WO2018097279A1 - Polymère (méth)acrylique, copolymère séquencé (méth)acrylique, dispersion de pigment, composition colorante photosensible, filtre coloré, composition d'encre, copolymère séquencé composite, agent de dispersion de pigment, et agent de revêtement - Google Patents

Polymère (méth)acrylique, copolymère séquencé (méth)acrylique, dispersion de pigment, composition colorante photosensible, filtre coloré, composition d'encre, copolymère séquencé composite, agent de dispersion de pigment, et agent de revêtement Download PDF

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WO2018097279A1
WO2018097279A1 PCT/JP2017/042352 JP2017042352W WO2018097279A1 WO 2018097279 A1 WO2018097279 A1 WO 2018097279A1 JP 2017042352 W JP2017042352 W JP 2017042352W WO 2018097279 A1 WO2018097279 A1 WO 2018097279A1
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group
meth
general formula
acrylic polymer
compound
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PCT/JP2017/042352
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English (en)
Japanese (ja)
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一敏 大庭
進 白鳥
彩子 宮本
ニシャド ペルール
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東洋インキＳｃホールディングス株式会社
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Priority to KR1020197013561A priority Critical patent/KR102516074B1/ko
Priority to CN201780073427.6A priority patent/CN110023350B/zh
Publication of WO2018097279A1 publication Critical patent/WO2018097279A1/fr

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    • 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

Definitions

  • the present invention relates to a (meth) acrylic block copolymer, a (meth) acrylic polymer that is an intermediate thereof, and a composite block copolymer, a pigment dispersant, a surface modifier, and a coating using the same. Further, the present invention relates to a pigment dispersion, a photosensitive coloring composition for a color filter, a photosensitive coloring composition, a color filter, and an ink composition, which contain the copolymer or the intermediate.
  • (Meth) acrylic block copolymers in which different types of polymer blocks are bonded are generally produced by successively polymerizing different monomers, and various polymerization methods have been developed so far.
  • production methods of block copolymers by living radical polymerization have been actively developed, and various polymerization methods that can control the structure and molecular weight distribution using such production methods have been developed.
  • the living radical polymerization method has been actively developed since around 1990. Especially for image recording materials and image display displays, the living radical polymerization method is used for living radical polymerization in order to prevent aggregation of pigments that have been refined to the nano level and to maintain a fine state.
  • a pigment dispersant using a produced block polymer is known as a material particularly excellent in dispersion stability (Patent Document 1). It is also in the limelight as a method for producing polymers used in cutting-edge fields such as nanotechnology.
  • typical polymerization methods include polymerization using a nitroxide-based catalyst / NMP method, atom transfer radical polymerization using a transition metal complex-based catalyst / ATRP method, Known are reversible addition-cleavage chain transfer polymerization / RAFT method using dithioester catalyst, polymerization using organic tellurium catalyst / TERP method, iodine transfer polymerization using iodine compound catalyst / RTCP method, etc. It has been.
  • the nitroxide-based catalyst has a drawback that it is necessary to introduce a special protective group into the polymer growth chain in combination with the catalyst, and this protective group is very expensive. Moreover, high temperature conditions (100 degreeC or more) are required for a polymerization reaction, and industrial control is very difficult. In addition, dithioester-based catalysts often have sulfur compound-derived odors and have many problems from the viewpoint of toxicity. There is also a disadvantage that the polymer to be produced has a color derived from sulfur.
  • the transition metal catalyst for example, a complex in which a ligand is coordinated to a compound having Cu, Ni, Re, Rh, Ru, etc. as a central metal is used, and an organic tellurium compound is used as a catalyst.
  • organic iodine compounds such as alkyl iodides are also used for the polymerization using metal tellurium compounds and iodine compounds as catalysts.
  • the present invention is intended to solve the above problems, and is a novel (meth) acrylic block copolymer that can be easily and inexpensively and easily industrially produced by a general-purpose radical polymerization method other than living radical polymerization.
  • Production method thereof, intermediate polymer thereof, pigment dispersant using the same, photosensitive coloring composition for color filter, and composite block copolymer using the intermediate polymer, surface by resin treatment The purpose is to provide a modifier, a coating agent and the like.
  • the present inventors have completed the present invention as a result of intensive studies to solve the above-mentioned problems. That is, according to the present invention, there is provided a novel (meth) acrylic block copolymer and polymerization method using, as an intermediate polymer, a (meth) acrylic polymer having an anhydride group in one end region described below. This solves the above problem.
  • two carboxyl groups are formed in one end region by polymerizing an ethylenically unsaturated monomer in the presence of a compound having two carboxyl groups and one or more thiol groups in the molecule.
  • the present invention relates to a (meth) acrylic polymer (A2) having an anhydride group in one terminal region, which is obtained by modifying two carboxyl groups of the (meth) acrylic polymer (A1) having an acid anhydride group.
  • a compound having two carboxyl groups and one or more thiol groups in the molecule is represented by the following general formula (1) ( D).
  • R 1 is a methylene group or an ethylene group.
  • the present invention relates to one or more terminal regions formed by polymerizing an ethylenically unsaturated monomer in the presence of a compound having one or more hydroxyl groups and one or more thiol groups in the molecule.
  • the compound having one or more hydroxyl groups and one or more thiol groups in the molecule is represented by the following general formula (2): (G),
  • the tricarboxylic anhydride chloride (E) is a compound (H1) represented by the following chemical formula (3)
  • the tetracarboxylic anhydride (F) is a compound (H2) represented by the following general formula (4).
  • R 2 is a divalent to tetravalent hydrocarbon group which may have a hetero atom, and n 1 is an integer of 1 to 3.
  • k 1 is 1 or 2.
  • the present invention also includes an acid anhydride group in the (meth) acrylic polymer (A2) according to the present invention, A compound having one or more amino groups and one or more thiol groups in the molecule, or
  • the present invention relates to a (meth) acrylic polymer (A3) having a thiol group in one terminal region, obtained by reacting a compound having one or more hydroxyl groups and one or more thiol groups in the molecule.
  • a compound having one or more amino groups and one or more thiol groups in the molecule is represented by the following general formula (5).
  • Compound (I1) The compound having one or more hydroxyl groups and one or more thiol groups in the molecule is the compound (I2) represented by the following general formula (6).
  • R 3 is a hydrogen atom, an alkyl group, or an aryl group
  • R 4 is a divalent to tetravalent hydrocarbon group which may have a hetero atom
  • n 2 is an integer of 1 to 3.
  • the present invention relates to one or more terminal regions formed by polymerizing an ethylenically unsaturated monomer in the presence of a compound having one or more hydroxyl groups and one or more thiol groups in the molecule.
  • a (meth) acrylic polymer (A1 ′) having a hydroxyl group One or more hydroxyl groups of the acrylic polymer (A1 ′) in the one end region; Reacting a compound having one or more isocyanate groups and one or more (meth) acryloyl groups in the molecule;
  • a (meth) acryl having a thiol group in one end region which is obtained by Michael addition reaction between the (meth) acryloyl group and a compound having one or more amino groups and one or more thiol groups in the molecule. It relates to a polymer (A3).
  • the present invention also provides a (meth) acrylic block copolymer (C) obtained by polymerizing an ethylenically unsaturated monomer in the presence of the (meth) acrylic polymer (A3) according to the present invention. )
  • the present invention also relates to a (meth) acrylic polymer (A2) represented by the following general formula (7).
  • (A) is a (meth) acrylic polymer residue
  • R 5 is a direct bond or a divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide group
  • L 1 is a direct bond or —O—C ( ⁇ O) —
  • X 1 is a tetravalent group represented by the following general formula (8), general formula (9), or general formula (10)
  • Y 1 is a hydrogen atom or —COOH.
  • R 6 is a methine group or an ethyne group.
  • Q 1 is a direct bond or a divalent group having 1 to 20 carbon atoms.
  • the present invention also relates to a (meth) acrylic polymer (A3) represented by the following general formula (11).
  • (A) is a (meth) acrylic polymer residue, R 7 is a direct bond or a divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide; L 2 is a direct bond or —O—C ( ⁇ O) —, X 2 is a tetravalent group represented by the following general formula (12), general formula (13), general formula (14), or general formula (15), Y 2 is a hydrogen atom or —COOH, one of Y 3 and Y 4 is a group represented by the following general formula (16) or general formula (17), and the other of Y 3 and Y 4 is It is a hydrogen atom or COOR 15 , and R 15 is a hydrogen atom, an alkyl group, an aryl group or a halogen atom. )
  • R 8 is a methine group or an ethyne group.
  • k 3 is 1 or 2.
  • Q 2 is a direct bond or a divalent group having 1 to 20 carbon atoms.
  • R 9 is an alkylene group.
  • M 1 is —NR 11 — or —O—
  • R 11 is a hydrogen atom, an alkyl group, or an arylene group
  • R 10 is a divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide.
  • R 12 and R 13 are each independently a divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide; R 14 is a hydrogen atom, an alkyl group, an aryl group or a halogen atom.
  • the present invention also relates to a (meth) acrylic block copolymer (C) represented by the following general formula (18).
  • (A) is a (meth) acrylic polymer residue
  • R 16 is a direct bond or a divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide
  • L 3 is a direct bond or —O—C ( ⁇ O) —
  • X 3 is a tetravalent group represented by the following general formula (19), general formula (20), general formula (21), or general formula (22)
  • Y 5 is a hydrogen atom or —COOH
  • One of Y 6 and Y 7 is a group represented by the following general formula (23) or general formula (24), the other of Y 6 and Y 7 is a hydrogen atom or COOR 24 , and R 24 is , A hydrogen atom, an alkyl group, an aryl group or a halogen atom.
  • R 17 is a methine group or an ethyne group.
  • k 4 is 1 or 2.
  • Q 3 is a direct bond or a divalent group having 1 to 20 carbon atoms.
  • R 18 is an alkylene group.
  • M 2 is —NR 20 — or —O—
  • R 20 is a hydrogen atom or an alkyl group
  • R 19 is a divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide
  • (B) is a (meth) acrylic polymer residue.
  • R 21 and R 22 are each independently a divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide;
  • R 23 is a hydrogen atom, an alkyl group, an aryl group or a halogen atom,
  • (B) is a (meth) acrylic polymer residue.
  • the present invention also relates to a pigment dispersion containing a pigment, a pigment dispersant, and an organic solvent, wherein the pigment dispersant is the block copolymer (C) according to the present invention.
  • the present invention also relates to a photosensitive coloring composition for a color filter containing the pigment dispersion according to the present invention.
  • the present invention also provides a photosensitive coloring composition for a color filter containing a pigment, a pigment dispersant, an alkali-soluble resin, a polyfunctional monomer, and a photoradical initiator, wherein the alkali-soluble resin is the invention. It is related with the photosensitive coloring composition which is the block copolymer (C) concerning.
  • the present invention also relates to a color filter comprising a filter segment formed from the photosensitive coloring composition according to the present invention.
  • the present invention also provides an ink composition containing a pigment, a pigment dispersant, a binder resin, and an organic solvent, wherein the pigment dispersant or the binder resin is the block copolymer (C) according to the present invention. Relates to the composition.
  • the present invention also relates to a composite block copolymer using a (meth) acrylic polymer (A2) having an acid anhydride group in one terminal region according to the present invention as a precursor.
  • the present invention also relates to a pigment dispersant using a (meth) acrylic polymer (A2) having an acid anhydride group in one terminal region according to the present invention.
  • the present invention also relates to a surface modifier or coating agent using a (meth) acrylic polymer (A2) having an acid anhydride group in one terminal region according to the present invention.
  • a novel (meth) acrylic block copolymer which can be easily and inexpensively and easily industrially produced by a general-purpose radical polymerization method other than living radical polymerization, a production method thereof, and an intermediate polymer thereof, and It is possible to provide a pigment dispersant using them, a photosensitive coloring composition for color filters, and a composite block copolymer using the intermediate polymer, a surface modifier by resin treatment, a coating agent, etc. became.
  • the present invention provides a novel (meth) acrylic polymer (A2) having an anhydride group in one terminal region, and a (meth) acrylic polymer (A3) having a thiol group in one terminal region obtained by using the same. And a (meth) acrylic block copolymer (C) obtained using the same. Moreover, it is related with the (meth) acrylic-type polymer (A3) which has a thiol group in the one terminal area
  • the method for producing the (meth) acrylic polymer (A2) having an anhydride group in one terminal region includes the following step (1-1) or (1-2). These steps include a step of producing a (meth) acrylic polymer (A1) or (A1 ′) using a chain transfer reaction of a thiol group.
  • (1-1) An ethylenically unsaturated monomer is polymerized in the presence of a compound having two carboxyl groups and one or more thiol groups in the molecule, and has two carboxyl groups in one terminal region. After obtaining the (meth) acrylic polymer (A1), the two carboxyl groups are modified to an acid anhydride group to obtain a (meth) acrylic polymer (A2) having an anhydride group at one end region.
  • the (meth) acrylic polymer (A1 ′) After obtaining the (meth) acrylic polymer (A1 ′), the one or more hydroxyl groups and the acid chloride group in the tricarboxylic anhydride chloride (E) or the tetracarboxylic anhydride (F) in the molecule
  • the method for producing the (meth) acrylic polymer (A3) having a thiol group in one terminal region includes the following step (2-1) or (2-2).
  • a compound having one or more hydroxyl groups of the acrylic polymer (A1 ′) in the one end region Reacting a compound having one or more isocyanate groups and one or more (meth) acryloyl groups in the molecule;
  • a (meth) acryl having a thiol group in one end region which is obtained by Michael addition reaction between the (meth) acryloyl group and a compound having one or more amino groups and one or more thiol groups in the molecule.
  • the manufacturing method of a (meth) acrylic-type block copolymer (C) includes the following process (3).
  • This process produces
  • the (meth) acrylic block copolymer (C) of the present invention does not require a difficult catalyst removal step such as a metal catalyst or an organic iodine compound as compared with a block copolymer using living radical polymerization or the like.
  • a difficult catalyst removal step such as a metal catalyst or an organic iodine compound
  • there are few problems of odor and coloring due to sulfur and the like and further, it is possible to carry out polymerization under the same conditions as general free radical polymerization systems in terms of synthesis conditions such as oxygen concentration. It is highly advantageous and it is possible to obtain a (meth) acrylic block copolymer by a general-purpose polymerization method.
  • the (meth) acrylic polymer (A1) or (A1 ′) or the (meth) acrylic polymer (B) may be composed of one type of ethylenically unsaturated monomer, or a plurality of types.
  • the ethylenically unsaturated monomer may be used.
  • the following specific example (I) is a specific example of obtaining the (meth) acrylic block copolymer (C) through the steps (1-1), (2-1), and (3).
  • [Specific example (I)] ⁇ Step (1-1): Synthesis of (meth) acrylic polymer (A2) having an anhydride group at one end region> An ethylenically unsaturated monomer is polymerized in the presence of the compound (D) represented by the general formula (1), which is a compound having two carboxyl groups and one or more thiol groups in the molecule, A (meth) acrylic polymer (A1) having two carboxyl groups in the terminal region is obtained (scheme (1) below).
  • R 1 is a methylene group or an ethylene group.
  • (A) is obtained by polymerizing any ethylenically unsaturated monomer (meth) acrylic polymer portion, .R 1 is (meth) acrylic polymer (A1) residue Is the same as in the general formula (1).)
  • the compound having two carboxyl groups and one or more thiol groups in the molecule is not particularly limited as long as it functions as a chain transfer agent.
  • a compound (D) represented by the general formula (1) is preferable.
  • Examples of the compound (D) represented by the general formula (1) include 2-mercaptosuccinic acid and 2-mercaptoglutaric acid. 2-Mercaptosuccinic acid is preferred.
  • compounds having two carboxyl groups and one or more thiol groups in the molecule include 2,2-methylenebis (thioglycolic acid), 2,3-dimercaptosuccinic acid, 4,5 -Examples include, but are not limited to, dimercaptophthalic acid.
  • a compound having two carboxyl groups and one or more thiol groups in the molecule can be used alone or in combination of two or more.
  • schemes (1-1) and (2-1), which are preferred specific examples of schemes (1) and (2), are shown. However, it is not limited to these.
  • Examples of the method for cyclizing the terminal carboxyl group as shown in the scheme (2) include acetic anhydride and 2,6-bis [(2,2,6,6-tetramethyl-1-piperidinyl) methyl] phenylboron.
  • An acid anhydride may be obtained by intramolecular dehydration condensation using an intramolecular condensation catalyst such as an acid. Further, a method of performing intramolecular dehydration condensation under a high temperature heating condition without using a catalyst may be used. Among these, from the viewpoint of production and cost, a system using acetic anhydride as a catalyst is more preferable. Moreover, it is not limited to these methods.
  • Compound (I1) represented by the following general formula (5) which is a compound having an acid anhydride group of the polymer (A2), one or more amino groups and one or more thiol groups in the molecule
  • the compound (I2) represented by the following general formula (6) which is a compound having one or more hydroxyl groups and one or more thiol groups in the molecule, is reacted to have a thiol group in one end region (meta )
  • An acrylic polymer (A3) is obtained (the following scheme (3)).
  • R 3 is a hydrogen atom, an alkyl group, or an aryl group
  • R 4 is a divalent to tetravalent hydrocarbon group which may have a hetero atom
  • n 2 is an integer of 1 to 3.
  • R 4 examples include O (oxygen), N (nitrogen), and S (sulfur). Of these, O is preferable.
  • examples of the divalent to tetravalent hydrocarbon group include an aliphatic hydrocarbon group, an aromatic hydrocarbon group, and a combination thereof.
  • R 4 is preferably selected from an alkylene group, an arylene group, and an alkylene oxide group. More preferably, it is an alkylene group.
  • scheme (3-1) which is a preferred specific example of scheme (3) is shown. However, it is not limited to these.
  • Examples of the compound (I1) represented by the general formula (5) include 2-aminoethanethiol, 3-aminopropyl-1-thiol, 1-aminopropyl-2-thiol, 4-amino-1- Aminoalkanethiols such as butanethiol; aminobenzenethiols such as 2-aminothiophenol, 3-aminothiophenol, 4-aminothiophenol; and the like. Preferred are aminoalkanethiols. These may be used alone or in combination of two or more in any combination. Moreover, it is not limited to these.
  • Examples of the compound (I2) represented by the general formula (6) include 2-mercaptoethanol, 2-mercaptohexanol, 2- [2- (2-mercaptoethoxy) ethylthio] ethanol, 2 -(2-mercaptoethoxy) ethanol, 2- (2-mercaptoethylthio) ethanol, 8-mercapto-3,6-dioxaoctane-1-ol, 11-mercapto-3,6,9-trioxaundecane- 1-ol, 3,6,9,12-tetraoxa-14-mercaptotetradecan-1-ol, 17-mercapto-3,6,9,12,15-pentaoxaheptadecan-1-ol, 2- (mercapto And thioalcohols such as methyl) -3-mercapto-1-propanol. These may be used alone or in combination of two or more in any combination. Moreover, it is not limited to these.
  • the ratio of the amino group or hydroxyl group (mol) of the compound (I1) and compound (I2) is 0.3 to 1.5 with respect to the acid anhydride group (mol) of the (meth) acrylic copolymer (A2). It is preferable that it is the range of these. Further, it is more preferably 0.8 to 1.2.
  • Step (3) Synthesis of (meth) acrylic block copolymer (C)> An ethylenically unsaturated monomer is polymerized in the presence of the (meth) acrylic polymer (A3) (scheme (4) or scheme (5) below).
  • scheme (4-1) which is a preferred specific example of scheme (4) is shown. However, it is not limited to these.
  • scheme (5-1) which is a preferred specific example of scheme (5) is shown. However, it is not limited to these.
  • R 2 is a divalent to tetravalent hydrocarbon group which may have a hetero atom, and n 1 is an integer of 1 to 3.
  • the divalent to tetravalent hydrocarbon group in R 2 can be the same as R 4 in the general formula (6).
  • (A) is a (meth) acrylic polymer part obtained by polymerizing an arbitrary ethylenically unsaturated monomer, and is a (meth) acrylic polymer (A1 ′) residue. 2 is the same as the general formula (2).)
  • scheme (6-1) which is a preferred specific example of scheme (6) is shown. However, it is not limited to these.
  • scheme (7-1) which is a preferred specific example of scheme (7) is shown. However, it is not limited to these.
  • scheme (8-1) which is a preferred specific example of scheme (8) is shown. However, it is not limited to these.
  • the tricarboxylic anhydride chloride (E) and the tetracarboxylic anhydride (F) are reacted in an equimolar number with one or more hydroxyl groups in the polymer (A1 ′). More specifically, When using tricarboxylic anhydride chloride (E), only one acid chloride group, and when using tetracarboxylic anhydride (F), only one acid anhydride group in two acid anhydride groups It is ideal to react.
  • the compound having one or more hydroxyl groups and one or more thiol groups in the molecule is not particularly limited as long as it functions as a chain transfer agent.
  • the compound (G) represented by the general formula (2) is preferable.
  • Examples of the compound (G) represented by the general formula (2) include 2-mercaptoethanol, 2-mercaptohexanol, 6-mercapto-1-hexanol, 3-mercapto-1-propanol, and 7-mercapto-1-heptanol.
  • the compound (G) examples include 2- (2-mercaptoethoxy) ethanol, 2- [2- (2-mercaptoethoxy) ethylthio] ethanol, 8-mercapto-3,6-dioxaoctane-1- All, 11-mercapto-3,6,9-trioxaundecan-1-ol, 17-mercapto-3,6,9,12,15-pentaoxaheptadecan-1-ol, 2- (mercaptomethyl)- 3-mercapto-1-propanol, dimercaprol, 2,2-dimethyl-3-mercapto-1-propanol, 2,2-bis (mercaptomethyl) -1-propanol, 8-mercapto-1-octanol, 10- Examples include, but are not limited to, mercapto-1-decanol, 11-mercapto-1-undecanol, and the like.
  • the compounds having one or more hydroxyl groups and one or more thiol groups in the molecule can
  • Examples of the tricarboxylic anhydride chloride (E) include trimellitic anhydride chloride, 4- (chlorocarbonyl) cyclohexane-1,2-dicarboxylic anhydride, N, N′-1,4-phenylenebis [octahydro-1, 3-dioxo-5-isobenzofurancarboxamide], 5- [4- (chlorocarbonyl) benzoyl] isobenzofuran-1,3-dione, 3,4-diphenyl-5- (chloroformyl) phthalic anhydride, 1, Examples include, but are not limited to, benzyl 3-dioxo-6- (chloroformyl) isobenzofuran-5-carboxylate, 1,3-dioxo-1,3-dihydroisobenzofuran-4-carboxylic acid chloride, etc. is not.
  • a tricarboxylic anhydride chloride (E) can be used individually by 1 type or
  • tetracarboxylic anhydride examples include pyromellitic anhydride, 1H, 3H-naphtho [2,3-c: 6,7-c ′] difuran-1,3,6,8-tetraone, 2,3,6,7-biphenylenetetracarboxylic acid 2,3: 6,7-dianhydride, 3,4,8,9-pyrenetetracarboxylic acid 3,4: 8,9-dianhydride, 5, 5′-bi [isobenzofuran] -1,1 ′, 3,3′-tetraone, 2,3,6,7-anthracenetetracarboxylic acid 2,3: 6,7-dianhydride, 4-methyl-1H , 3H-benzo [1,2-c: 4,5-c ′] difuran-1,3,5,7-tetraone, 1,4,5,8-naphthalenetetracarboxylic acid 1,8: 4,5- Dianhydride, 5,5 ′-(1,4-phenylene) bis (
  • the compound (I1) represented by the general formula (5) which is a compound having an acid anhydride group of the polymer (A2), one or more amino groups, and one or more thiol groups in the molecule;
  • the compound (I2) represented by the general formula (6) which is a compound having one or more hydroxyl groups and one or more thiol groups in the molecule, is reacted to have a thiol group in one terminal region (meta )
  • An acrylic polymer (A3) is obtained (the following scheme (9) or scheme (10)).
  • schemes (9-1) and (10-1), which are preferred specific examples of schemes (9) and (10), are shown. However, it is not limited to these.
  • Step (3) Synthesis of (meth) acrylic block copolymer (C)> An ethylenically unsaturated monomer is polymerized in the presence of the (meth) acrylic polymer (A3) (the following scheme (11) or the following scheme (12)).
  • (B) is a (meth) acrylic polymerized portion obtained by polymerizing an arbitrary ethylenically unsaturated monomer obtained in step (3). , As described above.)
  • (Meth) acrylic polymer (A3) having a thiol group at one end region The (meth) acrylic polymer (A1 ′) having one or more hydroxyl groups in the one end region is added to the one or more hydroxyl groups, one or more isocyanate groups and one or more (meth) in the molecule. The compound having an acryloyl group is reacted, and the (meth) acryloyl group and a compound having one or more amino groups and one or more thiol groups in the molecule are subjected to a Michael addition reaction in one end region. A (meth) acrylic polymer (A3) having a thiol group is obtained (scheme (13) below).
  • R 25 is a hydrogen atom or a methyl group
  • R 26 is a divalent to tetravalent hydrocarbon group which may have a hetero atom
  • W is an integer of 1 to 3. The other symbols are as described above.
  • the di- to tetravalent hydrocarbon group for R 26 may be the same as R 4 in the general formula (6).
  • a compound having an isocyanate group and one or more (meth) acryloyl groups has a (meth) acryloyl group having a valence of R 26 of the hydrocarbon group of R 26 .
  • scheme (13-1) which is a preferred specific example of scheme (13) is shown. However, it is not limited to these.
  • the synthesis conditions include one or more hydroxyl groups in the (meth) acrylic polymer (A1 ′) having one or more hydroxyl groups in one terminal region, one or more isocyanate groups and one or more ( A compound having a (meth) acryloyl group is mixed within a temperature range of 70 to 100 ° C., and then stirred and reacted for about 1 hour, whereby the (meth) acryloyl group, one or more amino groups in the molecule, and one A method in which a compound having the above thiol group is heated and stirred at 100 ° C. for 5 hours to cause a Michael addition reaction.
  • it is not limited to these methods.
  • Step (3) Synthesis of (meth) acrylic block copolymer (C)> An ethylenically unsaturated monomer is polymerized in the presence of the (meth) acrylic polymer (A3) (the following scheme (14)).
  • (B) is a (meth) acrylic polymerized portion obtained by polymerizing any ethylenically unsaturated monomer obtained in step (3). Other symbols are as described above. is there.)
  • a preferred structure of the (meth) acrylic polymer (A2) having an anhydride group in one end region obtained by the specific examples (I) and (II) can be represented by the following general formula (7).
  • (A) is a (meth) acrylic polymer residue
  • R 5 is a direct bond or a divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide group
  • L 1 is a direct bond or —O—C ( ⁇ O) —
  • X 1 is a tetravalent group represented by the following general formula (8), general formula (9), or general formula (10)
  • Y 1 is a hydrogen atom or —COOH.
  • R 6 is a methine group or an ethyne group.
  • Q 1 is a direct bond or a divalent group having 1 to 20 carbon atoms.
  • X 1 is a tetravalent group represented by the general formula (9), and k 2 is 1.
  • a preferred structure of the (meth) acrylic polymer (A3) having a thiol group in one terminal region obtained by the specific examples (I), (II) and (III) can be represented by the following general formula (11). .
  • (A) is a (meth) acrylic polymer residue, R 7 is a direct bond or a divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide; L 2 is a direct bond or —O—C ( ⁇ O) —, X 2 is a tetravalent group represented by the following general formula (12), general formula (13), general formula (14), or general formula (15), Y 2 is a hydrogen atom or —COOH, one of Y 3 and Y 4 is a group represented by the following general formula (16) or general formula (17), and the other of Y 3 and Y 4 is It is a hydrogen atom or COOR 15 , and R 15 is a hydrogen atom, an alkyl group, an aryl group or a halogen atom. )
  • R 8 is a methine group or an ethyne group.
  • k 3 is 1 or 2.
  • Q 2 is a direct bond or a divalent group having 1 to 20 carbon atoms.
  • R 9 is an alkylene group.
  • M 1 is —NR 11 — or —O—
  • R 11 is a hydrogen atom, an alkyl group, or an arylene group
  • R 10 is a divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide.
  • R 12 and R 13 are each independently a divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide; R 14 is a hydrogen atom, an alkyl group, an aryl group or a halogen atom.
  • a preferred structure of the (meth) acrylic block copolymer (C) obtained by the specific examples (I), (II) and (III) is such that the hydrogen atom of the thiol group in the one terminal region of the general formula (11) is It can be represented by the following general formula (18) converted into the polymer (B).
  • (A) is a (meth) acrylic polymer residue
  • R 16 is a direct bond or a divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide
  • L 3 is a direct bond or —O—C ( ⁇ O) —
  • X 3 is a tetravalent group represented by the following general formula (19), general formula (20), general formula (21), or general formula (22)
  • Y 5 is a hydrogen atom or —COOH
  • One of Y 6 and Y 7 is a group represented by the following general formula (23) or general formula (24), the other of Y 6 and Y 7 is a hydrogen atom or COOR 24 , and R 24 is , A hydrogen atom, an alkyl group, an aryl group or a halogen atom.
  • R 17 is a methine group or an ethyne group.
  • k 4 is 1 or 2.
  • Q 3 is a direct bond or a divalent group having 1 to 20 carbon atoms.
  • R 18 is an alkylene group.
  • M 2 is —NR 20 — or —O—
  • R 20 is a hydrogen atom or an alkyl group
  • R 19 is a divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide
  • (B) is a (meth) acrylic polymer residue.
  • R 21 and R 22 are each independently a divalent group selected from the group consisting of an alkylene group, an arylene group, and an alkylene oxide;
  • R 23 is a hydrogen atom, an alkyl group, an aryl group or a halogen atom,
  • (B) is a (meth) acrylic polymer residue.
  • ethylenically unsaturated monomer examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, and isobutyl (meth).
  • Alkyl (meth) acrylates such as acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, trimethylcyclohexyl (meth) acrylate, and isobornyl (meth) acrylate; Aromatic (meth) acrylates such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, and phenoxydiethylene glycol (meth) acrylate; Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate and oxetane (meth) acrylate; Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate and e
  • Monomers that can be used in combination with the above acrylic monomers include styrenes such as styrene and ⁇ -methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, isobutyl vinyl ether, and acetic acid. And fatty acid vinyls such as vinyl and vinyl propionate.
  • a method for polymerizing the (meth) acrylic polymer (A1) or (A1 ′) or the (meth) acrylic polymer (B) is not particularly limited, and the polymerization can be performed by a conventionally known method. Moreover, a polymerization initiator can also be used together arbitrarily. However, it is not limited to these.
  • the ethylenically unsaturated monomer for obtaining the (meth) acrylic polymer (B) preferably has a composition different from that of the polymer (A1) or (A1 ′).
  • the weight average molecular weight of the (meth) acrylic polymer (A1) or (A1 ′) or (meth) acrylic polymer (B) is preferably from 1,000 to 500,000, more preferably from 2,000 to 50,000, still more preferably from 2,000 to 50,000. 12000, particularly preferably 3000 to 8000.
  • the (meth) acrylic block copolymer (C) of the present invention can be used as a pigment dispersant, an alkali-soluble resin, and a binder resin, and is particularly suitable for a photosensitive coloring composition for a color filter. It can be used as a resin. Moreover, it can utilize as a pigment dispersant and binder resin suitable for a printing ink composition.
  • the (meth) acrylic block copolymer (C) can be suitably used as a pigment dispersant.
  • the pigment dispersant has a colorant affinity part having a property of adsorbing to a colorant such as a pigment, and a solvent affinity part compatible with the colorant carrier, and adsorbs to the colorant to color the colorant. It serves to stabilize dispersion in the agent carrier.
  • a (meth) acrylic heavy polymer containing an ethylenically unsaturated monomer having an affinity for the colorant is used.
  • a (meth) acrylic block copolymer (C) having a (meth) acrylic polymer (B) containing a combined (A1) or (A1 ′) and an ethylenically unsaturated monomer having affinity for the solvent Can be synthesized.
  • the pigment dispersant either one having an acidic substituent or one having a basic substituent can be suitably used.
  • the basic dispersant when used as a color filter coloring composition, the basic dispersant is dispersed. It is excellent in stability and is preferable. If the amine value of the basic dispersant is 10 mg KOH / g or more and 99 mg KOH / g or less, the solubility in the developer is improved, and development can be performed within a predetermined time in the development process. This is preferable because undissolved colored resin composition does not remain in the pixel portion. More preferably, it is 50 to 90 mgKOH / g.
  • the (meth) acrylic block copolymer (C) of the present invention is highly adsorbed to the pigment because the pigment adsorbing groups are arranged at high density, and has high dispersion stability because there is no crosslinking. Can be secured.
  • the pigment-type adsorbing group is randomly arranged in the random type dispersant, the viscosity may be increased by crosslinking.
  • the content of the (meth) acrylic block copolymer (C) is preferably 1 to 70 parts by weight and more preferably 10 to 60 parts by weight with respect to 100 parts by weight of the pigment.
  • the amount of the (meth) acrylic block copolymer (C) is 1 part by weight or more, the pigment dispersibility effect is easily obtained.
  • it is 70 weight part or less, when producing the pixel pattern of a color filter by this photolithographic method using this coloring composition, alkali developability will become favorable.
  • the (meth) acrylic block copolymer (C) of the present invention not only ensures high pigment dispersion stability, but also has high dispersibility and solvent resistance, which have heretofore been difficult as pigment dispersants for color filter applications. Can be made compatible.
  • the (meth) acrylic block copolymer (C) of the present invention is a new block type. It is possible to become a dispersing agent.
  • the (meth) acrylic block copolymer (C) of the present invention has a functional group having heat or photocrosslinkability in the (meth) acrylic polymer (A1) or (B) residue. Also good. Preferably, it is at least one selected from the group consisting of a furyl group, an active methylene group, an active methine group, a blocked isocyanate group, a blocked isothiocyanate group, an oxetane group, a t-butyl group, an acrylate group, and a methacrylate group.
  • the dispersion stability and the pigment dispersant for the developer It is possible to further improve chemical resistance while improving the solubility of.
  • the functional group can be introduced by polymerization using the ethylenically unsaturated monomer having the functional group.
  • Examples of the ethylenically unsaturated monomer having a furyl group include furfuryl methacrylate. However, it is not limited to these.
  • Examples of the ethylenically unsaturated monomer having an active methylene group or an active methine group include 2- (1,3 dioxobutoxy) ethyl (meth) acrylate and 2- (1,3 diester) (meth) acrylate.
  • the blocked isocyanate group or the blocked isothiocyanate group means a structure in which the isocyanate group or the isothiocyanate group is blocked by a protecting group that can be removed by heating. Is generated. Since these undergo a crosslinking reaction with a hydroxyl group or the like, it is preferable to use them together with a hydroxyl group or the like.
  • a ⁇ b is preferably 2 or more, and more preferably 5 or more.
  • Examples of the ethylenically unsaturated monomer having an isocyanate group or an isothiocyanate group include (meth) acryloyl isocyanate, 2-isocyanatoethyl (meth) acrylate, 2- (meth) acryloyloxyethoxyethyl isocyanate, 1 , 1- (bis (meth) acryloyloxymethyl) ethyl isocyanate, m- (meth) acryloylphenyl isocyanate, and other isocyanate group-containing (meth) acrylates, ⁇ , ⁇ -dimethyl-4-isopropenylbenzyl isocyanate, etc.
  • Examples include isocyanate group-containing styrene derivatives. However, it is not limited to these.
  • ethylenically unsaturated monomer having an oxetane group examples include ethylenically unsaturated monomers such as oxetane (meth) acrylate and (3-ethyloxetane-3-yl) methyl acrylate. However, it is not limited to these.
  • Examples of the ethylenically unsaturated monomer having a t-butyl group include t-butyl methacrylate and t-butyl acrylate. However, it is not limited to these.
  • a (meth) acrylic polymer having a hydroxyl group by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with a part of the ethylenically unsaturated monomer
  • examples include a method in which after obtaining (A1) or (B), all or part of the hydroxyl group is reacted with an isocyanate group or an isothiocyanate group in a (meth) acrylate having an isocyanate group or an isothiocyanate group.
  • the pigment dispersant according to the present invention has excellent chemical resistance and solvent resistance after the pigment dispersant and coloring composition containing the same are heat / photocured. , Heat resistance and alkali resistance can be obtained. This is because the thermal and photobridge functional groups (furyl group, active methylene group or active methine group, blocked isocyanate group, oxetane group, t-butyl group, acrylate group and methacrylate group, respectively) are crosslinked by baking.
  • the heat / photocrosslinkable functional group is used in an amount of 5 to 90 mol% in a total of 100 mol% of the ethylenically unsaturated monomer constituting the (meth) acrylic copolymer (A1) or (B). It is particularly preferable to use 20 to 60 mol%. If it is less than 5 mol%, the effect of crosslinking is small, and if it exceeds 90 mol%, the polymer may cause a crosslinking reaction during synthesis and may gel.
  • the colorant that can be used in the coloring composition of the present invention can be arbitrarily selected from conventionally known various pigments and dyes. These pigments / dyes can be used alone or in admixture of two or more at any ratio as required.
  • the content of the colorant is preferably 10% by weight or more, more preferably 15% by weight or more from the viewpoint of obtaining sufficient color reproducibility, based on the total nonvolatile components of the coloring composition (100% by weight), and most preferably Preferably it is 20 weight% or more. Further, from the viewpoint of the stability of the coloring composition, the preferred colorant content is 90% by weight or less, more preferably 80% by weight or less, and most preferably 70% by weight or less.
  • Red pigments include C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48: 1, 48: 2, 48: 3, 48: 4, 49, 49: 1, 49: 2, 50: 1, 52: 1, 52: 2, 53, 53: 1, 53: 2, 53: 3, 57, 57: 1, 57: 2, 58: 4, 60, 63, 63: 1, 63: 2, 64, 64: 1, 68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177,
  • C.I. I. Pigment Red 48 1, 122, 168, 177, 202, 206, 207, 209, 224, 242, or 254, more preferably C.I. I. Pigment Red 177, 209, 224, 242, or 254.
  • blue pigments examples include C.I. I. Pigment Blue 1, 1: 2, 9, 14, 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56: 1, 60, 61, 61: 1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like.
  • aluminum phthalocyanine pigments described in JP-A No. 2004-333817, Japanese Patent No. 4893859 and the like can also be used, and the invention is not particularly limited thereto.
  • green pigments examples include C.I. I. Pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55 or 58.
  • C.I. I. Pigment Green 7, 36 or 58 examples of green pigments.
  • zinc phthalocyanine pigments described in JP 2008-19383 A, JP 2007-320986 A, JP 2004-70342 A, and the like can be used, and the invention is not particularly limited thereto.
  • a halogenated zinc phthalocyanine pigment or an aluminum phthalocyanine pigment can obtain a high spectral transmittance and a wide color reproduction range that cannot be obtained with other green pigments.
  • These pigments have a problem that heat resistance and solvent resistance are slightly inferior to those conventionally used.
  • it is a coloring composition using these pigments, it is excellent in stability by dispersing using the (meth) acrylic block copolymer (C) which is the invention of the present application.
  • a colored composition having heat resistance and solvent resistance can be obtained.
  • a yellow pigment can be used in combination with the green coloring composition.
  • yellow pigments that can be used in combination include C.I. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180,
  • the colorant used as the green coloring composition preferably contains at least one of a halogenated zinc phthalocyanine pigment and an aluminum phthalocyanine pigment, and further contains a yellow pigment to provide excellent color characteristics. can do.
  • Particularly preferable pigment ratios include, for example, when a halogenated zinc phthalocyanine pigment and a yellow pigment are used, based on the total weight of the pigment component, the halogenated zinc phthalocyanine pigment is 50 to 100% by weight, and the yellow pigment is 0 to 50%. More preferably, the halogenated zinc phthalocyanine pigment is 50 to 90% by weight and the yellow pigment is 5 to 45% by weight, based on the total weight of the pigment component.
  • the aluminum phthalocyanine pigment is 5 to 70% by weight and the yellow pigment is 30 to 95% by weight, more preferably the pigment component based on the total weight of the pigment component. Based on the total weight, the aluminum phthalocyanine pigment is 15 to 60% by weight and the yellow pigment is 40 to 85% by weight.
  • Preferred pigment ratios are 50 to 100% by weight for the halogenated zinc phthalocyanine pigment, 0 to 50% by weight for the aluminum phthalocyanine pigment, and 0 to 50% by weight for the yellow pigment, based on the total weight of the pigment component.
  • the halogenated zinc phthalocyanine pigment is 50 to 90% by weight
  • the aluminum phthalocyanine pigment is 5 to 45% by weight
  • the yellow pigment is 5 to 45% by weight.
  • the chromaticity region can be expanded by such a composition ratio of the pigment.
  • Examples of purple pigments include C.I. I. Pigment Violet 1, 1: 1, 2, 2: 2, 3, 3: 1, 3: 3, 5, 5: 1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50 and the like.
  • C.I. I. Pigment violet 19 or 23 more preferably C.I. I. Pigment Violet 23.
  • the pigment dispersant can contain a dye within a range that does not lower the heat resistance for color matching.
  • the dyes are, among others, triphenylmethane dyes, triphenylmethane lake pigments, diphenylmethane dyes, diphenylmethane lake pigments, quinoline dyes, quinoline pigments Thiazine dyes, thiazole dyes, xanthene dyes, xanthene lake pigments, diketopyrrolopyrrole pigments, and the like can be used.
  • xanthene dyes xanthene dyes that are xanthene lake pigments
  • quinoline dyes quinoline dyes that are quinoline pigments
  • triphenylmethane dyes triphenylmethane dyes that are triphenylmethane lake pigments
  • a diketopyrrolopyrrole pigment that is a diketopyrrolopyrrole pigment.
  • the color filter having a high contrast ratio is excellent.
  • the pigment dispersion of the present invention may further contain a dye derivative.
  • a dye derivative By using the dye derivative, the effect of preventing re-aggregation of the pigment after dispersion is great, and the brightness and viscosity stability are improved. preferable.
  • the dye derivative include a compound in which a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, anthraquinone, acridone, or triazine.
  • the content of the pigment derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more with respect to 100 parts by weight of the pigment from the viewpoint of improving dispersibility. Further, from the viewpoint of heat resistance and light resistance, it is preferably 40 parts by weight or less, more preferably 35 parts by weight or less.
  • an acidic derivative of an organic pigment or a pigment derivative that is a metal salt thereof because of excellent stability.
  • the acidic derivative of an organic pigment or a metal salt thereof has a great effect of preventing re-aggregation of the pigment after dispersion because it further promotes the pigment adsorption of the pigment and the pigment dispersant and improves the dispersibility of the pigment. Therefore, when a pigment dispersion coloring composition obtained by dispersing a pigment in a pigment carrier using an acidic derivative of an organic pigment or a metal salt thereof, a color filter having excellent stability can be obtained.
  • a (meth) acrylic block copolymer consisting of a (meth) acrylic polymer (A1) having solvophilicity and a (meth) acrylic polymer (B) having a functional group containing a nitrogen atom Dispersibility improves more by using together with the pigment dispersant which is a coalescence (C). This is considered to promote the pigment adsorption of the dispersant by the acid-base interaction between the acidic substituent of the derivative arranged near the pigment and the basic substituent of the dispersant.
  • the structure of an acidic derivative of an organic pigment or a metal salt thereof is a compound represented by the following general formula (25).
  • Formula (25) V-Zd (In the general formula (25), V is an organic pigment residue, Z is an acidic substituent, d is a hydrogen atom or a metal ion.)
  • organic pigment constituting the organic pigment residue of V examples include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; copper phthalocyanine, halogenated copper phthalocyanine, zinc phthalocyanine, halogenated zinc phthalocyanine, Phthalocyanine pigments such as metal-free phthalocyanine; Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigment; dioxazine pigment; perinone pigment; Thioindigo pigments; isoindoline pigments; isoindolinone pigments; selenium pigments; quinophthalone pigments; dioxazine pigments; metal complex pigments.
  • diketopyrrolopyrrole pigments such as
  • the acidic derivative of the organic pigment or the metal salt thereof may be used alone or may contain both an acidic derivative and a metal salt, and each of them may be used as a mixture of two or more or other pigment derivatives.
  • Organic solvent is used to make it easy to form a filter segment by coating the pigment dispersion so that the dry film thickness is 0.2 to 5 ⁇ m. It does not specifically limit as an organic solvent, A conventionally well-known thing can be used individually or in mixture of 2 or more types by arbitrary ratios as needed.
  • the organic solvent is used in an amount of 800 to 4000 parts by weight with respect to 100 parts by weight of the pigment.
  • a filter segment having a desired uniform film thickness can be formed. To preferred.
  • the alkali-soluble resin that may be further added is an alkali-developable resin, and has an acid group such as a carboxyl group in its structure, and the acid group is neutralized with an aqueous alkali solution and becomes soluble in water. Can be developed.
  • a photosensitive resin having a photosensitive group such as an unsaturated bond group or a non-photosensitive resin can be used.
  • the photosensitive resin include a photosensitive cyclized rubber resin, a photosensitive phenol resin, a photosensitive polyacrylate resin, a photosensitive polyamide resin, a photosensitive polyimide resin, an unsaturated polyester resin, and a polyester.
  • examples thereof include acrylate resins, polyepoxy acrylate resins, polyurethane acrylate resins, polyether acrylate resins, and polyol acrylate resins.
  • non-photosensitive resin examples include cellulose acetate resin, nitrocellulose resin, styrene (co) polymer, polyvinyl butyral resin, aminoalkyd resin, polyester resin, amino resin-modified polyester resin, polyurethane Resin, acrylic polyol urethane resin, soluble polyamide resin, soluble polyimide resin, soluble polyamideimide resin, soluble polyesterimide resin, hydroxyethyl cellulose, styrene-maleic acid ester copolymer, (meth) acrylic acid ester Examples thereof include system (co) polymers. These alkali-soluble resins can be used singly or in combination of two or more.
  • the content of the alkali-soluble resin in the pigment colorant composition is preferably 5 to 300 parts by mass, more preferably 10 to 100 parts by mass with respect to 100 parts by mass of the pigment.
  • the (meth) acrylic copolymer (C) of the present invention may be used as an alkali-soluble resin.
  • the pattern shape obtained with the photosensitive composition or photosensitive coloring composition using the (meth) acrylic copolymer (C) of the present invention as an alkali-soluble resin is good, the development speed is fast, and it is suitable for color filter applications. ing. This is because the (meth) acrylic copolymer (C) having a block structure is used for the alkali-soluble resin, and the reason is unknown. This is thought to be due to improved performance. Also, the (meth) acrylic copolymer (C) newly developed in the present invention rather than the block type alkali-soluble resin having a narrow molecular weight distribution synthesized by living radical polymerization with the same composition and molecular weight. However, the developing performance tended to improve.
  • the composition is cured by ultraviolet irradiation, and a photopolymerization initiator is added to form a filter segment by a photolithography method, and a solvent development type or alkali development type photosensitive coloring is added. It can be prepared in the form of a composition.
  • photopolymerization initiators acetophenone compounds, benzoin compounds, benzophenone compounds, thioxanthone compounds, thioxanthone compounds, triazine compounds, oxime ester compounds, phosphine compounds, quinone compounds, borate compounds, carbazole compounds A compound, an imidazole compound, a titanocene compound, or the like is used.
  • photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.
  • the photopolymerization initiator preferably includes at least one photopolymerization initiator selected from the group consisting of acetophenone compounds, phosphine compounds, imidazole compounds, and oxime ester compounds.
  • the photopolymerization initiator By including these photopolymerization initiators, the pattern shape and linearity of the filter segment become better.
  • the content of the photopolymerization initiator is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the pigment, and more preferably 10 to 150 parts by weight from the viewpoint of photocurability and developability.
  • the photopolymerizable compound used in the present invention includes a monomer or oligomer that forms a resin by being cured by ultraviolet rays or heat.
  • Examples of the photopolymerizable compound include methyl (meth) acrylate, ethyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and cyclohexyl (meth) acrylate.
  • ⁇ -carboxyethyl (meth) acrylate polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylol Propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether (Meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic ester of methylolated melamine, epoxy Various acrylic and methacrylic esters
  • the content of the photopolymerizable monomer is preferably 10 to 300 parts by weight with respect to 100 parts by weight of the pigment, and more preferably 10 to 200 parts by weight from the viewpoint of photocurability and developability.
  • the photosensitive coloring composition of the present invention can contain other dispersants, sensitizers, polyfunctional thiols, ultraviolet absorbers, polymerization inhibitors, and storage stabilizers. Moreover, in order to improve adhesiveness with a transparent substrate etc., it is possible to contain an adhesion improver such as a silane coupling agent, or an amine compound that functions to reduce dissolved oxygen.
  • an adhesion improver such as a silane coupling agent, or an amine compound that functions to reduce dissolved oxygen.
  • the photosensitive coloring composition of the present invention comprises various pigments such as a three-roll mill, a two-roll mill, a sand mill, a kneader, and an attritor together with a pigment dispersant in a colorant carrier such as a binder resin and / or a solvent.
  • a pigment dispersion is produced by finely dispersing using a dispersing means, and a photopolymerization initiator, a photosensitive binder resin, a photopolymerizable compound, and optionally a sensitizer, a polyfunctional thiol, and an ultraviolet absorber.
  • a polymerization inhibitor, a storage stabilizer, a solvent, and other components can be mixed and stirred.
  • the photosensitive coloring composition containing two or more kinds of pigments is prepared by mixing each pigment dispersion separately in a colorant carrier and / or a solvent, and further mixing a photopolymerization initiator or photopolymerization property. It can be produced by mixing and stirring compounds and the like.
  • the color filter of the present invention is provided with a filter segment formed on the base material by forming the color composition color composition of the present invention, for example, a black matrix and red, green, and blue filter segments. Can be provided.
  • the filter segment may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment.
  • a base material such as a transparent substrate, a glass plate, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate is used.
  • a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or the resin plate in order to drive the liquid crystal after forming the panel.
  • a photosensitive coloring composition prepared as a solvent developing type or alkali developing type colored resist material is spray coated, spin coated, slit coated, roll coated, etc. on a transparent substrate.
  • the coating method is applied so that the dry film thickness is 0.2 to 10 ⁇ m and dried. Thereafter, ultraviolet exposure is performed through a mask having a predetermined pattern.
  • the filter segment can be formed by immersing in a solvent or an alkaline developer, or spraying the developer with a spray or the like to remove an uncured portion to form a desired pattern. Furthermore, in order to accelerate the polymerization of the filter segment formed by development, heating can be performed as necessary. According to the photolithography method, a filter segment with higher accuracy than the printing method can be formed.
  • an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used.
  • an antifoamer and surfactant can also be added to a developing solution.
  • a development processing method a shower development method, a spray development method, a dip (immersion) development method, a paddle (liquid accumulation) development method, or the like can be applied.
  • a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to prevent polymerization inhibition due to oxygen. After forming, UV exposure can also be performed.
  • the color filter of the present invention can be produced by an electrodeposition method, a transfer method or the like in addition to the above method.
  • Resin means those used as excipients, adhesives, and adhesives in the processing of various pigments, ceramics, non-woven fabrics, fibers, leather, paper, inks, paints, metals, etc., and acrylic resins, polyester resins, Also included are alcohol-soluble resins such as polyamide resins, polyurethane resins, and cellulose, and water-soluble resins. However, it is not limited to these.
  • the ink composition of the present invention is a composition containing gravure ink, flexo ink, screen ink, offset ink, UV curable ink, metal printing ink, conductive ink, and other functional inks including printing ink. Means that. However, it is not limited to these.
  • the (meth) acrylic polymer (A2) of the present invention can be used as a precursor of a composite block copolymer by utilizing the reactivity of an acid anhydride group. For example, by chemically reacting with a reactive functional group of another resin, it can be easily combined with various resins and a composite block copolymer can be obtained.
  • Specific methods for obtaining the composite block copolymer include, for example, an acrylic resin, a urethane resin, and a polyester having a functional group in a main chain or a side chain that can easily chemically react with an anhydride group such as a hydroxyl group or an amino group.
  • a composite block resin can be easily obtained by mixing with a resin such as a resin or a polyamide resin and causing a chemical reaction.
  • Examples of the composite block copolymer include, but are not limited to, diblock copolymers, triblock copolymers, multiblock copolymers, and graft copolymers.
  • the (meth) acrylic polymer (A2) of the present invention described above can be used as various surface modifiers and coating agents by utilizing the reactivity of acid anhydride groups.
  • the (meth) acrylic polymer (A2) of the present invention is combined with a reactive functional group such as a hydroxyl group or amino group of a pigment or dye, and used as a surface modifier (pigment dispersant) by chemical bonding. It can also be used as a coating agent or the like imparted with new functionalities such as barrier properties and wear resistance by reacting with a functional group on the surface of a substrate such as a packaging material or a package to form a composite.
  • a coating agent or the like imparted with new functionalities such as barrier properties and wear resistance by reacting with a functional group on the surface of a substrate such as a packaging material or a package to form a composite.
  • Pigment dispersant using (meth) acrylic polymer (A2) having an acid anhydride group in one terminal region The pigment dispersant using the (meth) acrylic polymer (A2) of the present invention described above will be described in detail.
  • an azo pigment it has a hydroxyl group in the structure of the pigment such as Pigment Red 57.1 and Pigment Red 48, 49, and the acid anhydride group and the chemical group of the (meth) acrylic polymer (A2) of the present invention. By making it react, it can be used as a surface modifier (pigment dispersant). The same can be applied to organic pigments used for resists for color filters as well as printing ink applications.
  • Advantages of using the pigment dispersant using the (meth) acrylic polymer (A2) having an acid anhydride group in one end region of the present invention include simplification of the dispersion process by resin treatment, pigment derivatives, etc. From the viewpoint of not having to use it, it is considered to be highly useful in increasing the brightness.
  • silicon compounds such as cellulose nanofiber and colloidal silica also have a hydroxyl group, and the above description applies. However, it is not limited to these.
  • the (meth) acrylic block copolymer and its intermediate polymer of the present invention can be used for various applications.
  • pigment dispersants such as color filters already described above, pigment surface treatment dye salt forming resins, resists, quantum dots, self-assembled monolayers, adhesives, lubricants, paints, inks, packaging materials, It can be used for the production of drugs, pesticides, personal care (hairdressing / cosmetics), semiconductors, displays, etc.
  • ⁇ Weight average molecular weight (Mw) and molecular weight distribution (PDI)> GPC (trade name: GPCV-2000, manufactured by Nippon Waters Co., Ltd., column: TSKgel, ⁇ -3000, mobile phase: 10 mM triethylamine / dimethylformamide solution) and polystyrene (molecular weight 427,000, 190,000, 96) as standard substances were used. , 400, 37, 400, 10, 200, 2,630, 440, 92), a calibration curve was prepared, and the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured. The molecular weight distribution (PDI Mw / Mn) was calculated from this measured value.
  • amine value was determined by potentiometric measurement using a 0.1N hydrochloric acid aqueous solution, and then converted to an equivalent of potassium hydroxide.
  • the amine value indicates the amine value (mgKOH / g) of the solid content.
  • Example 1 Block copolymer solution (A-1)) (Process (1-1))
  • A-1 Block copolymer solution (A-1))
  • a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 330 parts of PGMEA and 160 parts of MMA and 160 parts of nBMA were charged as the A block component and replaced with nitrogen gas.
  • the reaction vessel was heated to 80 ° C., and 14.4 parts of 2-mercaptosuccinic acid and 3.2 parts of AIBN were added as mercaptan chain transfer agents and reacted for 12 hours. It was confirmed that 95% had reacted by solid content measurement.
  • AB block copolymers (A-2) to (A-5) Ethylenically unsaturated monomer (A block component, B block component), mercaptan chain transfer agent in the same manner as AB block copolymer (A-1) so as to have a weight ratio to the raw material species shown in Table 1.
  • AB block copolymers (A-2) to (A-5) Ethylenically unsaturated monomer (A block component, B block component), mercaptan chain transfer agent in the same manner as AB block copolymer (A-1) so as to have a weight ratio to the raw material species shown in Table 1.
  • Example 6 AB block copolymer solution (A-6)
  • Process (1-2) In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 330 parts of PGMEA and 160 parts of MMA and 160 parts of nBMA were charged as the A block component and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and 14.4 parts of 2-mercaptoethanol and 3.2 parts of AIBN were added as mercaptan chain transfer agents and reacted for 12 hours. It was confirmed that 95% had reacted by solid content measurement.
  • Example 7 and 8 AB block copolymer (A-7), (A-8)
  • an ethylenically unsaturated monomer (A block component, B block component) and a mercaptan chain transfer agent were added so as to have a weight ratio to the raw material species shown in Table 2.
  • the AB block copolymers (A-7) and (A-8) were obtained by changing.
  • Example 9 AB block copolymer (A-9)
  • Process (1-2) In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 330 parts of PGMEA and 160 parts of MMA and 160 parts of nBMA were charged as the A block component and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., 6.4 parts of 2-mercaptoethanol and 3.2 parts of AIBN were added as mercaptan chain transfer agents, and reacted for 12 hours. It was confirmed that 95% had reacted by solid content measurement.
  • Example 10 and 11 Ethylenically unsaturated monomer (A block component, B block component) in the same manner as AB block copolymer (A-9), so as to be the charge ratio with the raw material species so as to be the weight ratio of Table 3
  • the product was synthesized by changing the mercaptan chain transfer agent.
  • Example 12 AB block copolymer solution (A-12)) (Process (2-2))
  • a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 330 parts of PGMEA and 160 parts of MMA and 160 parts of nBMA were charged as the A block component and replaced with nitrogen gas.
  • the reaction vessel was heated to 80 ° C., and 14.4 parts of 2-mercaptoethanol and 3.2 parts of AIBN were added as mercaptan chain transfer agents and reacted for 12 hours. It was confirmed that 95% had reacted by solid content measurement.
  • the primary amine group was reacted until Michael addition of 95% or more of the primary amino group of 2-aminoethanethiol to the acryloyl group was measured.
  • the obtained solution was reacted in the same manner as (A-1) to obtain an AB block copolymer (A-12) solution having a solid content of 50% by weight.
  • Example 13 AB block copolymer (A-13)
  • the product was synthesized by changing the mercaptan chain transfer agent.
  • Example 14 Composite AB block copolymer solution (A-14) using polymer (A2)
  • a composite AB block copolymer was synthesized by the following method using the polymer (A2-1) having an anhydride in one terminal region obtained as an intermediate in Example 1 as a precursor of the A block.
  • a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 127 parts of PGMEA and 80 parts of DMAEMA were charged and replaced with nitrogen gas.
  • the reaction vessel was heated to 80 ° C., 7.5 parts of 2-mercaptoethanol and 3.2 parts of AIBN were added as mercaptan chain transfer agents and reacted for 12 hours.
  • Example 15 Composite AB block copolymer solution (A-15) using polymer (A2)
  • the composition of the A block precursor and the B block precursor was changed so that the raw material species and the charging ratio were as shown in Table 5 in the weight ratio. Synthesized.
  • the ethylenically unsaturated monomer means a copolymer component
  • the ethylenically unsaturated monomer (crosslinking group) means a copolymer having a heat or photocrosslinkable functional group. It means a polymerization component.
  • Pigment dispersion (R-1)) As a pigment, C.I. I. Pigment Green 58 and 12 parts C.I. I. Pigment Yellow 138 was treated with a bead mill using 3 parts of Pigment Yellow 138, 12.5 parts of Pigment Dispersant (A-1) Solution (solid content: 40% by weight), and 72.5 parts of PGMEA as a solvent. 1) was adjusted.
  • Pigment dispersion (R-2 to 15), Comparative pigment dispersion (R-16 to 19) The pigment dispersion (R-2 to 15) and the comparative pigment dispersion (R-16) were the same as the pigment dispersion (R-1) except that the types of pigment dispersant were changed as shown in Table 2. To 19) were adjusted.
  • PG58 is C.I. I. Pigment Green 58 and PY138 are C.I. I. Pigment yellow 138, respectively.
  • the dispersion stability evaluations of the pigment dispersions (R-1 to 15) using the (meth) acrylic block copolymer of the present invention as the pigment dispersant were all good.
  • a comparative pigment dispersion (R-18, 19) synthesized by a living radical polymerization method (RAFT polymerization) gave good results.
  • the pigment dispersion (R-16, 17) using the comparative random copolymer as the pigment dispersant gave bad results.
  • Photosensitive coloring composition S-1 for color filter The following mixture was stirred and mixed to be uniform and then filtered through a 1.0 ⁇ m filter to obtain an alkali developing type photosensitive coloring composition (S-1) for color filters.
  • Pigment dispersion 1 (R-1) 40.0 parts Alkali-soluble resin 1 25.0 parts Photopolymerizable monomer (manufactured by Toa Gosei Co., Ltd.
  • Photosensitive coloring compositions for color filters S-2 to 15 and comparative compositions S-16 to 19 Photosensitive coloring compositions for color filters (S-2 to 19) were obtained in the same manner as in Example 1 except that the pigment dispersion shown in Table 9 was used.
  • Photosensitive coloring compositions S-20 and 21 for color filters comparative composition S-22
  • a photosensitive colored composition (S-20 to 22) for color filters was obtained in the same manner as in Example 1 except that the materials shown in Table 10 were used.
  • the alkali-soluble resins 2 and 3 the following block copolymers were used.
  • Example 16 (alkali-soluble resin 2); AB block copolymer solution (A-16))
  • the composition of the A block is MMA / St
  • the composition of the B block is MAA
  • a coalesced solution was obtained.
  • 40 parts of GMA (glycidyl methacrylate) and 3 parts of triethylbenzylammonium chloride were added and reacted for 5 hours while maintaining the inside of the system at 80 ° C.
  • This alkali-soluble resin 2 had an average molecular weight (Mw) of 14,500, a molecular weight distribution (PDI) of 2.15, and an acid value of 110 (mgKOH / g).
  • This alkali-soluble resin 3 had an average molecular weight (Mw) of 15,500, a molecular weight distribution (PDI) of 1.15, and an acid value of 110 (mgKOH / g).
  • a coating film of the photosensitive coloring composition was formed to a thickness of 25 ⁇ m on a 50 mm ⁇ 30 mm glass plate whose surface had been cleaned, and dried at 90 ° C. for 10 minutes.
  • the glass plate on which the coating film was formed was immersed in a 1% potassium hydroxide aqueous solution, and the solubility of the coating film in a 1% potassium hydroxide aqueous solution (alkali aqueous solution) was observed.
  • the solubility was evaluated according to the following criteria.
  • B The coating film is eluted from the glass plate within 10 minutes of immersion.
  • C The coating film remains on the glass plate after 10 minutes of immersion. If evaluation is A or B, it is excellent in alkali developability.
  • the photosensitive coloring composition was applied to a 100 mm x 100 mm, 250 ⁇ m thick polyethylene naphthalate film fixed with a pressure-sensitive adhesive on a glass substrate using a spin coater so that the final film thickness after drying under reduced pressure was 2.0 ⁇ m.
  • ultraviolet exposure was performed using an ultrahigh pressure mercury lamp at an illuminance of 20 mW / cm 2 and an exposure amount of 50 mJ / cm 2 .
  • the coated film was heated at 100 ° C. for 20 minutes, allowed to cool, and peeled off from the glass substrate to obtain a film for evaluation.
  • the obtained film was measured for chromaticity, immersed in propylene glycol monomethyl ether acetate for 10 minutes at room temperature, washed with ion-exchanged water, and air-dried. Thereafter, the film was visually observed and the chromaticity was measured, and the color difference ⁇ E was calculated.
  • the chromaticity was measured with a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.) using a C light source.
  • OSP-SP100 manufactured by Olympus Optical Co., Ltd.
  • the photosensitive coloring composition was applied onto an alkali-free glass substrate using a spin coater and then pre-baked on an 80 ° C. hot plate for 3 minutes to form a film having a thickness of 4.0 ⁇ m.
  • the obtained film was exposed to ultraviolet light having an intensity of 365 W / m 2 at 365 nm for 10 seconds through a photomask having a remaining pattern of 15 ⁇ m square.
  • development was performed with a 0.05 wt% aqueous solution of potassium hydroxide at 25 ° C. for 60 seconds, followed by washing with pure water for 1 minute.
  • an evaluation film having a predetermined pattern was formed by post-baking in an oven at 230 ° C. for 20 minutes.
  • Tables 9 and 10 show the evaluation results of alkali developability, chemical resistance and resolution.
  • “having a crosslinking group” means that the copolymer component of the pigment dispersant contains an ethylenically unsaturated monomer having a thermal or photocrosslinkable functional group.
  • the photosensitive coloring compositions of Examples 4, 5, 8, 11, 13, and 15 in which the (meth) acrylic block copolymer of the present invention having a crosslinkable functional group in the A block component was used as a pigment dispersant.
  • the chemical resistance of the product (S-4, 5, 8, 11, 13, 15) was all good, and all of the alkali developability, chemical resistance, and storage stability of the pigment dispersion were good results.
  • the photosensitive composition (S-17) of Comparative Example 2 having a crosslinkable functional group has poor storage stability of the pigment dispersion, and the photosensitive composition (S-29) of Comparative Example 4 is poor. The alkali developability was poor.
  • the photosensitive coloring compositions (S-20, 21) of Examples 20 and 21 using the (meth) acrylic block copolymer of the present invention as an alkali-soluble resin are those of Comparative Example 22. Evaluation results of better resolution than the photosensitive coloring composition (S-22) were shown.
  • a surface modifier solution (T-1) which is a (meth) acrylic polymer (A2) having an anhydride group in one terminal region having a solid content of 50% by weight was obtained.
  • Example 102 surface modifier solution (T-2)
  • Process (1-2) A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 330 parts of toluene and 150 parts of MMA, 150 parts of nBMA, and 20 parts of MAA as copolymerization components and replaced with nitrogen gas.
  • the reaction vessel was heated to 80 ° C., and 14.4 parts of 2-mercaptoethanol and 3.2 parts of AIBN were added as mercaptan chain transfer agents and reacted for 12 hours. It was confirmed that 95% had reacted by solid content measurement.
  • trimellitic anhydride chloride was charged into the reaction vessel and reacted at 75 ° C. for 4 hours.
  • FT-IR measurement the reaction was continued until the absorption peak at the acid chloride site of the raw trimellitic anhydride chloride disappeared.
  • a surface modifier solution (T-2) having a solid content of 50% by weight was obtained.
  • Table 11 shows the evaluation results of initial viscosity and storage stability.
  • PR57: 1 means C.I. I. Pigment Red 57: 1.
  • the use of the present invention examples include a photosensitive composition for color filters in particular, and this can contribute to improvement in image performance and economy of liquid crystal color displays used in various applications.
  • the (meth) acrylic block copolymer (C) that characterizes the present invention has excellent properties as a pigment dispersant, particularly dispersion stability, improved solubility of alkali developability, It is possible to satisfy chemical properties.
  • provision of alkali-soluble resins, photosensitive color compositions for color filters, composite block copolymers using intermediate polymers thereof, surface modifiers by coating with resins, coating agents, etc. is also possible.

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Abstract

L'invention concerne une technique destinée à permettre de synthétiser un copolymère séquencé permettant une production industrielle de manière simple et bon marché, au moyen d'un procédé de polymérisation par voie radicalaire générique autre qu'une polymérisation par voie radicalaire vivante. Plus précisément, l'invention fournit un nouveau copolymère séquencé (méth)acrylique ainsi qu'un procédé de fabrication de celui-ci. Selon l'invention, est produit un polymère (méth)acrylique (A2) qui est constitué par modification au moyen d'un groupe anhydride acide de deux groupes carboxyle contenus dans un polymère (méth)acrylique (A1) possédant deux groupes carboxyle dans une seule région terminaison, lequel polymère (méth)acrylique (A1) est obtenu par polymérisation d'un monomère éthyléniquement insaturé en présence d'un composé possédant deux groupes carboxyle et un groupe thiol ou plus dans chaque molécule. Le copolymère séquencé (méth)acrylique (C) de l'invention est constitué par polymérisation d'un monomère éthyléniquement insaturé en présence d'un polymère (méth)acrylique (A3) possédant un groupe thiol dans une seule région terminaison, lequel polymère (méth)acrylique (A3) est obtenu par réaction d'un composé possédant un groupe amino ou plus et un groupe thiol ou plus dans chaque molécule, ou d'un composé possédant un groupe hydroxyle ou plus et un groupe thiol ou plus dans chaque molécule, avec ledit groupe anhydride acide.
PCT/JP2017/042352 2016-11-28 2017-11-27 Polymère (méth)acrylique, copolymère séquencé (méth)acrylique, dispersion de pigment, composition colorante photosensible, filtre coloré, composition d'encre, copolymère séquencé composite, agent de dispersion de pigment, et agent de revêtement WO2018097279A1 (fr)

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KR1020197013561A KR102516074B1 (ko) 2016-11-28 2017-11-27 (메타)아크릴계 중합체, (메타)아크릴계 블록 공중합체, 안료 분산체, 감광성 착색 조성물, 컬러 필터, 잉크 조성물, 복합 블록 공중합체, 안료 분산제, 및, 코팅제
CN201780073427.6A CN110023350B (zh) 2016-11-28 2017-11-27 (甲基)丙烯酸系聚合物、共聚物、分散体、组合物、滤光片、分散剂、改良剂和涂布剂

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WO2019177075A1 (fr) * 2018-03-15 2019-09-19 富士フイルム株式会社 Composition de résine durcissable, matériau durci, élément optique de diffraction, élément optique multicouche de diffraction et procédé de fabrication de composition de résine durcissable
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CN112011193A (zh) * 2019-05-29 2020-12-01 阪田油墨股份有限公司 彩色滤光片用颜料分散组合物及彩色滤光片用颜料分散抗蚀剂组合物
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