compounds (A2) of the invention as priming paint, can be easy to utilize as surface modifier.
< purposes >
(methyl) acrylic block copolymer of the invention can be used in various uses with wherein mesosome condensate.Example Such as, the pigment dispersing agent of the colored filter that can be used for having been described above etc., surface of pigments handle dyestuff salt manufacturing tree Rouge, resist, quantum dot, self-organization monomolecular film, viscous solid, lubricant, coating, ink, packing timber, medicament, pesticide The production of agent, personal nursing (hair liquid cosmetics), semiconductor, display etc..
[embodiment]
Hereinafter, carrying out more specific description to the present invention by embodiment, but embodiment below is not to of the invention Interest field imposes any restrictions.Furthermore " part " expression " parts by weight " in embodiment, " % " expression " weight % ".
In addition, the measuring method of the weight average molecular weight (Mw) of resin, amine value, acid anhydrides valence is as described below.
< weight average molecular weight (Mw) and molecular weight distribution (PDI) >
Use gel permeation chromatography (Gel Permeation Chromatography, GPC) (trade name: GPCV- 2000, Japanese water generation (Japan waters) company manufacture, tubing string: TSKgel, α -3000, mobile phase: 10mM triethylamine/ Dimethyl formamide solution), using polystyrene (molecular weight 427,000,190,000,96,400,37,400,10,200, 2,630,440,92) as standard substance make calibration curve, measure weight average molecular weight (Mw), number average molecular weight (Mn).Molecular weight distribution (PDI=Mw/Mn) is calculated according to the measured value.
< amine value >
Amine value is the aqueous hydrochloric acid solution using 0.1N, and by potential difference measurement find out after, be converted into working as potassium hydroxide Amount.The amine value (mgKOH/g) of amine value expression solid component.
< acid anhydrides valence measures >
Acid anhydrides valence is to find out as follows.Specifically, there is (methyl) acrylic acid series of anhydride group in weighing a (g) Be dissolved in dimethylbenzene after polymer (A2), add b (mmol) anhydride group equivalent more than octyl amine, thus make anhydride group with The reaction of level-one amino.Thereafter, it is cooled to room temperature, and is titrated using the alcohol repellency chloric acid of crossing of 0.1M, thus to the octyl of remaining Amine amount is quantified.If titer is set as c (ml), (methyl) acrylic acid series polymeric compounds (A2) are found out according to the following formula Acid anhydrides valence X.
X=(b-0.1 × c)/a
Then, to pigment dispersing agent, alkali soluble resin used in Examples and Comparative Examples, pigment dispersion, photosensitive The manufacturing method of property coloured composition is illustrated.
Being referred to as raw material used in the synthesis of dispersing agent and alkali soluble resin below is as described below.
PGMEA: propylene glycol methyl ether acetate
AIBN:2,2- azobis isobutyronitrile
MMA: methyl methacrylate
NBMA: n-BMA
FMA: methacrylic acid chaff ester
AAEM:2- acetoacetoxyethyl methacrylate
AOI:2- (acryloxy) ethyl isocyanate
DMAEMA: dimethylaminoethyl methacrylate
BzMA: benzyl methacrylate
MAA: methacrylic acid
St: styrene
GMA: glycidyl methacrylate
The manufacture > of < pigment dispersing agent AB block copolymer (C)
(embodiment 1: block copolymer solution (A-1))
(step (1-1))
In the reaction vessel for having gas introduction tube, thermometer, condenser, blender, be packed into 330 parts of PGMEA and As 160 parts of 160 parts of MMA, the nBMA of A block component, benefit is preferably replaced with nitrogen.Reaction vessel is heated to be 80 DEG C, 3.2 parts of 14.4 parts of 2- mercapto succinic acid, AIBN as mercaptan (Mercaptan) tethers transfer agent are added, has been carried out 12 hours Reaction.It confirmed that 95% has reacted by solid component measurement.
After until resulting solution is cooled to 50 DEG C, it is packed into 9.8 parts of acetic anhydride in the reaction vessel, at 100 DEG C It has reacted 9 hours.In the measurement of acid anhydrides valence, reacts to the end dicarboxylic acids progress acid anhydrides of 95% or more chain-transferring agent and turn to Only.
(step (2-1))
After until resulting solution is cooled to 30 DEG C, be loaded as in the reaction vessel to B block ingredient into 7.4 parts of 2- aminoothyl mercaptan of the mercaptan tethers transfer agent of row polymerization, have carried out reacting for 2 hours at 30 DEG C.It is measured in amine value In, it reacts until the amino progress amide addition of 95% or more 2- aminoothyl mercaptan.
(step (3))
Resulting solution is cooled down, is packed into 127 parts of PGMEA and as 80 parts of DMAEMA of B block ingredient, in nitrogen It is warming up to 80 DEG C under air-flow, and then polymerize within 4 hours.Thereafter, confirmed in the solid component measurement by polymeric solution It after 95% is reacted, is cooled to room temperature, thus stops polymerization.Obtain the AB block copolymerization that solid component is 50 weight % Object (A-1) solution.
(embodiment 2~embodiment 5:AB block copolymer (A-2)~AB block copolymer (A-5))
Using method identical with AB block copolymer (A-1), changed in a manner of the raw material type and weight ratio that become table 1 Become unsaturated single amount body (A block component, B block ingredient) of ethylene, mercaptan tethers transfer agent and obtain AB block copolymer (A-2)~AB block copolymer (A-5).
[table 1]
Table 1
(embodiment 6:AB block copolymer solution (A-6))
(step (1-2))
In the reaction vessel for having gas introduction tube, thermometer, condenser, blender, be packed into 330 parts of PGMEA and As 160 parts of 160 parts of MMA, the nBMA of A block component, benefit is preferably replaced with nitrogen.Reaction vessel is heated to be 80 DEG C, 3.2 parts of 14.4 parts of 2 mercapto ethanol, AIBN as mercaptan tethers transfer agent are added, react within 12 hours.Pass through solid Composition measurement confirmed that 95% has reacted.
After resulting solution is cooled to 50 DEG C, it is packed into 38.8 parts of trimellitic anhydride acyl chlorides in the reaction vessel, It has been reacted at 75 DEG C 4 hours.In Fourier transform infrared spectrometry (Fourier Transform Infrared Spectroscopy, FT-IR) measurement in, react to raw material trimellitic anhydride acyl chlorides acyl chlorides position absorption wave crest Until disappearance.
(step (2-1))
In addition to the blending amount of 2- aminoothyl mercaptan is set as 14.2 parts, make in the same manner as dispersing agent (A-1) resulting molten Liquid is reacted.
(step (3))
It is carried out similarly resulting solution with (A-1) to react, and obtains the AB block that solid component is 50 weight % Copolymer (A-6) solution.
(embodiment 7, embodiment 8:AB block copolymer (A-7), AB block copolymer (A-8))
Using method identical with block copolymer (A-6), changed in a manner of the raw material type and weight ratio that become table 2 Unsaturated single amount body (A block component, B block ingredient) of ethylene, mercaptan tethers transfer agent and obtain AB block copolymer (A- 7), AB block copolymer (A-8).
[table 2]
Table 2
(embodiment 9:AB block copolymer (A-9))
(step (1-2))
In the reaction vessel for having gas introduction tube, thermometer, condenser, blender, be packed into 330 parts of PGMEA and As 160 parts of 160 parts of MMA, the nBMA of A block component, benefit is preferably replaced with nitrogen.Reaction vessel is heated to be 80 DEG C, 3.2 parts of 6.4 parts of 2 mercapto ethanol, AIBN as mercaptan tethers transfer agent are added, react within 12 hours.Pass through solid Composition measurement confirmed that 95% has reacted.
After until resulting solution is cooled to 50 DEG C, it is packed into 17.9 parts of pyromellitic dianhydride in the reaction vessel, It has been reacted at 75 DEG C 4 hours.In the measurement of acid anhydrides valence, react to the acid of only single terminal region of 95% or more chain-transferring agent Until anhydride group reaction terminates.
(step (2-1))
In addition to the blending amount of 2- aminoothyl mercaptan is set as 14.2 parts, make in the same manner as dispersing agent (A-1) resulting molten Liquid is reacted.
(step (3))
It is carried out similarly resulting solution with (A-1) to react, and obtains the AB block that solid component is 50 weight % Copolymer (A-9) solution.
(embodiment 10, embodiment 11:AB block copolymer (A-10)~AB block copolymer (A-11))
Using method identical with AB block copolymer (A-9), in a manner of becoming the weight ratio of table 3 and to become raw material Type and the mode for being packed into ratio change ethylene unsaturated single amount body (A block component, B block ingredient), mercaptan tethers transfer agent And it synthesizes.
[table 3]
Table 3
(embodiment 12:AB block copolymer solution (A-12))
(step (2-2))
In the reaction vessel for having gas introduction tube, thermometer, condenser, blender, be packed into 330 parts of PGMEA and As 160 parts of 160 parts of MMA, the nBMA of A block component, benefit is preferably replaced with nitrogen.Reaction vessel is heated to be 80 DEG C, 3.2 parts of 14.4 parts of 2 mercapto ethanol, AIBN as mercaptan tethers transfer agent are added, react within 12 hours.Pass through solid Composition measurement confirmed that 95% has reacted.
After until resulting solution is cooled to 50 DEG C, it is packed into 26.0 parts of AOI in the reaction vessel, it is anti-at 75 DEG C It has answered 4 hours.In the measurement using FT-IR, react until the wave crest of the isocyanate group from AOI disappears.
After until resulting solution is cooled to 30 DEG C, be loaded as in the reaction vessel to B block ingredient into 14.4 parts of 2- aminoothyl mercaptan of the mercaptan tethers transfer agent (assigning the 2nd section of polymerism initiator) of row polymerization, it is anti-at 30 DEG C It has answered 2 hours.In the measurement of level-one amine value, react to the level-one amino of 95% or more 2- aminoothyl mercaptan and the acryloyl Until base carries out Michael's addition.
(step (3))
It is carried out similarly resulting solution with (A-1) to react, and obtains the AB block that solid component is 50 weight % Copolymer (A-12) solution.
(embodiment 13:AB block copolymer (A-13))
Using method identical with AB block copolymer (A-12), in a manner of becoming the weight ratio of table 4 and to become original Material type and the mode for being packed into ratio change unsaturated single amount body (A block component, B block ingredient) of ethylene, mercaptan tethers shifts Agent and synthesize.
[table 4]
Table 4
(embodiment 14: having used the compound AB block copolymer solution (A-14) of polymer (A2))
Use in embodiment 1 as intermediate and obtain single terminal region have anhydride polymer (A2-1) make For the precursor of A block, compound AB block copolymer has been synthesized using following methods.
In the reaction vessel for having gas introduction tube, thermometer, condenser, blender, be packed into 127 parts of PGMEA and 80 parts of DMAEMA, benefit is preferably replaced with nitrogen.Reaction vessel is heated to be 80 DEG C, is added as mercaptan tethers transfer agent 7.5 parts of 2 mercapto ethanol, 3.2 parts of AIBN, react within 12 hours.It confirmed that 95% has reacted by solid component measurement, and Obtain the precursor of B block.
In the reaction vessel for having gas introduction tube, thermometer, condenser, blender, it is packed into the reaction vessel poly- The precursor for closing object (A2-1) and B block, has carried out reacting for 4 hours at 75 DEG C.In the measurement of acid anhydrides valence, reaction to 95% with On composite precursor resin 1 anhydride group reaction until.
(embodiment 15: having used the compound AB block copolymer solution (A-15) of polymer (A2))
Using method identical with AB block copolymer (A-14), in a manner of becoming the weight ratio of table 5 and to become original Material type changes the composition of the precursor of A block and the precursor of B block with the mode for being packed into ratio and synthesizes.
[table 5]
Table 5
(comparative example 1: random copolymer (a-1))
In the reaction vessel for having gas introduction tube, thermometer, condenser, blender, 457 parts of PGMEA of loading, MMA160 parts, 160 parts of nBMA, 80 parts of DMAEMA, benefit is preferably replaced with nitrogen.Reaction vessel is heated to be 80 DEG C, addition As 14.4 parts of 2 mercapto ethanol of mercaptan system polymerization initiator, react within 12 hours.It is measured and is confirmed by solid component 95% has reacted.
(comparative example 2: compare with random copolymer (a-2))
Using method identical with random copolymer (a-1), in a manner of becoming the weight ratio of table 6 feed change type with It is packed into ratio and synthesizes.
[table 6]
Table 6
(comparative example 3: compare with AB block copolymer (a-3) | RAFT polymerization)
In the reaction vessel for having gas introduction tube, thermometer, condenser, blender, be packed into 457 parts of PGMEA and As 160 parts of 160 parts of MMA, the nBMA of A block component, benefit is preferably replaced with nitrogen.Reaction vessel is heated to be 80 DEG C, Add 3.2 parts of AIBN, 4- cyano -4- [(dodecyl sulfonyl thiocarbonyl) sulfonyl] pentane acid methyl esters (4-Cyano-4- [(Dodecyl sulfanyl thiocarbonyl) sulfanyl] pentane acid methyl) 15 parts of (He Guangchun medicine works Industry product), react within 12 hours.It confirmed that 95% has reacted by solid component measurement.In turn, addition as B block at 80 parts of DMAEMA divided, and then polymerize within 2 hours.After 2 hours, confirmed to gather according to the solid component of polymeric solution Conjunction rate is 97% or more, is cooled to room temperature and stops polymerizeing.Obtain the pigment dispersing agent solution that solid component is 50 weight % (a-3)。
(comparative example 4: compare with AB block copolymer (a-4) | RAFT polymerization)
Using AB block copolymer (a-3) identical method is used compared with, change original in a manner of becoming the weight ratio of table 7 Material type and loading are compared and are synthesized.
[table 7]
Table 7
In 1~table of table 7, the unsaturated single amount body of so-called ethylene refers to copolymer composition, the unsaturated single amount body of so-called ethylene (crosslinking group) refers to the copolymer composition of the functional group with heat cross-linking or photocrosslinking reaction.
The adjustment > of < pigment dispersion
(pigment dispersion (R-1))
58 12 parts of C.I. naphthol green used as pigment are molten with 83 parts of C.I. pigment yellow 13, pigment dispersing agent (A-1) 12.5 parts of liquid (solid component be 40 weight %), as 72.5 parts of PGMEA of solvent, handled by ball mill, and adjust Pigment dispersion (R-1).
(pigment dispersion (R-2~R-15) compares with pigment dispersion (R-16~R-19))
Other than changing the type of pigment dispersing agent as shown in table 2, adjusted in the same manner as pigment dispersion (R-1) Pigment dispersion (R-2~R-15) compares with pigment dispersion (R-16~R-19).
The evaluation > of < pigment dispersion
The viscosity of resulting pigment dispersion is measured using E type viscosimeter (manufacture of Tokyo gauge).In addition, by resulting face Material dispersion is filled in front glass container, after standing 14 at 23 DEG C under air-tight state, again using E type viscosimeter Measure viscosity.Moreover, increment rate of the viscosity after saving 14 relative to rigid viscosity adjusted is calculated, increment rate is less than 5% the case where, is evaluated as (A), by 5% or more and it is less than 10% the case where be evaluated as (B), 10% or more situation is evaluated as (C).It shows the results of the evaluation in table 8.
[table 8]
Table 8
In table 8, so-called PG58 refers to that C.I. naphthol green 58, so-called PY138 refer to C.I. pigment yellow 13 8.
As shown in table 8, (methyl) acrylic block copolymer of the invention is used for face obtained by pigment dispersing agent Expect that the dispersion stabilization evaluation of dispersion (R-1~R-15) is all good.In addition, using living radical polymerization, (RAFT is poly- Close) and the comparison pigment dispersion (R-18, R-19) of synthesis is also good result.However, using random copolymer for comparing Result for pigment dispersion (R-16, R-17) obtained by pigment dispersing agent is poor.
The adjustment of < colored filter photosensitive coloring composition and evaluation >
(colored filter photosensitive coloring composition S-1)
After being stirred mixing in such a way that following mixtures become uniform, it is filtered using 1.0 μm of filter, And the colored filter of alkali developable is obtained with photosensitive coloring composition (S-1).
40.0 parts of pigment dispersion 1 (R-1)
1 25.0 parts of alkali soluble resin
1.5 parts of optical polymerism list amount body (East Asia Synesis Company manufacture | M402)
0.2 part of Photoepolymerizationinitiater initiater (manufacture of BASF (BASF) company | gorgeous good solid (IRGACURE) OXE02)
0.1 part of sensitizer (hodogaya chemical company manufacture | EAB-F)
33.2 parts of PGMEA
Alkali soluble resin 1 is copolymerized using the alkali for being MAA/MMA/St=30/30/40 using weight ratio of the GMA to composition Object be modified obtained by, average molecular weight (Mw) be 15,000, molecular weight distribution (PDI) is 2.05, acid value 110 (mgKOH/g) resin.
(colored filter photosensitive coloring composition S-2~colored filter photosensitive coloring composition S-15, ratio Compared with composition S-16~compare with composition S-19)
Other than using pigment dispersion shown in table 9, colored filter is obtained similarly to Example 1 with photosensitive Property coloured composition (S-2~S-19).
(colored filter photosensitive coloring composition S-20, colored filter photosensitive coloring composition S-21, ratio Compared with composition S-22)
Other than using material shown in table 10, colored filter photosensitive color is obtained similarly to Example 1 Composition (S-20~S-22).Alkali soluble resin 2 and alkali soluble resin 3 use block copolymer shown in following.
The manufacture > of < alkali soluble resin block copolymer (C)
(embodiment 16 (alkali soluble resin 2): AB block copolymer solution (A-16))
The group for obtaining A block similarly to Example 1 becomes MMA/St, the group of B block becomes MAA and ratio of components (quality Than) be MMA/St/MAA=30/40/30 AB block copolymer solution.
Secondly, cooling down to resulting solution, and 30 parts of PGMEA are added, then one side will remain 80 in system DEG C, 40 parts of addition GMA (glycidyl methacrylate) with 3 parts of triethyl benzyl ammonia chloride on one side and progress is reacted for 5 hours. It confirmed that 95% has reacted by solid component measurement.The alkali soluble resin 2 is that average molecular weight (Mw) is 14,500, divides Son amount distribution (PDI) is that 2.15, acid value is 110 (mgKOH/g).
(comparative example 5 (alkali soluble resin 3): AB block copolymer (a-5) | RAFT polymerization)
By using 4- cyano -4- [(dodecyl sulfonyl thiocarbonyl) sulfonyl] 3 parts of pentane acid methyl esters (and light Pure medicine industrial goods) RAFT polymerization, obtain A block group become MMA/St, B block group become MAA and ratio of components (quality Than) be MMA/St/MAA=30/40/30 block copolymer solution.
Secondly, cooling down to resulting solution, and 30 parts of PGMEA are added, then one side will remain 80 in system DEG C, 40 parts of addition GMA (glycidyl methacrylate) with 3 parts of triethyl benzyl ammonia chloride on one side and progress is reacted for 5 hours. It confirmed that 95% has reacted by solid component measurement.The alkali soluble resin 3 is that average molecular weight (Mw) is 15,500, divides Son amount distribution (PDI) is that 1.15, acid value is 110 (mgKOH/g).
(alkali-developable evaluation)
On the glass plate of the 50mm × 30mm cleaned to surface, photosensitive color group is formed with 25 μm of thickness The coated film for closing object, carries out drying in 10 minutes at 90 DEG C.Secondly, the glass plate for being formed with coated film is impregnated in 1% hydrogen-oxygen Change in aqueous solutions of potassium, observes dissolubility of the coated film in 1% potassium hydroxide aqueous solution (aqueous alkali).It is commented by following benchmark Dissolubility described in valence.
< evaluation criteria >
A: dipping 5 minutes within coated film from glass plate it is molten from.
B: dipping 10 minutes within coated film from glass plate it is molten from.
C: coated film remains on glass plate after dipping 10 minutes.
If being evaluated as A or B, alkali-developable is excellent.
(chemical-resistant evaluation)
In 100mm × 100mm, 250 μ m-thicks being fixed on photosensitive coloring composition using sticker on glass substrate Polyethylene naphthalate film on, using spin coater by the final film thickness after being dried under reduced pressure become 2.0 μm in a manner of into Row coating, after being dried under reduced pressure, using extra-high-pressure mercury vapour lamp, in illumination 20mW/cm2, light exposure 50mJ/cm2It is lower to carry out purple Outer line exposing.Coated film is heated 20 minutes at 100 DEG C, and places cooling, is removed from glass substrate, and obtains evaluation and uses Film.About resulting film, coloration is measured, and film impregnates to 10 minutes at room temperature in propylene glycol methyl ether acetate, then It is cleaned, and is carried out air-dried using ion exchange water.Thereafter, film is visually observed and determination of colority, and is calculated outstanding Poor Δ E.Furthermore coloration is to utilize microspectrophotometer (Olympus (Olympus) Optical Co., Ltd system for having used illuminant-C " OSP-SP100 " made) it is determined.The grade of evaluation is as described below.
< evaluation criteria >
A+: appearance is unchanged, Δ E≤1.0: very good level
A: appearance is unchanged, 1.0 < Δ E≤2.0: good level
B: appearance is unchanged, 2.0 < Δ E≤3.0: excellent level
B+: appearance changes and/or 3.0 < Δ E: level that can be practical
(evaluation of analysis degree)
After using spin coater to be coated with the photosensitive coloring composition on alkali-free glass substrate, in 80 DEG C of heat 3 minutes prebake conditions are carried out on plate, and form the envelope that film thickness is 4.0 μm.Then, it is situated between on resulting envelope and sees every with 15 μm The photomask of the residual pattern of side, by ultraviolet exposure 10 seconds that the intensity under 365nm is 250W/m2.Thereafter, pass through hydroxide 0.05 weight % aqueous solution of potassium, carries out developing for 60 seconds at 25 DEG C, then clean within 1 minute using pure water.Thereafter, it is drying It is toasted after twenty minutes at 230 DEG C in case, the evaluated for film of predetermined pattern is consequently formed.When forming pattern, residual is schemed The case where analyzable situation of case is evaluated as good (A), the position that will there is a part can not analyze is evaluated as slightly bad (B), bad (C) will be evaluated as the case where can not analyzing completely.
Alkali-developable, chemical-resistant, analysis degree evaluation result is shown in table in 9, table 10.
[table 9]
Table 9
[table 10]
Table 10
In table 9, table 10, so-called crosslinking base refer in the copolymer composition of pigment dispersing agent comprising with heat cross-linking or The unsaturated single amount body of the ethylene of the functional group of photocrosslinking reaction.
As shown in table 9, by (methyl) acrylic block copolymer of the invention for the embodiment 1 in pigment dispersing agent The photosensitive coloring composition (S-1~S-15) of~embodiment 15 all shows good alkali-developable evaluation result.With this Relatively, comparative example 3, comparative example 4 photosensitive coloring composition (S-18, S-19) alkali-developable evaluation result it is poor.
In addition, (methyl) acrylic block of the invention in A block component with bridging property functional group is copolymerized Object in pigment dispersing agent embodiment 4, embodiment 5, embodiment 8, embodiment 11, embodiment 13, embodiment 15 it is photosensitive The chemical-resistant of property coloured composition (S-4, S-5, S-8, S-11, S-13, S-15) is all good, alkali-developable, chemically-resistant Moral character, pigment dispersion storage stability all good results.
In contrast, the pigment dispersion of the photosensitive composite (S-17) of the comparative example 2 of the functional group with bridging property Storage stability it is poor, the result of the alkali-developable of the photosensitive composite (S-29) of comparative example 4 is poor.
As shown in table 10, by (methyl) acrylic block copolymer of the invention for the implementation in alkali soluble resin Example 20, embodiment 21 photosensitive coloring composition (S-20, S-21) show the photosensitive coloring composition than comparative example 22 (S-22) evaluation result of more good analysis degree.
The manufacture > of < surface modifier polymer (A2)
(embodiment 101: surfaction agent solution (T-1))
(step (1-1))
In the reaction vessel for having gas introduction tube, thermometer, condenser, blender, it is packed into 330 parts of toluene and makees For 20 parts of 150 parts of 150 parts of MMA, nBMA, the MAA of copolymer composition, benefit is preferably replaced with nitrogen.Reaction vessel is heated to be 80 DEG C, 3.2 parts of 14.4 parts of 2- mercapto succinic acid, AIBN as mercaptan tethers transfer agent are added, react within 12 hours. It confirmed that 95% has reacted by solid component measurement.
After until resulting solution is cooled to 50 DEG C, it is packed into 9.8 parts of acetic anhydride in the reaction vessel, at 100 DEG C It has reacted 9 hours.In the measurement of acid anhydrides valence, reacts to the end dicarboxylic acids progress acid anhydrides of 95% or more chain-transferring agent and turn to Only.Obtaining as solid component is 50 weight % in (methyl) acrylic acid series polymeric compounds of single terminal region with anhydride group (A2) surfaction agent solution (T-1).
(embodiment 102: surfaction agent solution (T-2))
(step (1-2))
In the reaction vessel for having gas introduction tube, thermometer, condenser, blender, it is packed into 330 parts of toluene and makees For 20 parts of 150 parts of 150 parts of MMA, nBMA, the MAA of copolymer composition, benefit is preferably replaced with nitrogen.Reaction vessel is heated to be 80 DEG C, 3.2 parts of 14.4 parts of 2 mercapto ethanol, AIBN as mercaptan tethers transfer agent are added, react within 12 hours.It is logical Crossing solid component measurement confirmed that 95% has reacted.
After until resulting solution is cooled to 50 DEG C, it is packed into trimellitic anhydride acyl chlorides 38.8 in the reaction vessel Part, it has been reacted at 75 DEG C 4 hours.In the measurement of FT-IR, react to the acyl chlorides position of the trimellitic anhydride acyl chlorides of raw material Absorption wave crest disappear until.Obtain the surfaction agent solution (T-2) that solid component is 50 weight %.
(embodiment 103: surfaction agent solution (T-3))
(step (1-2))
Other than trimellitic anhydride acyl chlorides is changed into 40.2 parts of pyromellitic dianhydride, in the same manner as embodiment 102 Obtain the surfaction agent solution (T- as (methyl) acrylic acid series polymeric compounds (A2) in single terminal region with anhydride group 3)。
(comparative example 101: surfaction agent solution (T-4))
In the reaction vessel for having gas introduction tube, thermometer, condenser, blender, it is packed into 330 parts of toluene and makees For 20 parts of 150 parts of 150 parts of MMA, nBMA, the MAA of copolymer composition, benefit is preferably replaced with nitrogen.Reaction vessel is heated to be 80 DEG C, 3.2 parts of 14.4 parts of 2 mercapto ethanol, AIBN as mercaptan tethers transfer agent are added, react within 12 hours.It is logical Crossing solid component measurement confirmed that 95% has reacted.Obtain the surfaction agent solution (T-4) that solid component is 50 weight %.
< surfaction/pigment dispersion adjustment >
(surfaction/pigment dispersion (U-1))
12.5 parts of 15 parts of C.I. paratonere 57:1, surfaction agent solution (T-1) (solid components used as pigment 40 weight %), as 72.5 parts of toluene of solvent, handled by ball mill, and adjust surfaction/pigment dispersion (U-1)。
(surfaction/pigment dispersion (U-2~U-3) compares with surfaction/pigment dispersion (U-4))
It is same with surfaction/pigment dispersion (U-1) other than being changed to shown in table 11 by the type of surface modifier It adjusts to sample surfaction/pigment dispersion (U-2~U-3), compare with surfaction/pigment dispersion (U-4).
< surfaction/pigment dispersion evaluation >
The viscosity of resulting surfaction/pigment dispersion is measured using E type viscosimeter (manufacture of Tokyo gauge).In addition, Resulting surfaction/pigment dispersion is filled in front glass container, stands 14 at 23 DEG C under air-tight state Afterwards, viscosity is measured again using E type viscosimeter.Moreover, calculating the viscosity after saving 14 relative to rigid viscosity adjusted Increment rate, increment rate is less than 5% the case where is evaluated as A, by 5% or more and it is less than 10% the case where be evaluated as B, by 10% Above situation is evaluated as C.
By initial viscosity, storage stability evaluation result is shown in table in 11.
[table 11]
Table 11
In table 11, so-called PR57:1 refers to C.I. paratonere 57:1.
As shown in table 11, in single terminal region there are (methyl) acrylic acid series polymeric compounds (A2) of anhydride group to use for of the invention Surfaction/pigment dispersion (U-1~U-3) of 101~embodiment of embodiment 103 in surface modifier is all shown Good initial viscosity and storage stability.In contrast, the evaluation of surfaction/pigment dispersion (U-4) of comparative example 101 As a result poor.
Think that reason is: about by it is of the invention single terminal region have anhydride group (methyl) acrylic acid series polymeric compounds (A2) surfaction/pigment dispersion (U-1~U-3) for 101~embodiment of embodiment 103 in surface modifier leads to The functional group's (hydroxyl) crossed in surface of pigments and (methyl) acrylic acid series polymeric compounds (A2) benefit in single terminal region with anhydride group It is reacted with chemical bonded refractory, and surface of pigments is improved using resin.
As example of applying flexibly of the invention, colored filter photosensitive composite can be especially enumerated, thus can help to The raising of the image property of liquid color display used in multiple use or the raising of economy, it is therefore contemplated that it is utilized. More specifically, (methyl) the acrylic block copolymer (C) for assigning feature to the present invention has as pigment dispersing agent Excellent characteristic can especially meet dispersion stabilization, the dissolubility of alkali-developable improves, chemical-resistant.In addition, it is possible to provide such as Lower pigment dispersing agent: excellent for a small amount of usage amount and dispersion stabilization and developability, chemical-resistant is also excellent.In addition, Not only can provide pigment dispersing agent, and can provide alkali soluble resin, colored filter photosensitive coloring composition with And using the wherein polymeric compound block copolymer of mesosome, by surface modifier, smears of resin treatment etc..
This application claims by based on the Japanese publication Patent 2016-230276 to file an application on November 28th, 2016 All the elements disclosed in it are incorporated into the application by priority.

Claims (19)

1. a kind of (methyl) acrylic acid series polymeric compounds (A2), being will be two possessed by (methyl) acrylic acid series polymeric compounds (A1) Carboxy-modified to form at anhydride group and described (methyl) acrylic acid series polymeric compounds (A2) have anhydride group in single terminal region, described (methyl) acrylic acid series polymeric compounds (A1) are that there are two the compounds of carboxyl and more than one mercapto in tool in the molecule In the presence of amount body unsaturated single to ethylene be polymerized, and (methyl) acrylic acid series polymeric compounds (A1) are in single end There are two carboxyls for region tool.
2. (methyl) acrylic acid series polymeric compounds (A2) according to claim 1, wherein there are two carboxylics in intramolecular tool The compound of base and more than one mercapto is compound (D) represented by the following general formula (1)；
[changing 1]
General formula (1)
(in general formula (1), R1For methylene or ethylidene).
3. a kind of (methyl) acrylic acid series polymeric compounds (A2), are made one possessed by (methyl) acrylic acid series polymeric compounds (A1') A above hydroxyl, with
Acid chloride group in tricarboxylic acid anhydride acyl chlorides (E) or
An anhydride group in the intramolecular of tetracarboxylic anhydride (F) is reacted, and (methyl) acrylic acid series polymeric compounds (A2) There is more than one anhydride group in single terminal region, wherein described (methyl) acrylic acid series polymeric compounds (A1') are in molecule In the presence of the interior compound with more than one hydroxyl and more than one mercapto single amount body unsaturated to ethylene into Row is polymerized, and (methyl) acrylic acid series polymeric compounds (A1') have more than one hydroxyl in single terminal region.
4. (methyl) acrylic acid series polymeric compounds (A2) according to claim 3, wherein the intramolecular have one with On hydroxyl and more than one mercapto compound be the following general formula (2) represented by compound (G),
The tricarboxylic acid anhydride acyl chlorides (E) is compound (H1) represented by following chemical formula (3),
The tetracarboxylic anhydride (F) is compound (H2) represented by the following general formula (4)；
[changing 2]
General formula (2)
(in general formula (2), R2For that can have the alkyl of heteroatomic divalent~tetravalence, n1Integer for 1~3)
[changing 3]
Chemical formula (3)
[changing 4]
General formula (4)
(in general formula (4), k1It is 1 or 2).
5. a kind of (methyl) acrylic acid series polymeric compounds (A3) are to make (methyl) third according to any one of claims 1 to 4 Anhydride group in olefin(e) acid based polymer (A2) and
In the molecule the compound with more than one amino and more than one mercapto or
In the molecule there is more than one hydroxyl to react with the compound of more than one mercapto, and (methyl) Acrylic acid series polymeric compounds (A3) have mercapto in single terminal region.
6. (methyl) acrylic acid series polymeric compounds (A3) according to claim 5, wherein the intramolecular have one with On amino and more than one mercapto compound be the following general formula (5) represented by compound (I1),
The compound in the intramolecular with more than one hydroxyl and more than one mercapto is the following general formula (6) institute table The compound (I2) shown；
[changing 5]
General formula (5)
[changing 6]
General formula (6)
(in general formula (5) and general formula (6),
R3For hydrogen atom, alkyl or aryl,
R4For that can have the alkyl of heteroatomic divalent~tetravalence, n2Integer for 1~3).
7. a kind of (methyl) acrylic acid series polymeric compounds (A3), be in (methyl) acrylic acid series polymeric compounds (A1'),
Make the acrylic acid series polymeric compounds (A1') more than one hydroxyl possessed by single terminal region and
In the molecule there is more than one isocyanate group to react with the compound of more than one (methyl) acryloyl group,
And then makes (methyl) acryloyl group and there is more than one amino and more than one mercapto in the molecule Compound carries out Michael addition reaction and forms, and (methyl) acrylic acid series polymeric compounds (A3) have sulphur in single terminal region Alcohol radical, wherein described (methyl) acrylic acid series polymeric compounds (A1') be in have in the molecule more than one hydroxyl and one with On mercapto compound in the presence of amount body unsaturated single to ethylene be polymerized, and (methyl) acrylic acid Based polymer (A1') has more than one hydroxyl in single terminal region.
8. a kind of (methyl) acrylic block copolymer (C), is in (the first as described in any one of claim 5 to 7 Base) in the presence of acrylic acid series polymeric compounds (A3), single amount body unsaturated to ethylene is polymerized.
9. a kind of (methyl) acrylic acid series polymeric compounds (A2) are indicated by the following general formula (7)；
[changing 7]
General formula (7)
(in general formula (7), (A) is (methyl) acrylic acid series polymeric compounds residue,
R5For the bilvalent radical being directly bonded or in the group as composed by alkylidene, arlydene and epoxy alkyl,
L1To be directly bonded or-O-C (=O)-,
X1For tetravalence base shown in the following general formula (8), general formula (9) or general formula (10),
Y1For hydrogen atom or-COOH)
[changing 8]
General formula (8)
(in general formula (8), R6For three base of methine, ethylidine or 1,1,2- second)
[changing 9]
General formula (9)
(in general formula (9), k2It is 1 or 2)
[changing 10]
General formula (10)
(in general formula (10), Q1For be directly bonded or the bilvalent radical of carbon number 1~20).
10. a kind of (methyl) acrylic acid series polymeric compounds (A3) are indicated by the following general formula (11)；
[changing 11]
General formula (11)
(in general formula (11), (A) is (methyl) acrylic acid series polymeric compounds residue,
R7For the bilvalent radical being directly bonded or in the group as composed by alkylidene, arlydene and alkylene oxide,
L2To be directly bonded or-O-C (=O)-,
X2For tetravalence base shown in the following general formula (12), general formula (13), general formula (14) or general formula (15),
Y2For hydrogen atom or-COOH, Y3And Y4In any one be base shown in the following general formula (16) or general formula (17), Y3And Y4In Another one is hydrogen atom or COOR15, R15For hydrogen atom, alkyl, aryl or halogen atom)
[changing 12]
General formula (12)
(in general formula (12), R8For methine, ethylidine or 1,1,2- second, three base)
[changing 13]
General formula (13)
(in general formula (13), k3It is 1 or 2)
[changing 14]
General formula (14)
(in general formula (14), Q2For be directly bonded or the bilvalent radical of carbon number 1~20)
[changing 15]
General formula (15)
(in general formula (15), R9For alkylidene)
[changing 16]
General formula (16)
(in general formula (16), M1For-NR11Or-O-, R11For hydrogen atom, alkyl or arlydene,
R10For the bilvalent radical in the group as composed by alkylidene, arlydene and alkylene oxide)
[changing 17]
General formula (17)
(in general formula (17), R12、R13Separately in the group as composed by alkylidene, arlydene and alkylene oxide Bilvalent radical,
R14For hydrogen atom, alkyl, aryl or halogen atom).
11. a kind of (methyl) acrylic block copolymer (C) is indicated by the following general formula (18)；
[changing 18]
General formula (18)
(in general formula (18), (A) is (methyl) acrylic acid series polymeric compounds residue,
R16For the bilvalent radical being directly bonded or in the group as composed by alkylidene, arlydene and alkylene oxide,
L3To be directly bonded or-O-C (=O)-,
X3For tetravalence base shown in the following general formula (19), general formula (20), general formula (21) or general formula (22),
Y5For hydrogen atom or-COOH,
Y6And Y7In any one be base shown in the following general formula (23) or general formula (24), Y6And Y7The other of for hydrogen atom or COOR24, R24For hydrogen atom, alkyl, aryl or halogen atom)
[changing 19]
General formula (19)
(in general formula (19), R17For methine, ethylidine or 1,1,2- second, three base)
[changing 20]
General formula (20)
(in general formula (20), k4It is 1 or 2)
[changing 21]
General formula (21)
(in general formula (21), Q3For be directly bonded or the bilvalent radical of carbon number 1~20)
[changing 22]
General formula (22)
(in general formula (22), R18For alkylidene)
[changing 23]
General formula (23)
(in general formula (23), M2For-NR20Or-O-, R20For hydrogen atom or alkyl,
R19For comprising the bilvalent radical selected from least one of group as composed by alkylidene, arlydene and alkylene oxide,
It (B) is (methyl) acrylic acid series polymeric compounds residue)
[changing 24]
General formula (24)
(in general formula (24), R21、R22Separately in the group as composed by alkylidene, arlydene and alkylene oxide Bilvalent radical,
R23For hydrogen atom, alkyl, aryl or halogen atom,
It (B) is (methyl) acrylic acid series polymeric compounds residue).
12. a kind of pigment dispersion, containing pigment, pigment dispersing agent and organic solvent, and the pigment dispersing agent is as weighed Benefit require 8 or 11 described in block copolymer (C).
13. a kind of photosensitive coloring composition, containing pigment dispersion as claimed in claim 12, and the photonasty Color composition is used for colored filter.
14. a kind of photosensitive coloring composition contains pigment, pigment dispersing agent, alkali soluble resin, multi-functional single amount body And optical free radical initiator, and the photosensitive coloring composition is used for colored filter, the alkali soluble resin is as weighed Benefit require 8 or 11 described in block copolymer (C).
15. a kind of colored filter comprising the filter formed by photosensitive coloring composition according to claim 13 or 14 Mating plate section.
16. a kind of printing ink composition, containing pigment, pigment dispersing agent, adhesive resin and organic solvent, and pigment dispersing agent Or adhesive resin is the block copolymer (C) as described in claim 8 or 11.
17. a kind of compound block copolymer, it uses have acid anhydrides in single terminal region as described in Claims 1-4 or 9 (methyl) acrylic acid series polymeric compounds (A2) of base are used as precursor.
18. a kind of pigment dispersing agent, it uses as described in Claims 1-4 or 9 single terminal region has anhydride group (methyl) acrylic acid series polymeric compounds (A2).
19. a kind of surface modifier or smears, it uses having as described in Claims 1-4 or 9 in single terminal region (methyl) acrylic acid series polymeric compounds (A2) of anhydride group.
CN201780073427.6A 2016-11-28 2017-11-27 (meth) acrylic polymer, copolymer, dispersion, composition, optical filter, dispersant, modifier, and coating agent Active CN110023350B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2016230276 2016-11-28
JP2016-230276 2016-11-28
PCT/JP2017/042352 WO2018097279A1 (en) 2016-11-28 2017-11-27 (meth)acrylic polymer, (meth)acrylic block copolymer, pigment dispersion, photosensitive coloring composition, color filter, ink composition, composite block copolymer, pigment dispersant, and coating agent

Publications (2)

Publication Number Publication Date
CN110023350A true CN110023350A (en) 2019-07-16
CN110023350B CN110023350B (en) 2022-01-11

Family

ID=62195170

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780073427.6A Active CN110023350B (en) 2016-11-28 2017-11-27 (meth) acrylic polymer, copolymer, dispersion, composition, optical filter, dispersant, modifier, and coating agent

Country Status (5)

Country Link
JP (1) JP6965703B2 (en)
KR (1) KR102516074B1 (en)
CN (1) CN110023350B (en)
TW (1) TWI757377B (en)
WO (1) WO2018097279A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110068987A (en) * 2018-01-23 2019-07-30 阪田油墨股份有限公司 Colored filter pigment dispensing composition and colored filter anti-corrosion agent composition

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7150005B2 (en) 2018-03-15 2022-10-07 富士フイルム株式会社 Curable resin composition, cured product, diffractive optical element, multilayer diffractive optical element, and method for producing curable resin composition
WO2020203837A1 (en) * 2019-03-29 2020-10-08 三菱ケミカル株式会社 High-molecular-weight compound and method for producing same, composition and method for producing same, resin composition, additive for lubricating oils, and lubricating oil
JP7299069B2 (en) * 2019-05-29 2023-06-27 サカタインクス株式会社 Pigment dispersion composition for color filter and pigment dispersion resist composition for color filter
WO2021039409A1 (en) * 2019-08-27 2021-03-04 富士フイルム株式会社 Curable composition, cured product, color filter, solid-state imaging element and image display device
JP7507006B2 (en) 2020-04-30 2024-06-27 サカタインクス株式会社 Pigment dispersion composition for black matrix, resist composition for black matrix, and black matrix
JPWO2022176788A1 (en) * 2021-02-18 2022-08-25

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59189112A (en) * 1983-04-08 1984-10-26 Kuraray Co Ltd Production of block copolymer
JP2001310909A (en) * 2000-02-24 2001-11-06 Soken Chem & Eng Co Ltd Acrylic polymer, curable acrylic polymer and cured material, and use thereof
CN101490128A (en) * 2006-07-14 2009-07-22 东洋油墨制造株式会社 Polyester dispersant, process for production of the same, and pigment composition using the same
JP2010204231A (en) * 2009-03-02 2010-09-16 Toyo Ink Mfg Co Ltd Color composition for color filter, and color filter
JP2012021070A (en) * 2010-07-14 2012-02-02 Toyo Ink Sc Holdings Co Ltd Dispersion
JP2013540188A (en) * 2010-10-06 2013-10-31 ノバルティス アーゲー Chain-extending polysiloxane crosslinker with dangling hydrophilic polymer chain

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1116595A (en) 1974-10-30 1982-01-19 George B. Hoey 3,5-disubstituted-2,4,6-triiodoanilides of polyhydroxy-monobasic acids
AU3919500A (en) 1999-03-23 2000-10-09 Carnegie Wave Energy Limited Catalytic processes for the controlled polymerization of free radically (co)polymerizable monomers and functional polymeric systems prepared thereby
JP2007031654A (en) * 2005-07-29 2007-02-08 Toyo Ink Mfg Co Ltd Method for producing pigment composition and printing ink and printed matter
JP5396712B2 (en) * 2007-03-02 2014-01-22 東洋インキＳｃホールディングス株式会社 Dispersant, and pigment composition and pigment dispersion using the same
JP5470945B2 (en) * 2008-03-24 2014-04-16 東洋インキＳｃホールディングス株式会社 Dispersant, and pigment composition, pigment dispersion, and inkjet ink using the same
JP2012184414A (en) * 2011-02-16 2012-09-27 Toyo Ink Sc Holdings Co Ltd Coloring composition, and color filter and method of manufacturing the same
JP6028360B2 (en) * 2011-06-29 2016-11-16 東洋インキＳｃホールディングス株式会社 Photosensitive resin composition and cured product thereof, and method for producing photosensitive resin
JP2016184099A (en) * 2015-03-26 2016-10-20 東洋インキＳｃホールディングス株式会社 Production method of filter segment for color filter, filter segment for color filter, color filter, and colored composition for etching system
EP3650510B1 (en) * 2017-07-03 2022-05-04 Kao Corporation Production method for aqueous pigment dispersion

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS59189112A (en) * 1983-04-08 1984-10-26 Kuraray Co Ltd Production of block copolymer
JP2001310909A (en) * 2000-02-24 2001-11-06 Soken Chem & Eng Co Ltd Acrylic polymer, curable acrylic polymer and cured material, and use thereof
CN101490128A (en) * 2006-07-14 2009-07-22 东洋油墨制造株式会社 Polyester dispersant, process for production of the same, and pigment composition using the same
JP2010204231A (en) * 2009-03-02 2010-09-16 Toyo Ink Mfg Co Ltd Color composition for color filter, and color filter
JP2012021070A (en) * 2010-07-14 2012-02-02 Toyo Ink Sc Holdings Co Ltd Dispersion
JP2013540188A (en) * 2010-10-06 2013-10-31 ノバルティス アーゲー Chain-extending polysiloxane crosslinker with dangling hydrophilic polymer chain

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110068987A (en) * 2018-01-23 2019-07-30 阪田油墨股份有限公司 Colored filter pigment dispensing composition and colored filter anti-corrosion agent composition

Also Published As

Publication number Publication date
TW201825541A (en) 2018-07-16
CN110023350B (en) 2022-01-11
KR102516074B1 (en) 2023-03-30
JP6965703B2 (en) 2021-11-10
JP2018090788A (en) 2018-06-14
KR20190087421A (en) 2019-07-24
TWI757377B (en) 2022-03-11
WO2018097279A1 (en) 2018-05-31

Similar Documents

Publication Publication Date Title
CN110023350A (en) (methyl) acrylic acid series polymeric compounds, (methyl) acrylic block copolymer, pigment dispersion, photosensitive coloring composition, colored filter, printing ink composition, compound block copolymer, pigment dispersing agent and smears
CN101373329B (en) Colored cured composition
TWI553027B (en) Block copolymers, dispersants and pigment dispersion compositions
TWI608057B (en) Blue pigment dispersion composition for color filter and blue pigment dispersion resist composition for color filter containing the same
CN101441413A (en) Green coloring composition for filter and filter
CN104411746A (en) Curable composition, cured film and display element
CN101726999B (en) Coloring combination, color filter and color liquid crystal display element
CN103913949A (en) Dying photosensitive resin composition
TW201945506A (en) Dispersant composition, coloring composition and color filter
JP2020066687A (en) Coloring composition and color filter
JPH01200353A (en) Radiation sensitive coloring resin composition
CN106967043A (en) Compound, polymer, colouring agent, photosensitive resin composition, photo-sensitive resin and colored filter
TW201712075A (en) Colored photosensitive resin composition and color filter made using the same capable of exhibiting excellent sensitivity due to a sufficient curing in the low-temperature heating process
JP6758166B2 (en) Colored Radiation Composition and Color Filter
JP2020066688A (en) Coloring composition and color filter
TWI818051B (en) Dispersant composition, coloring composition, and color filter
JPH07325400A (en) Polymer composition for color filter
CN103998532A (en) Colored photosensitive composition, color filter and method for producing same, and display device
JP2013145364A (en) Pigment dispersion for color filter and photosensitive coloring composition
CN106467680A (en) Fluorescent dye dispersion, spontaneous emission Photosensitve resin composition and preparation method, color conversion filter device and the display device including it
TW201635032A (en) Colored photosensitive resin composition and color filter manufactured by the same
JP7324623B2 (en) Block copolymer, dispersant, coloring composition, and color filter
JP7348804B2 (en) Dispersant compositions, coloring compositions and color filters
JP7344106B2 (en) Colored compositions and color filters
JP6797483B2 (en) Block copolymers, dispersants, coloring compositions and color filters

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant