WO2018079659A1 - Copolymère bloc, agent dispersant, et composition de dispersion de pigment - Google Patents

Copolymère bloc, agent dispersant, et composition de dispersion de pigment Download PDF

Info

Publication number
WO2018079659A1
WO2018079659A1 PCT/JP2017/038717 JP2017038717W WO2018079659A1 WO 2018079659 A1 WO2018079659 A1 WO 2018079659A1 JP 2017038717 W JP2017038717 W JP 2017038717W WO 2018079659 A1 WO2018079659 A1 WO 2018079659A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
block copolymer
block
mass
aromatic
Prior art date
Application number
PCT/JP2017/038717
Other languages
English (en)
Japanese (ja)
Inventor
清水達彦
梅本光
Original Assignee
大塚化学株式会社
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 大塚化学株式会社 filed Critical 大塚化学株式会社
Priority to JP2018505485A priority Critical patent/JP6316531B1/ja
Priority to KR1020187012560A priority patent/KR102032076B1/ko
Priority to CN201780004006.8A priority patent/CN108431064B/zh
Publication of WO2018079659A1 publication Critical patent/WO2018079659A1/fr

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
    • 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
    • C08F293/005—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 using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • 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
    • C08F6/00—Post-polymerisation treatments
    • C08F6/06—Treatment of polymer solutions
    • 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
    • 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

Definitions

  • the present invention relates to a block copolymer, a dispersant, and a pigment dispersion composition.
  • a pigment dispersion method for example, a coating film made of a pigment dispersion composition in which a pigment, a dispersant, and a dispersion medium (solvent) are mixed is formed on a substrate, exposed through a photomask having a desired pattern shape, and alkali developed. Is done.
  • a transparent electrode for driving the liquid crystal is formed thereon by vapor deposition or sputtering, and further an orientation for aligning the liquid crystal in a certain direction.
  • a film is formed.
  • these transparent electrodes and alignment films their formation is generally performed at a high temperature of 200 ° C. or higher.
  • heat resistance such as a decrease in contrast ratio of the color filter and a change in hue becomes a problem before and after the process involving high heat.
  • Patent Document 1 in order to obtain a color filter having excellent heat resistance, an AB block comprising an A block having a quaternary ammonium base in the side chain and a B block not having a quaternary ammonium base. It is disclosed that a copolymer is used as a pigment dispersant for a color filter (see Patent Document 1 (claim 1, paragraphs 0049 to 0058)).
  • Patent Document 2 an AB block copolymer comprising an A block having an acidic group in the side chain and a B block having an amino group or a quaternary ammonium base in the side chain is used as a pigment dispersant.
  • the coating characteristics, long-term storage stability, and alkali developability are improved (see Patent Document 2 (Claim 1, paragraphs 0031 to 0034, 0038 to 0040)).
  • the present invention has been made in view of the above circumstances, and an object thereof is to provide a block copolymer that can be used as, for example, a dispersant and has excellent heat resistance.
  • the block copolymer of the present invention that has been able to solve the above-mentioned problems includes an A block containing a structural unit derived from a vinyl monomer having an acidic group, a structural unit represented by the general formula (1), and a general formula ( And a B block including the structural unit represented by 2).
  • R ⁇ 11> , R ⁇ 12 > and R ⁇ 13 > show the chain or cyclic hydrocarbon group which may have a substituent each independently. Two or more of R 11 , R 12 and R 13 may be bonded to each other to form a cyclic structure.
  • X 1 represents a divalent linking group.
  • R 14 represents a hydrogen atom or a methyl group.
  • Y ⁇ represents at least one selected from the group consisting of an aromatic dicarboxylic imide anion, an aromatic sulfonate anion, an aromatic phosphonate anion, and an aromatic carboxylate anion.
  • R 21 and R 22 each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R 21 and R 22 may be bonded to each other to form a cyclic structure.
  • X 2 represents a divalent linking group.
  • R 23 represents a hydrogen atom or a methyl group.
  • a conventional polymer having a quaternary ammonium base generally uses a halogen anion as a counter ion of a quaternary ammonium cation.
  • a polymer containing a halogen anion is considered to be inferior in heat resistance because it causes a counterion elimination reaction in a high temperature atmosphere.
  • the counter ion of the quaternary ammonium cation in the B block is an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonic acid anion, or an aromatic carboxylic acid anion, Excellent in properties.
  • the block copolymer of this invention has A block which has an acidic group, and B block which has a specific structure, it can be used as a dispersing agent.
  • the block copolymer is preferably an AB type block copolymer.
  • the content of the structural unit derived from the vinyl monomer having an acidic group is preferably 2% by mass to 20% by mass in 100% by mass of the A block.
  • the content of the structural unit represented by the general formula (1) is preferably 30% by mass to 85% by mass in 100% by mass of the B block.
  • the content of the A block is preferably 35% by mass to 85% by mass in 100% by mass of the block copolymer.
  • the present invention includes a first composition containing the block copolymer and a second composition obtained by washing the first composition with water and drying.
  • the molecular weight distribution (PDI) of the block copolymer contained in the first composition is preferably 2.0 or less.
  • the dispersing agent containing the said block copolymer, a 1st composition, or a 2nd composition is contained in this invention.
  • the present invention includes a pigment dispersion composition containing the dispersant, a pigment, and a dispersion medium. Examples of such a composition include a pigment dispersion composition for a color filter.
  • the production method of the block copolymer of the present invention is represented by an A block containing a structural unit derived from a vinyl monomer having an acidic group, a structural unit represented by the following formula (2), and the following formula (3).
  • R 21 and R 22 each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R 21 and R 22 may be bonded to each other to form a cyclic structure.
  • X 2 represents a divalent linking group.
  • R 23 represents a hydrogen atom or a methyl group.
  • R 31 , R 32 and R 33 each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R 31 , R 32 and R 33 may be bonded to each other to form a cyclic structure.
  • X 3 represents a divalent linking group.
  • R 34 represents a hydrogen atom or a methyl group.
  • X ⁇ represents a halogen anion.
  • an aromatic dicarboxylic acid imide, aromatic sulfonic acid, aromatic phosphonic acid or an alkali metal salt of aromatic carboxylic acid is used to convert the counter ion of the quaternary ammonium cation from the halogen anion to the aromatic dicarboxylic acid. It becomes easy to exchange (anion exchange) with an acid imide anion, an aromatic sulfonate anion, an aromatic phosphonate anion or an aromatic carboxylate anion.
  • each ion is classified based on the HASB rule.
  • halide ions eg, chloride ions
  • Alkali metal ions eg, potassium ions
  • Aromatic dicarboxylic imide anions, aromatic sulfonate anions, aromatic phosphonate anions and aromatic carboxylate anions having a ⁇ -electron system of aromatic rings are considered to be classified as soft bases.
  • Quaternary ammonium ions in the polymer are considered to be classified as soft acids.
  • a combination of an acid and a base having the same degree of hardness such as a soft base for a soft acid and a hard base for a hard acid, has a strong binding force. It is considered that the anion exchange is facilitated by generating an ion pair having a strong binding force in the anion exchange.
  • the production method preferably prepares the block copolymer precursor using living radical polymerization.
  • the production method preferably includes a step (C) of washing the block copolymer obtained in the step (B) with water.
  • a block copolymer that can be used as a dispersant and has excellent heat resistance can be provided.
  • the block copolymer of the present invention is represented by an A block containing a structural unit derived from a vinyl monomer having an acidic group, a structural unit represented by the general formula (1) described later, and a general formula (2) described later. And a B block including a structural unit.
  • a block can be rephrased as “A segment”, and “B block” can be rephrased as “B segment”.
  • the “vinyl monomer” refers to a monomer having a carbon-carbon double bond capable of radical polymerization in the molecule.
  • the “structural unit derived from a vinyl monomer” refers to a structural unit in which a carbon-carbon double bond capable of radical polymerization of a vinyl monomer is polymerized into a carbon-carbon single bond.
  • (Meth) acryl means “at least one of acrylic and methacrylic”.
  • “(Meth) acrylate” means “at least one of acrylate and methacrylate”.
  • “(Meth) acryloyl” refers to “at least one of acryloyl and methacryloyl”.
  • the A block is a polymer block having a structural unit derived from a vinyl monomer having an acidic group. It is thought that alkali development becomes easy because A block has an acidic group. Therefore, the block copolymer can be suitably used in a pigment dispersion composition for a color filter used for producing a color filter employing alkali development.
  • a block may have only 1 type of structural unit derived from the vinyl monomer which has an acidic group, and may have 2 or more types.
  • the vinyl monomer having an acidic group is preferably at least one selected from a vinyl monomer having a carboxy group, a vinyl monomer having a sulfonic acid group, or a vinyl monomer having a phosphoric acid group.
  • at least one selected from a (meth) acrylic monomer having a carboxy group, a (meth) acrylic monomer having a sulfonic acid group, or a (meth) acrylic monomer having a phosphoric acid group is preferable.
  • vinyl monomers having a carboxy group examples include (meth) acrylic acid; hydroxy groups such as 2- (meth) acryloyloxyethyl succinate, 2- (meth) acryloyloxyethyl maleate, 2- (meth) acryloyloxyethyl phthalate A monomer obtained by reacting an acid anhydride such as maleic anhydride, succinic anhydride or phthalic anhydride with a vinyl monomer (preferably hydroxyalkyl (meth) acrylate) having a carboxylic acid; crotonic acid, maleic acid, itaconic acid and the like.
  • an acid anhydride such as maleic anhydride, succinic anhydride or phthalic anhydride
  • a vinyl monomer preferably hydroxyalkyl (meth) acrylate
  • vinyl monomer having a sulfonic acid group examples include vinyl sulfonic acid, styrene sulfonic acid, ethyl disulfonate (meth) acrylate, methylpropyl sulfonic acid (meth) acrylamide, and ethyl sulfonate (meth) acrylamide.
  • Examples of the vinyl monomer having a phosphate group include 2- (phosphonooxy) ethyl (meth) acrylate.
  • the content of the structural unit derived from the vinyl monomer having an acidic group is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 7% by mass or more, and 20% by mass in 100% by mass of the A block. % Or less is preferable, more preferably 18% by mass or less, and still more preferably 16% by mass or less. If the content of the structural unit derived from the vinyl monomer having an acidic group is 2% by mass or more, the dissolution rate when neutralized with an alkali is increased in alkali development, and if it is 20% by mass or less, the hydrophilicity is high. However, it is possible to prevent the formed pixels from becoming messy.
  • the A block may have a structural unit other than the structural unit derived from the vinyl monomer having an acidic group.
  • the other structural unit that can be contained in the A block is not particularly limited as long as it is formed by a vinyl monomer that can be copolymerized with both a vinyl monomer having an acidic group and a vinyl monomer that forms the B block described later.
  • Vinyl monomers that can form other structural units of the A block may be used alone or in combination of two or more.
  • Examples of the ⁇ -olefin include 1-hexene, 1-octene, 1-decene and the like.
  • Examples of the aromatic vinyl monomer include styrene, ⁇ -methylstyrene, 4-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methoxystyrene, 2-hydroxymethylstyrene, 1-vinylnaphthalene and the like.
  • Examples of the vinyl monomer containing a heterocycle include 2-vinylthiophene, N-methyl-2-vinylpyrrole, 1-vinyl-2-pyrrolidone, 2-vinylpyridine, 4-vinylpyridine and the like.
  • Examples of the vinylamide include N-vinylformamide, N-vinylacetamide, N-vinyl- ⁇ -captolactam and the like.
  • Examples of vinyl carboxylate include vinyl acetate, vinyl pivalate, vinyl benzoate and the like.
  • Examples of dienes include butadiene, isoprene, 4-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene and the like.
  • (Meth) acrylic monomers include (meth) acrylates having a chain alkyl group (straight chain alkyl group or branched chain alkyl group); (meth) acrylates having a cyclic alkyl group (monocyclic structure); aromatic ring groups (Meth) acrylate having (meth) acrylamide; (meth) acrylate having a polyethylene glycol structural unit; (meth) acrylate having a hydroxy group; caprolactone adduct of (meth) acrylate having a hydroxy group; ) Acrylate; (meth) acrylate having a cyclic ether group.
  • Examples of the (meth) acrylate having a chain alkyl group include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (Meth) acrylate, tert-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and the like.
  • Examples of the (meth) acrylate having a cyclic alkyl group include cyclohexyl (meth) acrylate, methylcyclohexyl (meth) acrylate, and cyclododecyl (meth) acrylate.
  • Examples of the (meth) acrylate having an aromatic ring group include benzyl (meth) acrylate, phenyl (meth) acrylate, and phenoxyethyl (meth) acrylate.
  • Examples of (meth) acrylamide include (meth) acrylamide, N-methyl (meth) acrylamide, N-isopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide and the like.
  • Examples of the (meth) acrylate having a hydroxy group include 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate and the like. (Meth) acrylate etc. are mentioned.
  • the caprolactone adduct of (meth) acrylate having a hydroxy group includes a 1 mol adduct of caprolactone of 2-hydroxyethyl (meth) acrylate, a 2 mol adduct of caprolactone of 2-hydroxyethyl (meth) acrylate, and 2-hydroxyethyl (meth).
  • Examples include acrylate caprolactone 3 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 4 mol adduct, 2-hydroxyethyl (meth) acrylate caprolactone 5 mol adduct, and the like.
  • Examples of the (meth) acrylate having an alkoxy group include methoxyethyl (meth) acrylate and ethoxyethyl (meth) acrylate.
  • Examples of the (meth) acrylate having a cyclic ether group include glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (meth) acryloylmorpholine, 2- (4-morpholinyl) ethyl (meth) acrylate, (3- Ethyl oxetane-3-yl) methyl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclic trimethylolpropane formal (meth) acrylate, 2- [(2-Tetrahydropyranyl) oxy] ethyl (meth) acrylate, 1,3-dioxane- (meth) acrylate and the like.
  • the vinyl monomer that can form another structural unit that can be included in the A block is preferably a (meth) acrylic monomer, (meth) acrylate having a chain alkyl group, (meth) acrylate having an aromatic ring group, polyethylene glycol structure At least one selected from the group consisting of (meth) acrylates having units, (meth) acrylates having hydroxy groups, caprolactone adducts of (meth) acrylates having hydroxy groups, and (meth) acrylates having cyclic ether groups More preferably.
  • the vinyl monomer that can be used in the A block can be used alone or in combination of two or more.
  • the total content of these structural units is preferably 30% by mass or more, more preferably 35% by mass or more, and further preferably 40% by mass or more in 100% by mass of the A block.
  • 98 mass% or less is preferable, More preferably, it is 95 mass% or less, More preferably, it is 90 mass% or less.
  • a block is (meth) acrylamide, (meth) acrylate having a polyethylene glycol structural unit, (meth) acrylate having a hydroxy group, caprolactone adduct of (meth) acrylate having a hydroxy group, (meth) acrylate having an alkoxy group And having a structural unit derived from at least one vinyl monomer selected from the group consisting of (meth) acrylates having a cyclic ether group, the total content of these structural units is 100% by mass in the A block. Is preferably 2% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, preferably 70% by mass or less, more preferably 65% by mass or less, and further preferably 60% by mass or less. .
  • the A block preferably has no amino group. That is, it is preferable that the vinyl monomer constituting the A block does not contain a vinyl monomer having an amino group.
  • the pigment when used as a pigment dispersant, the pigment is adsorbed by both the A block and the B block, and the dispersion performance of the pigment is lowered.
  • the content of the structural unit derived from the vinyl monomer having an amino group in the A block is preferably 2% by mass or less, more preferably 1% by mass or less, still more preferably 0.1% by mass or less, and most preferably 0% by mass. %.
  • the various structural units contained in the A block may be contained in any form such as random copolymerization and block copolymerization in the A block. From the viewpoint of uniformity, it is preferably contained in the form of random copolymerization.
  • the A block may be formed of a copolymer of a structural unit composed of an a1 block and a structural unit composed of an a2 block.
  • the B block is a polymer block having a structural unit represented by the general formula (1) and a structural unit represented by the general formula (2). Since the B block has a quaternary ammonium base in addition to a tertiary amino group, it is considered to have a high affinity with the pigment.
  • the structural unit represented by the general formula (1) has a quaternary ammonium salt in the structure, and as its anion component, an aromatic dicarboxylic acid imide anion, an aromatic sulfonate anion, an aromatic phosphonate anion and an aromatic It has at least one selected from the group consisting of carboxylate anions.
  • the structural unit represented by the general formula (1) in the B block may be only one type or may have two or more types.
  • R ⁇ 11> , R ⁇ 12 > and R ⁇ 13 > show the chain or cyclic hydrocarbon group which may have a substituent each independently. Two or more of R 11 , R 12 and R 13 may be bonded to each other to form a cyclic structure.
  • X 1 represents a divalent linking group.
  • R 14 represents a hydrogen atom or a methyl group.
  • Y ⁇ represents at least one selected from the group consisting of an aromatic dicarboxylic imide anion, an aromatic sulfonate anion, an aromatic phosphonate anion, and an aromatic carboxylate anion.
  • the chain hydrocarbon group represented by R 11 to R 13 includes both straight and branched chain groups.
  • Examples of the group represented by R 11 to R 13 include an alkyl group having 1 to 4 carbon atoms which may have a substituent, and an aralkyl group having 7 to 16 carbon atoms which may have a substituent.
  • a methyl group, an ethyl group, a propyl group, and a benzyl group (—CH 2 C 6 H 5 ) are more preferable.
  • Examples of the cyclic structure formed by bonding two or more of R 11 to R 13 to each other include a 5- to 7-membered nitrogen-containing heteromonocycle or a condensed ring formed by condensing two of these.
  • the nitrogen-containing heterocycle preferably has no aromaticity, and more preferably a saturated ring. Specific examples include structures represented by the following formulas (11-1), (11-2), and (11-3).
  • R 61 is any one of R 11 to R 13 .
  • R 62 represents an alkyl group having 1 to 6 carbon atoms.
  • l represents an integer of 0 to 5.
  • m represents an integer of 0 to 4.
  • n represents an integer of 0 to 4. When l is 2 to 5, m is 2 to 4, and n is 2 to 4, a plurality of R 62 may be the same or different.
  • examples of the divalent linking group X 1 include a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, a —CONH—R 15 — group, a —COO—R 16 — group
  • R 15 and R 16 are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms.
  • the divalent linking group X 1 is preferably a —COO—R 16 — group, more preferably a —COO—R 17 — group (wherein R 17 is a methylene group, an alkylene group having 2 to 4 carbon atoms).
  • Y ⁇ as a counter ion represents at least one selected from the group consisting of an aromatic dicarboxylic imide anion, an aromatic sulfonate anion, an aromatic phosphonate anion and an aromatic carboxylate anion.
  • Y ⁇ as the counter ion is preferably an aromatic dicarboxylic acid imide anion or an aromatic sulfonic acid anion.
  • An aromatic dicarboxylic acid imide anion is an anion of an aromatic dicarboxylic acid imide and is obtained by removing a proton from nitrogen constituting dicarbomide.
  • the aromatic dicarboxylic imide has an aromatic ring and an imide group (—C ( ⁇ O) NHC ( ⁇ O) —) directly bonded to the aromatic ring in the molecule. Both ends of the imide group may be bonded to one aromatic ring, or may be bonded to different aromatic rings.
  • the aromatic dicarboxylic acid imide anion those represented by the general formula (12) are preferable.
  • Ring A represents an aromatic ring which may have a substituent.
  • the aromatic ring constituting the ring A is a ring structure having aromaticity.
  • the aromatic ring includes both single rings and condensed rings.
  • As the monocycle a 5- or 6-membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are preferable.
  • the condensed ring is preferably a 2-5 condensed ring, and is preferably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring.
  • Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.
  • the aromatic dicarboxylic acid imide anion includes 1,3-dioxo-1,3-dihydro-2H-isoindole-2-ide (formula (12-1)); 1,3-dioxo-1,3-dihydro- 2H-benzo [f] isoindole-2-id (formula (12-2)); 1,3-dioxo-1,3-dihydro-2H-benzo [g] isoindole-2-id (formula (12-) 3)); 5-phenyl-1,3-dioxo-1,3-dihydro-2H-isoindole-2-ide (formula (12-4)); 1,3-dioxo-1,3-dihydro-2H -Naphtho [2,3-f] isoindole-2-id (formula (12-5)); 1,3-dioxo-1,3-dihydro-2H-naphtho [2,
  • the aromatic sulfonic acid anion is an anion of aromatic sulfonic acid.
  • the aromatic sulfonic acid has an aromatic ring and a sulfonic acid group directly bonded to the aromatic ring in the molecule.
  • an aromatic sulfonate anion what is represented by following formula (13) is preferable.
  • Ar represents the aromatic ring which may have a substituent.
  • the aromatic ring constituting Ar is a ring structure having aromaticity.
  • the aromatic ring includes both single rings and condensed rings.
  • As the monocycle a 5- or 6-membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are preferable.
  • the condensed ring is preferably a 2-5 condensed ring, and is preferably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring.
  • Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.
  • aromatic sulfonate anions examples include benzenesulfonate anion (formula (13-1)); 1-naphthalenesulfonate anion (formula (13-2)); 2-naphthalenesulfonate anion (formula (13-3)) 4-biphenylsulfonate anion (formula (13-4)); 2-anthracenesulfonate anion (formula (13-5)); 1-anthracenesulfonate anion (formula (13-6)); 3-phenanthrenesulfone Acid anion (formula (13-7)); p-styrene sulfonate anion (formula (13-8)); p-toluenesulfonate anion (formula (13-9)).
  • Aromatic phosphonic acids have an aromatic ring and a phosphonic acid group directly bonded to the aromatic ring in the molecule.
  • aromatic phosphonate anion what is represented by following formula (14) is preferable.
  • Ar represents the aromatic ring which may have a substituent.
  • the aromatic ring constituting Ar is a ring structure having aromaticity.
  • the aromatic ring includes both single rings and condensed rings.
  • As the monocycle a 5- or 6-membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are preferable.
  • the condensed ring is preferably a 2-5 condensed ring, and is preferably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring.
  • Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.
  • benzenephosphonate anion (formula (14-1)); 1-naphthalenephosphonate anion (formula (14-2)); 2-naphthalenephosphonate anion (formula (14-3)) 4-biphenylphosphonate anion (formula (14-4)); 2-anthracenephosphonate anion (formula (14-5)); 1-anthracenephosphonate anion (formula (14-6)); 3-phenanthrenephosphone Acid anion (formula (14-7)); and the like.
  • the aromatic carboxylic acid anion is an anion of an aromatic carboxylic acid.
  • the aromatic carboxylic acid has an aromatic ring and a carboxy group directly bonded to the aromatic ring in the molecule.
  • an aromatic carboxylate anion what is represented by following formula (15) is preferable.
  • Ar represents the aromatic ring which may have a substituent.
  • the aromatic ring constituting Ar is a ring structure having aromaticity.
  • the aromatic ring includes both single rings and condensed rings.
  • As the monocycle a 5- or 6-membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are preferable.
  • the condensed ring is preferably a 2-5 condensed ring, and is preferably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring.
  • Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.
  • aromatic carboxylate anion examples include benzoate anion (formula (15-1)); 1-naphthalenecarboxylate anion (formula (15-2)); 2-naphthalenecarboxylate anion (formula (15-3)); 4-biphenylcarboxylate anion (formula (15-4)); 2-anthracenecarboxylate anion (formula (15-5)); 1-anthracenecarboxylate anion (formula (15-6)); 3-phenanthrenecarboxylic acid An anion (formula (15-7)); p-styrene carboxylate anion (formula (15-8)); p-toluenecarboxylate anion (formula (15-9)).
  • the content of the structural unit represented by the general formula (1) is preferably 30% by mass or more, more preferably 35% by mass or more, still more preferably 40% by mass or more, and 85% by mass in 100% by mass of the B block. % Or less, more preferably 80% by mass or less, and still more preferably 75% by mass or less.
  • the structural unit represented by the general formula (2) has a tertiary amine structure.
  • the structural unit represented by the general formula (2) in the B block may be only one type, or may have two or more types.
  • R 21 and R 22 each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R 21 and R 22 may be bonded to each other to form a cyclic structure.
  • X 2 represents a divalent linking group.
  • R 23 represents a hydrogen atom or a methyl group.
  • the chain hydrocarbon group represented by R 21 or R 22 includes both linear and branched chains.
  • Examples of the group represented by R 21 or R 22 include an alkyl group having 1 to 4 carbon atoms which may have a substituent, and an aralkyl group having 7 to 16 carbon atoms which may have a substituent.
  • a methyl group, an ethyl group, a propyl group, and a benzyl group are more preferable.
  • Examples of the cyclic structure formed by bonding R 21 or R 22 to each other include a 5- to 7-membered nitrogen-containing heteromonocycle or a condensed ring formed by condensing two of these.
  • the nitrogen-containing heterocycle preferably has no aromaticity, and more preferably a saturated ring.
  • Specific examples include structures represented by the following formulas (21-1), (21-2), and (21-3).
  • R 71 represents an alkyl group having 1 to 6 carbon atoms.
  • l represents an integer of 0 to 5.
  • m represents an integer of 0 to 4.
  • n represents an integer of 0 to 4.
  • l is 2 to 5
  • m is 2 to 4
  • n is 2 to 4, a plurality of R 71 may be the same or different.
  • examples of the divalent linking group X 2 include a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, a —CONH—R 24 — group, and a —COO—R 25 — group.
  • R 24 and R 25 are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms].
  • the content of the structural unit represented by the general formula (2) is preferably 15% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and 70% by mass in 100% by mass of the B block. % Or less, more preferably 65% by mass or less, and still more preferably 60% by mass or less.
  • the B block may be only the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2), or may include other structural units. From the viewpoint of maintaining affinity with the pigment, the total content of the structural unit represented by the general formula (1) and the structural unit represented by the general formula (2) in the B block is 80% by mass or more. More preferably, it is 90 mass% or more, More preferably, it is 95 mass% or more. Moreover, it is preferable that B block does not contain substantially the structural unit derived from the vinyl monomer which has the acidic group which A block has. That is, the content of the structural unit derived from the vinyl monomer having an acidic group in the A block is preferably 5% by mass or less, and more preferably 2% by mass or less in 100% by mass of the B block.
  • vinyl monomer that can form another structural unit of the B block include the same ones as exemplified as specific examples of the vinyl monomer that can form the other structural unit of the A block.
  • the various structural units contained in the B block may be contained in any form such as random copolymerization and block copolymerization in the B block. From the viewpoint of uniformity, it is preferably contained in the form of random copolymerization.
  • the B block may be formed of a copolymer of a structural unit composed of a b1 block and a structural unit composed of a b2 block.
  • the structure of the block copolymer of the present invention is preferably a linear block copolymer.
  • the linear block copolymer may have any structure (arrangement). From the viewpoint of the physical properties of the linear block copolymer or the physical properties of the composition, the A block is A and the B block is B.
  • a diblock copolymer represented by AB when expressed as, (a-B) m type, (a-B) m -A type, (B-a) m -B type (m is an integer of 1 or more, for example, an integer of 1 to 3) the group consisting of It is preferably a copolymer having at least one structure selected from Among these, a diblock copolymer represented by AB is preferable from the viewpoint of handleability during processing and physical properties of the composition.
  • the diblock copolymer represented by AB it is derived from a structural unit derived from a vinyl monomer having an acidic group in the A block and a vinyl monomer having a tertiary amino group in the B block. It is considered that the structural unit and the structural unit derived from the vinyl monomer having a quaternary ammonium base are localized, so that the pigment, the solvent, and the binder resin (alkali-soluble resin) can be efficiently operated suitably.
  • the content of the A block is preferably 35% by mass or more, more preferably 40% by mass or more, still more preferably 45% by mass or more, and preferably 85% by mass or less, in 100% by mass of the entire block copolymer. More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less.
  • the content of the B block is preferably 15% by mass or more, more preferably 20% by mass or more, still more preferably 25% by mass or more, and preferably 65% by mass or less, in 100% by mass of the entire block copolymer. More preferably, it is 60 mass% or less, More preferably, it is 55 mass% or less.
  • the first composition of the present invention contains the block copolymer.
  • the first composition contains components other than the block copolymer.
  • the impurity resulting from the manufacturing method of a block copolymer is mentioned.
  • at least one alkali selected from the group consisting of a quaternizing agent described later, aromatic dicarboxylic imide, aromatic sulfonic acid, aromatic phosphonic acid and aromatic carboxylic acid is used.
  • a metal salt examples include a halogen component derived from the quaternizing agent and an alkali metal component derived from an alkali metal salt such as an aromatic dicarboxylic acid imide.
  • the first composition is prepared by filtering impurities such as precipitated salts (a salt of a halogen component derived from the quaternizing agent and an alkali metal component derived from an alkali metal salt such as aromatic dicarboxylic acid imide). It is preferable to remove.
  • impurities such as precipitated salts (a salt of a halogen component derived from the quaternizing agent and an alkali metal component derived from an alkali metal salt such as aromatic dicarboxylic acid imide). It is preferable to remove.
  • the molecular weight of the block copolymer contained in the first composition is measured by a gel permeation chromatography (hereinafter referred to as “GPC”) method.
  • the block copolymer preferably has a weight average molecular weight (Mw) of 5000 or more, more preferably 6000 or more, further preferably 7000 or more, preferably 15000 or less, more preferably 12000 or less, and still more preferably 10,000 or less. .
  • Mw weight average molecular weight
  • the molecular weight distribution (PDI) of the block copolymer contained in the first composition is preferably 2.0 or less, and more preferably 1.6 or less.
  • the molecular weight distribution (PDI) is determined by (weight average molecular weight (Mw) of block copolymer) / (number average molecular weight (Mn) of block copolymer). The smaller the PDI, the narrower the molecular weight distribution and the more uniform the copolymer. When the value is 1.0, the molecular weight distribution is the narrowest. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.0, one having a low molecular weight or one having a high molecular weight is included.
  • the amine value of the first composition is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 30 mgKOH / g or more, and 200 mgKOH / g from the viewpoint of the adsorptivity to the pigment and the pigment dispersibility.
  • g or less is preferable, more preferably 150 mgKOH / g or less, and still more preferably 100 mgKOH / g or less.
  • the acid value of the first composition is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 15 mgKOH / g or more, preferably 50 mgKOH / g or less, more preferably 40 mgKOH / g or less, More preferably, it is 35 mgKOH / g or less.
  • the binder resin alkali-soluble resin
  • the second composition of the present invention is obtained by washing the first composition with water and drying.
  • the second composition after washing and drying has a reduced content of salt (a salt of a halogen component derived from the quaternizing agent and an alkali metal component derived from an alkali metal salt such as an aromatic dicarboxylic acid imide).
  • salt a salt of a halogen component derived from the quaternizing agent and an alkali metal component derived from an alkali metal salt such as an aromatic dicarboxylic acid imide.
  • the impurity resulting from the manufacturing method of a block copolymer is contained like the said 1st composition.
  • the said 1st composition is a composition containing the said block copolymer, and the reaction liquid at the time of synthesize
  • the block copolymer contained in the second composition may or may not have the structural unit represented by the general formula (1).
  • said 2nd composition contains other components other than a block copolymer.
  • the other components include aromatic dicarboxylic imides, aromatic sulfonic acids, aromatic phosphonic acids, and aromatic carboxylic acids. These aromatic dicarboxylic imides, aromatic sulfonic acids, aromatic phosphonic acids and aromatic carboxylic acids may be anions or alkali metal salts.
  • the molecular weight of the block copolymer contained in the second composition is measured by a GPC method.
  • the block copolymer preferably has a weight average molecular weight (Mw) of 5000 or more, more preferably 6000 or more, further preferably 7000 or more, preferably 15000 or less, more preferably 12000 or less, and still more preferably 10,000 or less. .
  • Mw weight average molecular weight
  • the weight average molecular weight is within the above range, the dispersion performance when used as a dispersant becomes better.
  • the molecular weight distribution (PDI) of the block copolymer contained in the second composition is preferably 2.0 or less, and more preferably 1.6 or less. When the molecular weight distribution (PDI) of the block copolymer exceeds 2.0, one having a low molecular weight or one having a high molecular weight is included.
  • the amine value of the second composition is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 30 mgKOH / g or more, and 200 mgKOH / g from the viewpoint of the adsorptivity to the pigment and the pigment dispersibility.
  • g or less is preferable, more preferably 150 mgKOH / g or less, and still more preferably 100 mgKOH / g or less.
  • the acid value of the second composition is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, further preferably 15 mgKOH / g or more, preferably 50 mgKOH / g or less, more preferably 40 mgKOH / g or less, More preferably, it is 35 mgKOH / g or less.
  • the second composition preferably has a halogen anion content of 8000 ppm or less, more preferably 6000 ppm or less, and even more preferably 4000 ppm or less.
  • the method for producing a block copolymer of the present invention comprises an A block containing a structural unit derived from a vinyl monomer having an acidic group, a structural unit represented by the general formula (2) described later, and a general formula (3) described later.
  • the “block copolymer precursor” refers to a block copolymer before anion exchange.
  • a block copolymer precursor is prepared.
  • the block copolymer precursor includes an A block including a structural unit derived from a vinyl monomer having an acidic group, a structural unit represented by the general formula (2), and a structural unit represented by the general formula (3).
  • R 21 and R 22 each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R 21 and R 22 may be bonded to each other to form a cyclic structure.
  • X 2 represents a divalent linking group.
  • R 23 represents a hydrogen atom or a methyl group.
  • R 21 to R 23 and X 2 in the formula (2) are the same as those described in the description of the above (B block).
  • R 31 , R 32 and R 33 each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R 31 , R 32 and R 33 may be bonded to each other to form a cyclic structure.
  • X 3 represents a divalent linking group.
  • R 34 represents a hydrogen atom or a methyl group.
  • X ⁇ represents a halogen anion.
  • the chain hydrocarbon group represented by R 31 to R 33 includes both linear and branched chains.
  • Examples of the group represented by R 31 to R 33 include an alkyl group having 1 to 4 carbon atoms which may have a substituent, and an aralkyl group having 7 to 16 carbon atoms which may have a substituent.
  • a methyl group, an ethyl group, a propyl group, and a benzyl group are more preferable.
  • Examples of the cyclic structure formed by bonding two or more of R 31 to R 33 to each other include a 5- to 7-membered nitrogen-containing heteromonocycle or a condensed ring formed by condensing two of these.
  • the nitrogen-containing heterocycle preferably has no aromaticity, and more preferably a saturated ring. Specific examples include structures represented by the following formulas (31-1), (31-2), and (31-3).
  • R 81 is any one of R 31 to R 33 .
  • R 82 represents an alkyl group having 1 to 6 carbon atoms.
  • l represents an integer of 0 to 5.
  • m represents an integer of 0 to 4.
  • n represents an integer of 0 to 4.
  • l is 2 to 5
  • m is 2 to 4
  • n is 2 to 4, a plurality of R 82 may be the same or different.
  • examples of the divalent linking group X 3 include a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, a —CONH—R 35 — group, a —COO—R 36 — group.
  • R 35 and R 36 are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms].
  • Examples of X ⁇ include halogen anions such as chloride ion, bromide ion and iodide ion, and chloride ion is preferable.
  • the A block can be obtained, for example, by polymerizing a monomer composition containing a vinyl monomer having an acidic group.
  • the vinyl monomer having an acidic group used in the step (A) those described above can be used, and are selected from a vinyl monomer having a carboxy group, a vinyl monomer having a sulfonic acid group, or a vinyl monomer having a phosphate group. At least one of these is preferred. Moreover, in addition to the vinyl monomer which has an acidic group, you may mix
  • the B block is a monomer containing a vinyl monomer that can form the structural unit represented by the general formula (2) and a vinyl monomer that can form the structural unit represented by the general formula (3).
  • a method of polymerizing the composition after polymerizing a monomer composition containing a vinyl monomer capable of forming the structural unit represented by the general formula (2), the polymer is represented by the general formula (2) in the obtained polymer. And a method of quaternizing a tertiary amine structure of a part of the structural unit.
  • vinyl monomer which can form the structural unit represented by the said General formula (2) For example, dimethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) Examples include acrylate, diethylaminoethyl (meth) acrylate, diethylaminopropyl (meth) acrylate, diethylaminobutyl (meth) acrylate, and the like.
  • the vinyl monomer that can form the structural unit represented by the general formula (2) may be used alone or in combination of two or more.
  • the vinyl monomer that can form the structural unit represented by the general formula (3) is not particularly limited.
  • the quaternizing agent includes alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide, etc.
  • alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide, etc.
  • An aralkyl halide such as benzyl chloride, benzyl bromide or benzyl iodide; Among these, aralkyl halides such as benzyl chloride, benzyl bromide and benzyl iodide are preferable, and benzyl chloride is more preferable.
  • the amount of the structural unit represented by the general formula (3) can be estimated by measuring the amount of the alkyl group and aralkyl group introduced by quaternization.
  • step (A) a method of first producing an A block and polymerizing a monomer of a B block into the A block; a method of producing a B block first and polymerizing a monomer of the A block into the B block; A method in which the A block and the B block are coupled after the A block and the B block are manufactured separately; the vinyl that can form the structural unit represented by the general formula (2) in the A block by first manufacturing the A block A method of polymerizing a monomer composition containing a monomer and quaternizing a tertiary amine structure of a part of the structural unit represented by the general formula (2) in the obtained polymer; A monomer composition containing a vinyl monomer capable of forming the structural unit represented is polymerized, and a monomer of an A block is polymerized to this polymer, and the structure represented by the general formula (2) in the obtained polymer Part 3 of the unit A method for quaternizing a min structure; A block and a block having a structural unit represented by the general formula
  • the polymerization method is not particularly limited, but living radical polymerization is preferred. That is, the first block copolymer is preferably polymerized using living radical polymerization.
  • living radical polymerization not only the initiation reaction and the growth reaction, but also the termination of the growth end occurs due to the termination reaction and the chain transfer reaction, and the polymer tends to be a mixture of polymers having various molecular weights and heterogeneous compositions.
  • the living radical polymerization method maintains the simplicity and versatility of the conventional radical polymerization method, the termination reaction and chain transfer are unlikely to occur, and the growth end grows without being deactivated. This is preferable in that it is easy to produce a polymer having a uniform composition.
  • a method using a transition metal catalyst ATRP method
  • RAFT method a method using a sulfur-based reversible chain transfer agent
  • TERP method a method to be used since the ATRP method uses an amine-based complex, it may not be used unless the acidic group of the vinyl monomer having an acidic group is protected.
  • the RAFT method when various monomers are used, it is difficult to obtain a low molecular weight distribution, and there may be a problem such as sulfur odor or coloring.
  • the TERP method is preferably used from the viewpoints of diversity of usable monomers, molecular weight control in the polymer region, uniform composition, or coloring.
  • the TERP method is a method of polymerizing a radical polymerizable compound (vinyl monomer) using an organic tellurium compound as a polymerization initiator.
  • a radical polymerizable compound vinyl monomer
  • organic tellurium compound organic tellurium compound
  • Specific polymerization methods of the TERP method include the following (a) to (d).
  • (A) A method in which a vinyl monomer is polymerized using an organic tellurium compound represented by the general formula (4).
  • (B) A method in which a vinyl monomer is polymerized using a mixture of an organic tellurium compound represented by the general formula (4) and an azo polymerization initiator.
  • (C) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (4) and an organic ditellurium compound represented by the general formula (5).
  • (D) A method of polymerizing a vinyl monomer using a mixture of an organic tellurium compound represented by the general formula (4), an azo polymerization initiator, and an organic ditellurium compound represented by the general formula (5).
  • R 41 represents an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group.
  • R 42 and R 43 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • R 44 represents an alkyl group having 1 to 8 carbon atoms, an aryl group, a substituted aryl group, an aromatic heterocyclic group, an alkoxy group, an acyl group, an amide group, an oxycarbonyl group, a cyano group, an allyl group or a propargyl group.
  • R 41 represents an alkyl group having 1 to 8 carbon atoms, an aryl group or an aromatic heterocyclic group.
  • the group represented by R 41 is an alkyl group having 1 to 8 carbon atoms, an aryl group, or an aromatic heterocyclic group, and is specifically as follows.
  • Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl.
  • a linear or branched alkyl group such as a octyl group and a cyclic alkyl group such as a cyclohexyl group.
  • a linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or ethyl group is more preferable.
  • the aryl group include a phenyl group and a naphthyl group.
  • the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.
  • the groups represented by R 42 and R 43 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and each group is specifically as follows.
  • Examples of the alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl.
  • a linear or branched alkyl group such as a octyl group and a cyclic alkyl group such as a cyclohexyl group.
  • a linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or ethyl group is more preferable.
  • the group represented by R 44 is a C 1-8 alkyl group, aryl group, substituted aryl group, aromatic heterocyclic group, alkoxy group, acyl group, amide group, oxycarbonyl group, cyano group, allyl group or A propargyl group, specifically as follows.
  • alkyl group having 1 to 8 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, and heptyl.
  • a linear or branched alkyl group such as an octyl group, a cyclic alkyl group such as a cyclohexyl group, and the like.
  • a linear or branched alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or ethyl group is more preferable.
  • the aryl group include a phenyl group and a naphthyl group.
  • a phenyl group is preferred.
  • the substituted aryl group include a phenyl group having a substituent and a naphthyl group having a substituent.
  • Examples of the substituent of the aryl group having a substituent include a halogen atom, a hydroxy group, an alkoxy group, an amino group, a nitro group, a cyano group, and a carbonyl-containing group represented by —COR 441 (R 441 is a carbon number) 1-8 alkyl groups, aryl groups, alkoxy groups having 1 to 8 carbon atoms or aryloxy groups), sulfonyl groups, trifluoromethyl groups, and the like. These substituents are preferably substituted by 1 or 2 substituents.
  • Examples of the aromatic heterocyclic group include a pyridyl group, a furyl group, and a thienyl group.
  • the alkoxy group is preferably a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an oxygen atom.
  • a methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, sec-butoxy group, tet- A butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, and the like can be given.
  • the acyl group include an acetyl group, a propionyl group, and a benzoyl group.
  • Examples of the amide group include —CONR 4421 R 4422 (R 4421 and R 4422 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group).
  • R 4421 and R 4422 are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group.
  • a group represented by —COOR 443 R 443 is a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group
  • examples thereof include a carboxyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group.
  • oxycarbonyl groups include methoxycarbonyl group and ethoxycarbonyl group.
  • R 4441 and R 4442 are each independently a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R 4443 , R 4444 and R 4445 are Each independently represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms or an aryl group, and each substituent may be linked by a cyclic structure.
  • R 4451 and R 4452 are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • R 4453 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • Aryl group or silyl group are a hydrogen atom or an alkyl group having 1 to 8 carbon atoms
  • organic tellurium compound represented by the general formula (4) examples include (methylterranylmethyl) benzene, (methylterranylmethyl) naphthalene, ethyl-2-methyl-2-methylterranyl-propionate, ethyl-2- Methyl-2-n-butylterranyl-propionate, (2-trimethylsiloxyethyl) -2-methyl-2-methylterranyl-propionate, (2-hydroxyethyl) -2-methyl-2-methylterranyl-propionate or (3-trimethylsilylpropargyl ) -2-methyl-2-methylterranyl-propinate, etc.
  • Organics described in WO 2004/14848, WO 2004/14962, WO 2004/072126, and WO 2004/096870 Illustrate all tellurium compounds Rukoto can.
  • organic ditellurium compound represented by the general formula (5) examples include dimethyl ditelluride, diethyl ditelluride, di-n-propyl ditelluride, diisopropyl ditelluride, dicyclopropyl ditelluride, Di-n-butylditelluride, di-s-butylditelluride, di-t-butylditelluride, dicyclobutylditelluride, diphenylditelluride, bis- (p-methoxyphenyl) ditelluride, bis- (p-aminophenyl) ditelluride, Examples thereof include bis- (p-nitrophenyl) ditelluride, bis- (p-cyanophenyl) ditelluride, bis- (p-sulfonylphenyl) ditelluride, dinaphthyl ditelluride or dipyridyl ditelluride.
  • the azo polymerization initiator can be used without particular limitation as long as it is an azo polymerization initiator used in normal radical polymerization.
  • 2,2′-azobis isobutyronitrile) (AIBN), 2,2′-azobis (2-methylbutyronitrile) (AMBN), 2,2′-azobis (2,4-dimethylvaleronitrile) (ADVN), 1,1′-azobis (1-cyclohexanecarbonitrile) (ACHN), dimethyl-2,2′-azobisisobutyrate (MAIB), 4,4′-azobis (4-cyanovaleric acid) (ACVA), 1,1′-azobis (1-acetoxy-1-phenylethane), 2,2′-azobis (2-methylbutyramide), 2,2′-azobis (4-methoxy-2,4- Dimethylvaleronitrile) (V-70), 2,2′-azobis (2-methylamidinopropane) dihydrochloride, 2,2′-azobis [2- (2-imida
  • the polymerization step is a container substituted with an inert gas.
  • an inert gas For the purpose of promoting reaction, controlling molecular weight and molecular weight distribution, etc., depending on the type of vinyl monomer, the vinyl monomer and the organic tellurium compound of the general formula (4).
  • An azo polymerization initiator and / or an organic ditellurium compound of the general formula (5) is mixed.
  • the inert gas include nitrogen, argon, helium and the like. Argon and nitrogen are preferable.
  • the amount of vinyl monomer used may be appropriately adjusted depending on the physical properties of the target copolymer.
  • the vinyl monomer is preferably 5 to 10,000 mol per mol of the organic tellurium compound.
  • the amount of the azo polymerization initiator used is usually an organic compound of the general formula (4).
  • the azo polymerization initiator is preferably 0.01 mol to 10 mol with respect to 1 mol of the tellurium compound.
  • the organic ditellurium compound of the general formula (5) is preferably 0.01 mol to 100 mol per 1 mol of the organic tellurium compound of the general formula (4).
  • the organic tellurium compound of the general formula (4) when the organic tellurium compound of the general formula (4), the organic ditellurium compound of the general formula (5) and the azo polymerization initiator are used in combination, Usually, the azo polymerization initiator is preferably used in an amount of 0.01 mol to 100 mol with respect to 1 mol in total of the organic tellurium compound of the general formula (4) and the organic ditellurium compound of the general formula (5).
  • the polymerization reaction can be carried out without a solvent, but it may be carried out using an aprotic solvent or a protic solvent generally used in radical polymerization and stirring the mixture.
  • aprotic solvents that can be used include benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, propylene glycol monomethyl ether acetate, chloroform
  • Examples include carbon chloride, tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate or trifluoromethylbenzene.
  • protic solvent examples include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, and diacetone alcohol.
  • the amount of the solvent used may be adjusted as appropriate. For example, it is preferably 0.01 ml or more, more preferably 0.05 ml or more, still more preferably 0.1 ml or more, and 50 ml or less with respect to 1 g of vinyl monomer. More preferably, it is 10 ml or less, More preferably, it is 1 ml or less.
  • the reaction temperature and reaction time may be appropriately adjusted depending on the molecular weight or molecular weight distribution of the copolymer to be obtained, but are usually stirred at 0 to 150 ° C. for 1 minute to 100 hours.
  • the TERP method can obtain a high yield and a precise molecular weight distribution even at a low polymerization temperature and a short polymerization time.
  • the pressure is usually normal pressure, but it may be increased or decreased.
  • the intended copolymer can be separated from the obtained reaction mixture by removing the solvent used, residual vinyl monomer and the like by a normal separation and purification means.
  • the growth terminal of the copolymer obtained by the polymerization reaction is in the form of -TeR 41 (wherein R 41 is the same as described above), and it is deactivated by the operation in the air after the completion of the polymerization reaction.
  • Tellurium atoms may remain. Since the copolymer in which the tellurium atom remains at the terminal is colored or inferior in thermal stability, it is preferable to remove the tellurium atom.
  • a radical reduction method using tributylstannane or a thiol compound As a method for removing tellurium atoms, a radical reduction method using tributylstannane or a thiol compound; a method of adsorbing with activated carbon, silica gel, activated alumina, activated clay, molecular sieves, polymer adsorbent, etc .; Method of adsorbing metal: Add peroxide such as hydrogen peroxide or benzoyl peroxide, or blow air or oxygen into the system to oxidatively decompose tellurium atoms at the end of the copolymer.
  • peroxide such as hydrogen peroxide or benzoyl peroxide
  • Liquid-liquid extraction method or solid-liquid extraction method that removes residual tellurium compounds by combining solvents; purification method in solution state such as ultrafiltration that extracts and removes only those having a specific molecular weight or less can be used. These methods can also be used in combination.
  • a method of quaternizing a tertiary amine structure of a part of the structural unit represented by the general formula (2) in the polymer a method of bringing the polymer into contact with a quaternizing agent can be mentioned. Specifically, after polymerizing a monomer composition containing a vinyl monomer that can form the structural unit represented by the general formula (2), a quaternizing agent is added to the reaction solution, followed by stirring. It is done.
  • the temperature of the reaction solution to which the quaternizing agent is added is preferably 55 ° C. to 65 ° C., and the stirring time is preferably 5 hours to 20 hours.
  • the solvent to be added for dilution include a solvent that can be used for the polymerization reaction, a protic solvent is preferable, and methanol is more preferable.
  • the molecular weight of the block copolymer precursor is measured by the GPC method.
  • the weight average molecular weight (Mw) of the block copolymer precursor is preferably 5000 or more, more preferably 6000 or more, further preferably 7000 or more, preferably 15000 or less, more preferably 12000 or less, and still more preferably 10,000. It is as follows.
  • the molecular weight distribution (PDI) of the block copolymer precursor is preferably 2.0 or less, and more preferably 1.6 or less.
  • the content of A block in the block copolymer precursor is preferably 35% by mass or more, more preferably 40% by mass or more, and still more preferably 45% by mass or more in 100% by mass of the entire block copolymer. Yes, 85 mass% or less is preferable, More preferably, it is 80 mass% or less, More preferably, it is 75 mass% or less.
  • the content of B block in the block copolymer precursor is preferably 15% by mass or more, more preferably 20% by mass or more, and further preferably 25% by mass or more, in 100% by mass of the entire block copolymer. Yes, 65 mass% or less is preferable, More preferably, it is 60 mass% or less, More preferably, it is 55 mass% or less.
  • the amine value of the block copolymer precursor is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more, and still more preferably 30 mgKOH / g or more, from the viewpoints of adsorptivity to pigment and pigment dispersibility. 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, and still more preferably 100 mgKOH / g or less.
  • the amine value of the block copolymer precursor is derived from the structural unit represented by the general formula (2).
  • the acid value of the precursor of the block copolymer is preferably 5 mgKOH / g or more, more preferably 10 mgKOH / g or more, still more preferably 15 mgKOH / g or more, preferably 50 mgKOH / g or less, more preferably 40 mgKOH / g. g or less, more preferably 35 mgKOH / g or less.
  • Step (B) In the step (B), after completion of the step (A), the precursor of the obtained block copolymer is selected from the group consisting of aromatic dicarboxylic imide, aromatic sulfonic acid, aromatic phosphonic acid and aromatic carboxylic acid. At least one alkali metal salt is allowed to act to obtain a block copolymer.
  • the halogen anion of the structural unit represented by the general formula (3) is exchanged for an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonium ion, or an aromatic carboxylate anion (anion). Exchange).
  • alkali metal in at least one alkali metal salt selected from the group consisting of aromatic dicarboxylic imide, aromatic sulfonic acid, aromatic phosphonic acid and aromatic carboxylic acid include lithium, sodium, potassium, rubidium, cesium, There is francium, and among these, lithium, sodium, and potassium are preferable because of economical advantages.
  • alkali metal salt of aromatic dicarboxylic acid imide examples include those represented by the general formula (6).
  • ring A represents an aromatic ring which may have a substituent group
  • M 1 is an alkali metal
  • the aromatic ring constituting the ring A is a ring structure having aromaticity.
  • the aromatic ring includes both single rings and condensed rings.
  • a 5- or 6-membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are preferable.
  • the condensed ring is preferably a 2-5 condensed ring, and is preferably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring.
  • Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.
  • Examples of the alkali metal represented by M 1 include lithium, sodium, potassium, rubidium, cesium, and francium.
  • alkali metal salt of the aromatic dicarboxylic acid imide examples include those represented by general formulas (6-1) to (6-7).
  • M 1 represents an alkali metal.
  • alkali metal salt of aromatic sulfonic acid examples include those represented by the general formula (7).
  • Ar represents an aromatic ring which may have a substituent
  • M 2 represents an alkali metal
  • the aromatic ring constituting Ar is a ring structure having aromaticity.
  • the aromatic ring includes both single rings and condensed rings.
  • As the monocycle a 5- or 6-membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are preferable.
  • the condensed ring is preferably a 2-5 condensed ring, and is preferably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring.
  • Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.
  • Examples of the alkali metal represented by M 2 include lithium, sodium, potassium, rubidium, cesium, and francium.
  • alkali metal salt of aromatic sulfonic acid examples include those represented by general formulas (7-1) to (7-9).
  • M 2 represents an alkali metal.
  • alkali metal salt of aromatic phosphonic acid examples include those represented by the general formula (8).
  • Ar represents an aromatic ring which may have a substituent
  • M 3 represents an alkali metal.
  • the aromatic ring constituting Ar is a ring structure having aromaticity.
  • the aromatic ring includes both single rings and condensed rings.
  • a 5- or 6-membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are preferable.
  • the condensed ring is preferably a 2-5 condensed ring, and is preferably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring.
  • Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.
  • Examples of the alkali metal represented by M 3 include lithium, sodium, potassium, rubidium, cesium, and francium.
  • alkali metal salt of aromatic phosphonic acid examples include those represented by general formulas (8-1) to (8-7).
  • M 3 represents an alkali metal.
  • alkali metal salt of aromatic carboxylic acid examples include those represented by the general formula (9).
  • Ar represents an aromatic ring which may have a substituent
  • M 4 represents an alkali metal
  • the aromatic ring constituting Ar is a ring structure having aromaticity.
  • the aromatic ring includes both single rings and condensed rings.
  • a 5- or 6-membered ring is preferable, and a benzene ring, a furan ring, a thiophene ring, and a pyrrole ring are preferable.
  • the condensed ring is preferably a 2-5 condensed ring, and is preferably a naphthalene ring, an anthracene ring, a phenanthrene ring or an indole ring.
  • Examples of the substituent that the aromatic ring may have include an alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 14 carbon atoms, a nitro group, a cyano group, and a halogen group.
  • Examples of the alkali metal represented by M 4 include lithium, sodium, potassium, rubidium, cesium, and francium.
  • alkali metal salt of aromatic carboxylic acid examples include those represented by general formulas (9-1) to (9-9).
  • step (B) as a method of allowing the alkali metal salt to act on the block copolymer precursor, a method in which the alkali metal salt is added to a solution in which the block copolymer precursor is dissolved and stirred. Is mentioned.
  • the alkali metal salt may be added to the reaction solution after the polymerization in the step (A).
  • the precursor of the block copolymer is isolated from the polymerization solution after completion of the step (A), and the alkali metal salt is added to a solution obtained by dissolving the precursor in a new solvent. It is preferable.
  • an aprotic solvent or a protic solvent can be used as a solvent capable of dissolving the block copolymer precursor.
  • aprotic solvents that can be used include benzene, toluene, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, 2-butanone (methyl ethyl ketone), dioxane, propylene glycol monomethyl ether acetate, chloroform
  • Examples include carbon chloride, tetrahydrofuran (THF), ethyl acetate, propylene glycol monomethyl ether acetate or trifluoromethylbenzene.
  • protic solvent examples include water, methanol, ethanol, isopropanol, n-butanol, ethyl cellosolve, butyl cellosolve, 1-methoxy-2-propanol, hexafluoroisopropanol, and diacetone alcohol.
  • the amount of the solvent used for dissolving the block copolymer precursor may be appropriately adjusted.
  • it is usually 2 ml to 10 ml with respect to 1 g of the block copolymer precursor.
  • the range is preferably 2 ml to 5 ml.
  • the amount of the at least one alkali metal salt selected from the group consisting of aromatic dicarboxylic imide, aromatic sulfonic acid, aromatic phosphonic acid and aromatic carboxylic acid in step (B) is a quaternary ammonium group. Is preferably 0.5 equivalents or more, more preferably 0.9 equivalents or more, preferably 1.1 equivalents or less, and more preferably 1.0 equivalents or less.
  • the solution temperature at the time of contacting the block copolymer precursor with the alkali metal salt is usually 55 ° C. to 70 ° C., preferably 55 ° C. to 65 ° C., and the stirring time is usually 18 hours to 24 hours, preferably 20 hours to 22 hours.
  • the first composition containing the block copolymer is obtained by removing the solvent from the reaction solution.
  • the obtained first composition is an impurity such as a precipitated salt (a salt of a halogen component derived from the quaternizing agent and an alkali metal component derived from an alkali metal salt such as aromatic dicarboxylic imide). Is preferably removed by filtration.
  • the method for producing the block copolymer preferably includes a step (C) of washing the block copolymer obtained in the step (B) with water.
  • a known washing method can be used, but liquid separation washing is preferable. Separation washing may be performed on the solution after completion of the step (B), or the first composition obtained by isolating the first composition of the block copolymer from the solution after completion of the step (B). You may perform with respect to the solution which melt
  • the liquid separation cleaning As a specific example of the liquid separation cleaning, a solvent in which a block copolymer is dissolved and water are mixed, and then the separated aqueous layer is extracted.
  • the content of the salt contained in the first composition a salt of a halogen component derived from the quaternizing agent and an alkali metal component derived from an alkali metal salt such as an aromatic dicarboxylic acid imide
  • the second composition of the target block copolymer can be obtained by removing the solvent of the phase in which the block copolymer is dissolved under reduced pressure.
  • the solvent for the above-described liquid separation operation may be any solvent that can dissolve the block copolymer and can be phase-separated from water. Examples thereof include ethyl acetate, butyl acetate, isopropyl acetate, and methyl isobutyl ketone. These may be used in combination. Moreover, the water used for washing may contain alcohol or the like.
  • the amount of water used is preferably 0.1 to 10 times, more preferably 0.5 times the volume of the solvent phase in which the block copolymer is dissolved. ⁇ 5 times the amount.
  • the liquid temperature at the time of liquid separation washing is preferably 10 ° C. to 60 ° C., more preferably 30 ° C. to 50 ° C., and particularly preferably 35 ° C. to 45 ° C.
  • the dispersant of the present invention contains the block copolymer, the first composition or the second composition as a main component.
  • the said dispersing agent consists only of the block copolymer of this invention, a 1st composition, or a 2nd composition.
  • the pigment dispersion composition of the present invention contains the dispersant, a pigment, and a dispersion medium. In this case, the type and particle size of the pigment used are different depending on the application and are not particularly limited.
  • the pigment dispersion composition can be used for a color filter.
  • the tertiary amino group and quaternary ammonium base in the structure (B block) are strongly bonded to the acidic group of the pigment treated with the acidic pigment or the acidic group-containing dye derivative.
  • the B block adsorbs to the pigment, or the aromatic part of the aromatic dicarboxylic acid imide anion which is a counter ion of the quaternary ammonium base adsorbs to the pigment skeleton part of the pigment, thereby improving the pigment dispersibility. It is thought to exert its effect. That is, since the dispersant of the present invention is a component that favorably disperses the pigment by this action, the type of pigment to be dispersed is not particularly limited.
  • the content of the dispersant is preferably 5 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the pigment. More preferably, it is ⁇ 50 parts by mass.
  • the pigment may be either an organic pigment or an inorganic pigment, but an organic pigment containing an organic compound as a main component is particularly preferable.
  • examples of the pigment include pigments of various colors such as a red pigment, a yellow pigment, an orange pigment, a blue pigment, a green pigment, and a purple pigment.
  • the structure of the pigment is azo pigments such as monoazo pigments, diazo pigments, condensed diazo pigments, diketopyrrolopyrrole pigments, phthalocyanine pigments, isoindolinone pigments, isoindoline pigments, quinacridone pigments, indigo Examples thereof include polycyclic pigments such as pigments, thioindigo pigments, quinophthalone pigments, dioxazine pigments, anthraquinone pigments, perylene pigments, and perinone pigments. Only one type of pigment may be contained in the pigment dispersion composition, or a plurality of types may be used.
  • pigments include C.I. I. Pigment® Red 7, 9, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 81: 1, 81: 2, 81: 3, 122, 123, 146, 149, 168, 177, Red pigments such as 178, 179, 187, 200, 202, 208, 210, 215, 224, 254, 255, 264; I.
  • Orange pigments such as Pigment Orange 36, 38, 43;
  • the upper limit of the pigment content in the pigment dispersion composition is usually 80% by mass, preferably 70% by mass, and more preferably 60% by mass in the total solid content of the pigment dispersion composition.
  • the lower limit of the pigment content in the pigment dispersion composition is usually 10% by mass, preferably 20% by mass, and preferably 30% by mass in the total solid content of the pigment dispersion composition. More preferred.
  • a conventionally known organic solvent can be used as the dispersion medium.
  • Glycol monoalkyl ethers such as ter, 3-methyl-3-methoxybutanol, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, tripropylene glycol
  • Monohydric or polyhydric alcohols Monohydric or polyhydric alcohols; aliphatic hydrocarbons such as n-pentane, n-octane, diisobutylene, n-hexane, hexene, isoprene, dipentene, dodecane; cyclohexane, methylcyclohexane, methylcyclohexene, bicyclohexyl, etc.
  • Alicyclic hydrocarbons such as benzene, toluene, xylene, cumene; amyl formate, ethyl formate, ethyl acetate, butyl acetate Propyl acetate, amyl acetate, methyl isobutyrate, ethylene glycol acetate, ethyl propionate, propyl propionate, butyl butyrate, isobutyl butyrate, methyl isobutyrate, ethyl caprylate, butyl stearate, ethyl benzoate, 3-ethoxypropion Chain or cyclic esters such as methyl acid, ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, ⁇ -butyrolactone; Alkoxycarboxylic acids such as 3-
  • the organic solvent is preferably glycol alkyl ether acetates, monovalent or polyhydric alcohols from the viewpoints of dispersibility of pigments, solubility of the dispersant, applicability of the pigment dispersion composition, and the like.
  • the solvent contained in the pigment dispersion composition may be only one type or a plurality of types.
  • the content of the dispersion medium in the pigment dispersion composition is not particularly limited and can be appropriately adjusted.
  • the upper limit of the content of the dispersion medium in the pigment dispersion composition is usually 99% by mass.
  • the lower limit of the content of the dispersion medium in the pigment dispersion composition is usually 70% by mass and preferably 80% by mass in consideration of the viscosity suitable for application of the pigment dispersion composition.
  • the dispersion medium can be used as a solvent for dissolving and removing precipitates formed from the pigment dispersion composition.
  • an acidic group further having an acidic group is used in order to adsorb and adsorb the tertiary amino group and quaternary ammonium base in the block copolymer characterizing the present invention used as a dispersant. It is preferable to contain a pigment derivative of This dye derivative has an acidic functional group introduced into the dye skeleton.
  • the dye skeleton the same or similar skeleton as the pigment constituting the pigment dispersion composition and the same or similar skeleton as the raw material of the pigment are preferable.
  • the dye skeleton include azo dye skeleton, phthalocyanine dye skeleton, anthraquinone dye skeleton, triazine dye skeleton, acridine dye skeleton, and perylene dye skeleton.
  • the acidic group introduced into the dye skeleton is preferably a carboxyl group, a phosphoric acid group, or a sulfonic acid group.
  • a sulfonic acid group is preferable from the viewpoint of synthesis and the strength of acidity.
  • the acidic group may be directly bonded to the dye skeleton, but may be bonded to the dye skeleton via a hydrocarbon group such as an alkyl group or an aryl group; an ester, ether, sulfonamide, or urethane bond.
  • a hydrocarbon group such as an alkyl group or an aryl group
  • an ester, ether, sulfonamide, or urethane bond may be directly bonded to the dye skeleton, but may be bonded to the dye skeleton via a hydrocarbon group such as an alkyl group or an aryl group; an ester, ether, sulfonamide, or urethane bond.
  • the pigment dispersion composition of the present invention may contain a binder resin.
  • the binder resin may be a polymer, for example.
  • specific examples of monomers constituting the polymer include, for example, carboxyl groups such as (meth) acrylic acid, maleic acid, fumaric acid, itaconic acid, citraconic acid, crotonic acid, and maleic anhydride Containing unsaturated monomer: methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, octyl (meth) acrylate, lauryl (meth) acrylate, (meth) (Meth) acrylic such as 2-hydroxyethyl acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, methyl cyclohexyl (meth) acrylate, isobornyl (meth) (Meth)
  • Acid ester styrene, ⁇ -methylstyrene, 4-methylstyrene ( -Methylstyrene), 2-methylstyrene (o-methylstyrene), 3-methylstyrene (m-methylstyrene), 4-methoxystyrene (p-methoxystyrene), p-tert-butylstyrene, pn-butyl And aromatic unsaturated monomers (styrene monomers) such as styrene and p-tert-butoxystyrene.
  • styrene monomers such as styrene and p-tert-butoxystyrene.
  • the binder resin is preferably a copolymer of a carboxyl group-containing unsaturated monomer and a (meth) acrylic acid ester.
  • a copolymer of (meth) acrylic acid and butyl (meth) acrylate a copolymer of (meth) acrylic acid and benzyl (meth) acrylate
  • a copolymer of acrylic acid, butyl (meth) acrylate, and benzyl (meth) acrylate a copolymer of acrylic acid, butyl (meth) acrylate, and benzyl (meth) acrylate.
  • the binder resin is particularly preferably a copolymer of (meth) acrylic acid and benzyl (meth) acrylate.
  • the content of (meth) acrylic acid is usually 5% by mass to 90% by mass in all monomer components, and 10% by mass to It is preferably 70% by mass, and more preferably 20% by mass to 70% by mass.
  • Mw is preferably from 3,000 to 100,000, more preferably from 5,000 to 50,000, and even more preferably from 5,000 to 20,000. When the Mw of the binder resin is 3,000 or more, the heat resistance, film strength, etc. of the coating film formed from the pigment dispersion composition are good, and when the Mw is 100,000 or less, the aqueous alkaline solution of this coating film Developability due to is further improved.
  • the acid value of the binder resin is preferably 20 mgKOH / g to 170 mgKOH / g, and more preferably 50 mgKOH / g to 150 mgKOH / g. 90 mg KOH / g to 150 mg KOH / g is more preferable.
  • the acid value of the binder resin is 20 mgKOH or more / g, the alkali developability when the pigment dispersion composition is used as a coating film is further improved, and when it is 170 mgKOH / g or less, the heat resistance is improved.
  • the binder resin contained in the pigment dispersion composition may be only one type or a plurality of types.
  • the content of the binder resin is preferably 5 parts by mass to 200 parts by mass, more preferably 10 parts by mass to 100 parts by mass with respect to 100 parts by mass of the pigment. More preferred is from 50 parts by weight to 50 parts by weight.
  • the pigment dispersion composition is obtained by mixing a pigment, a dispersant, a dispersion medium, a dye derivative, a binder resin, and the like using a mixing and dispersing machine such as a paint shaker, a bead mill, a ball mill, a dissolver, or a kneader.
  • the pigment dispersion composition is preferably filtered after mixing.
  • the pigment dispersion composition may contain other additives as necessary.
  • other additives include a photopolymerizable monomer, a photopolymerization initiator, a pH adjuster, an antioxidant, an ultraviolet absorber, a light stabilizer, an antiseptic, and an antifungal agent.
  • the photopolymerizable monomer is preferably a compound having at least two ethylenically unsaturated double bonds that are compatible with the binder resin. As such a compound, when the pigment dispersion composition is used as a colorant for a color filter, it has alkali solubility and has one or more acidic groups and two or more ethylenically unsaturated bonds in one molecule.
  • a compound is preferable, and a compound having one or more acidic groups and three or more ethylenically unsaturated bonds in one molecule is more preferable.
  • the compound having at least two ethylenically unsaturated double bonds include polyfunctional (meth) acrylates such as bifunctional (meth) acrylate and trifunctional or higher functional (meth) acrylate. Among these, trifunctional or higher functional (meth) acrylates are preferable.
  • an acidic group-containing polyfunctional (meth) acrylate is more preferable, and a trifunctional or higher acidic group-containing polyfunctionality is preferred.
  • the acidic group is not particularly limited as long as it can be alkali-developed.
  • the acidic group is preferably a carboxy group from the viewpoint of further improving the alkali developability and the handleability of the resin composition.
  • a coating film of the pigment dispersion composition can be formed on the substrate by applying the pigment dispersion composition onto the substrate by a spin coating method, a roll coating method, a slit coating method or the like. After applying the pigment dispersion composition on the substrate, drying (desolvation treatment) or the like may be performed as necessary.
  • the heat resistance of the block copolymer that characterizes the present invention used for the dispersant is excellent. It can be expected to suppress a decrease in contrast ratio and a change in hue.
  • the measurement conditions were a column temperature of 40 ° C., a sample concentration of 100 mg / mL, a sample injection amount of 10 ⁇ L, and a flow rate of 0.6 mL / min.
  • a calibration curve was prepared using polystyrene (manufactured by Tosoh Corporation, TSK Standard) as a standard substance, and a weight average molecular weight (Mw) and a number average molecular weight (Mn) were measured. Molecular weight distribution (PDI) was calculated from these measured values.
  • the amine value is expressed by the mass of potassium hydroxide (KOH) equivalent to the basic component per gram of the solid content.
  • KOH potassium hydroxide
  • the measurement sample was dissolved in tetrahydrofuran, and the obtained solution was neutralized with 0.1 mol / L hydrochloric acid / 2-propanol solution using a potentiometric titrator (trade name: 915 KF Ti-touch, manufactured by Metrohm). .
  • the amine value (B) was calculated by the following formula using the inflection point of the titration pH curve as the titration end point.
  • the acid value represents the mass of potassium hydroxide required to neutralize acidic components per gram of solid content.
  • the measurement sample was dissolved in tetrahydrofuron, and the resulting solution was subjected to neutralization titration with a 0.5 mol / L potassium hydroxide / ethanol solution.
  • the acid value (A) was calculated by the following formula.
  • A 56.11 ⁇ Vs ⁇ 0.5 ⁇ f / w
  • Vs Amount of 0.5 mol / L potassium hydroxide / ethanol solution required for titration (mL)
  • f Potency of 0.5 mol / L potassium hydroxide / ethanol solution
  • the measurement was performed using a thermogravimetric / differential thermal simultaneous measurement apparatus (TG-DTA) (TG-DTA6300, manufactured by SII Nanotechnology).
  • TG-DTA thermogravimetric / differential thermal simultaneous measurement apparatus
  • the measurement sample was dried under reduced pressure at 130 ° C. for 2 hours before measurement.
  • the measurement conditions were a sample mass of about 10 mg, an air inflow rate of 200 ml / min, a heating rate of 10 ° C./min, and a measurement temperature range of 40 ° C. to 600 ° C.
  • the temperature at which the sample mass decreased by 10% was read from the obtained TG curve, and this was taken as the heating weight decrease temperature.
  • Sample preparation was performed as follows. About 10 mg of the second composition substance was put into a combustion furnace (trade name: AQF-2100H, manufactured by Mitsubishi Chemical Analytech). The heater of the combustion furnace was 900 ° C. (inside), the gas flow rate was 200 mL / min of argon, 400 mL / min of oxygen, 100 mL / min of argon for humidification, and the residence time of the combustion furnace was 15 minutes. The exhaust gas was captured by a collector (trade name: AU-250, manufactured by Mitsubishi Chemical Analytech). The sample solution was prepared by using ultrapure water as the absorbing solution and diluting 35 mL of the obtained water absorbing solution to 50 mL using ultrapure water.
  • the content of the halogen anion was measured using ion chromatography (trade name: DIONEX ICS-1600, manufactured by Thermo Scientific).
  • the column used was Ion Pac AS-14A (manufactured by DIONEX), and the eluent used was an eluent for anion analysis (trade name: AS12A, manufactured by DIONEX).
  • the measurement conditions were a sample injection volume of 25 ⁇ L and a flow rate of 1.5 mL / min.
  • a calibration curve (calibration curve) was prepared using a standard solution having a chlorine anion concentration of 1 ppm and 2 ppm as a standard substance, and the chlorine anion concentration was calculated.
  • Precursor No. of the obtained block copolymer 1 had an Mw of 7618, a PDI of 1.30, an acid value of 32 mgKOH / g, an amine value of 64 mgKOH / g, and a heating weight loss temperature of 254 ° C.
  • Block copolymer precursor Nos. 2 to 12 Block copolymer precursor no.
  • the block copolymer precursor No. 1 was prepared in the same manner as in the preparation method of No. 1. 2 to 12 were produced.
  • Tables 1 and 2 show the raw material monomers, organic tellurium compounds, organic ditellurium compounds, azo polymerization initiators, solvents, quaternizing agents, reaction conditions, and polymerization rates used.
  • Tables 3 and 4 show the composition of precursors of each block copolymer, Mw, PDI, acid value, amine value, and heating weight reduction temperature.
  • Block copolymer second composition No. 51 The block copolymer precursor No. obtained above. 1 PMA 110g and MP 110g were added to 87.5g and dissolved. Anion exchange was performed by adding 11.2 g of PIK to the obtained solution and reacting at 60 ° C. for 20 hours. The obtained reaction solution was cooled, ethyl acetate and water were added, and the mixture was stirred at 40 ° C. for 1 hour. Liquid separation was performed to obtain an organic layer. The obtained organic layer was concentrated under reduced pressure and dried to obtain a second composition No. 2 of the block copolymer. 51 was obtained. The second composition No. of the obtained block copolymer.
  • Mw of the block copolymer contained was 7852, and PDI was 1.21.
  • the acid value of the second composition was 32 mg KOH / g, the amine value was 89 mg KOH / g, the heating weight reduction temperature was 291 ° C., and the chlorine anion content was 3501 ppm (solid content conversion).
  • a blended composition was prepared by preparing 3 parts by mass, 3 parts by mass of MP, and 81 parts by mass of PMA, and stirring for 2 hours with a planetary ball mill (0.3 mm zirconia beads). The viscosity of the obtained pigment dispersion composition was 4.0 mPa ⁇ s.
  • a blended composition was prepared by preparing 3 parts by mass, 3 parts by mass of MP, and 81 parts by mass of PMA, and stirring for 2 hours with a planetary ball mill (0.3 mm zirconia beads). The viscosity of the obtained pigment dispersion composition was 3.0 mPa ⁇ s.
  • the present invention includes the following embodiments.
  • (Embodiment 1) It has an A block containing a structural unit derived from a vinyl monomer having an acidic group, and a B block containing a structural unit represented by the following general formula (1) and a structural unit represented by the following general formula (2).
  • R ⁇ 11> , R ⁇ 12 > and R ⁇ 13 > show the chain or cyclic hydrocarbon group which may have a substituent each independently. Two or more of R 11 , R 12 and R 13 may be bonded to each other to form a cyclic structure.
  • X 1 represents a divalent linking group.
  • R 14 represents a hydrogen atom or a methyl group.
  • Y ⁇ represents at least one selected from the group consisting of an aromatic dicarboxylic imide anion, an aromatic sulfonate anion, an aromatic phosphonate anion, and an aromatic carboxylate anion.
  • R 21 and R 22 each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R 21 and R 22 may be bonded to each other to form a cyclic structure.
  • X 2 represents a divalent linking group.
  • R 23 represents a hydrogen atom or a methyl group.
  • Embodiment 2 The block copolymer according to embodiment 1, which is an AB type block copolymer.
  • Embodiment 7 The 1st composition of Embodiment 6 whose molecular weight distribution (PDI) of the said block copolymer is 2.0 or less.
  • Embodiment 9 A dispersant comprising the block copolymer according to any one of Embodiments 1 to 6, the first composition according to Embodiment 7, or the second composition according to Embodiment 8.
  • a pigment dispersion composition comprising the dispersant according to embodiment 9, a pigment, and a dispersion medium.
  • the precursor of the block copolymer obtained in the step (A) is at least one alkali selected from the group consisting of aromatic dicarboxylic imides, aromatic sulfonic acids, aromatic phosphonic acids and aromatic carboxylic acids.
  • R 21 and R 22 each independently represent a chain or cyclic hydrocarbon group which may have a substituent. R 21 and R 22 may be bonded to each other to form a cyclic structure.
  • X 2 represents a divalent linking group.
  • R 23 represents a hydrogen atom or a methyl group.
  • R 31 , R 32 and R 33 each independently represent a chain or cyclic hydrocarbon group which may have a substituent. Two or more of R 31 , R 32 and R 33 may be bonded to each other to form a cyclic structure.
  • X 3 represents a divalent linking group.
  • R 34 represents a hydrogen atom or a methyl group.
  • X ⁇ represents a halogen anion.
  • Embodiment 14 The manufacturing method of the block copolymer of Embodiment 12 or 13 provided with the process (C) which wash
  • the block copolymer of the present invention alkali development is facilitated because the A block has an acidic group.
  • the counter ion of the quaternary ammonium cation of the B block is an aromatic dicarboxylic acid imide anion, an aromatic sulfonic acid anion, an aromatic phosphonic acid anion or an aromatic carboxylic acid anion, the heat resistance is excellent. Therefore, the block copolymer of this invention can be used conveniently for the pigment dispersion composition for color filters used for manufacture of the color filter which employ

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Graft Or Block Polymers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Optical Filters (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Pigments, Carbon Blacks, Or Wood Stains (AREA)

Abstract

Le problème décrit par la présente invention est d'obtenir un copolymère bloc qui peut être utilisé comme agent dispersant, et qui présente une meilleure résistance à la chaleur. La solution selon l'invention porte sur un copolymère bloc qui est caractérisé en ce qu'il comprend un bloc A comprenant un motif structural dérivé d'un monomère vinylique possédant un groupe acide, et un bloc B comprenant un motif structural représenté par la formule générale (1) et un motif structural représenté par la formule générale (2). [Dans les formules (1) et (2), R11, R12, R13, R21, et R22 représentent chacun indépendamment un groupe hydrocarboné linéaire ou cyclique éventuellement substitué. Au moins deux parmi R11, R12 et R13 peuvent être liés ensemble pour former une structure cyclique. R21 et R22 peuvent être liés ensemble pour former une structure cyclique. X1 et X2 représentent un groupe de liaison divalent. R14 et R23 représentent indépendamment un atome d'hydrogène ou un groupe méthyle. Y- représente au moins un élément choisi dans le groupe constitué d'anions imide d'acide dicarboxylique aromatique, d'anions d'acide sulfonique aromatique, d'anions d'acide phosphonique aromatique, et d'anions d'acide carboxylique aromatique.]
PCT/JP2017/038717 2016-10-31 2017-10-26 Copolymère bloc, agent dispersant, et composition de dispersion de pigment WO2018079659A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2018505485A JP6316531B1 (ja) 2016-10-31 2017-10-26 ブロック共重合体、分散剤および顔料分散組成物
KR1020187012560A KR102032076B1 (ko) 2016-10-31 2017-10-26 블록 공중합체, 분산제 및 안료 분산 조성물
CN201780004006.8A CN108431064B (zh) 2016-10-31 2017-10-26 嵌段共聚物、分散剂和颜料分散组合物

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016-213522 2016-10-31
JP2016213522 2016-10-31

Publications (1)

Publication Number Publication Date
WO2018079659A1 true WO2018079659A1 (fr) 2018-05-03

Family

ID=62025027

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/038717 WO2018079659A1 (fr) 2016-10-31 2017-10-26 Copolymère bloc, agent dispersant, et composition de dispersion de pigment

Country Status (5)

Country Link
JP (1) JP6316531B1 (fr)
KR (1) KR102032076B1 (fr)
CN (1) CN108431064B (fr)
TW (1) TWI670286B (fr)
WO (1) WO2018079659A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2021039787A1 (fr) * 2019-08-26 2021-03-04
KR20210043707A (ko) 2019-09-06 2021-04-21 미쯔비시 케미컬 주식회사 감광성 착색 조성물, 경화물, 화상 표시 장치, 및 화상 표시 장치용의 안료 분산액
JP2021063180A (ja) * 2019-10-15 2021-04-22 大塚化学株式会社 分散剤組成物、着色組成物およびカラーフィルタ
JP2021075660A (ja) * 2019-11-12 2021-05-20 大日精化工業株式会社 顔料分散液
JP2022003133A (ja) * 2019-08-26 2022-01-11 国立大学法人富山大学 微粒子吸着防止ポリマー

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7235474B2 (ja) * 2018-10-25 2023-03-08 大塚化学株式会社 着色組成物、および、カラーフィルタ
JP7235475B2 (ja) * 2018-10-25 2023-03-08 大塚化学株式会社 着色組成物、および、カラーフィルタ
EP4325599A1 (fr) * 2022-07-08 2024-02-21 Contemporary Amperex Technology Co., Limited Agent de dispersion et son procédé de préparation, composition de bouillie et son procédé de préparation, et feuille d'électrode et dispositif la comprenant

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010079244A (ja) * 2008-08-26 2010-04-08 Dainippon Printing Co Ltd カラーフィルタ用ネガ型レジスト組成物、カラーフィルタ及び液晶表示装置
WO2012001945A1 (fr) * 2010-06-30 2012-01-05 日本曹達株式会社 Nouveau copolymère
WO2015198422A1 (fr) * 2014-06-25 2015-12-30 大日精化工業株式会社 Copolymère séquencé a-b, son procédé de production, composition de pigment de traitement à base de résine, son procédé de production, dispersion de pigment, et solution de type dispersion de pigment
JP2017082198A (ja) * 2015-09-23 2017-05-18 ベーイプシロンカー ヘミー ゲゼルシャフト ミット ベシュレンクター ハフトゥング 低アミン価の湿潤及び／又は分散剤を含有する着色剤組成物

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4133267B2 (ja) * 2002-11-29 2008-08-13 三菱化学株式会社 顔料分散組成物及びこれを用いたカラーフィルター
CN102027029B (zh) * 2008-05-15 2014-05-28 帝斯曼知识产权资产管理有限公司 利用raft得到的嵌段共聚物
JP2012068559A (ja) 2010-09-27 2012-04-05 Toyo Ink Sc Holdings Co Ltd カラーフィルタ用着色組成物及びカラーフィルタ
JP5892510B2 (ja) * 2012-03-28 2016-03-23 大日精化工業株式会社 高分子分散剤の製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010079244A (ja) * 2008-08-26 2010-04-08 Dainippon Printing Co Ltd カラーフィルタ用ネガ型レジスト組成物、カラーフィルタ及び液晶表示装置
WO2012001945A1 (fr) * 2010-06-30 2012-01-05 日本曹達株式会社 Nouveau copolymère
WO2015198422A1 (fr) * 2014-06-25 2015-12-30 大日精化工業株式会社 Copolymère séquencé a-b, son procédé de production, composition de pigment de traitement à base de résine, son procédé de production, dispersion de pigment, et solution de type dispersion de pigment
JP2017082198A (ja) * 2015-09-23 2017-05-18 ベーイプシロンカー ヘミー ゲゼルシャフト ミット ベシュレンクター ハフトゥング 低アミン価の湿潤及び／又は分散剤を含有する着色剤組成物

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP7186409B2 (ja) 2019-08-26 2022-12-09 国立大学法人富山大学 微粒子吸着防止ポリマー
WO2021039787A1 (fr) * 2019-08-26 2021-03-04 国立大学法人富山大学 Polymère empêchant l'adsorption de particules fines
JPWO2021039787A1 (fr) * 2019-08-26 2021-03-04
CN114402004B (zh) * 2019-08-26 2023-10-24 国立大学法人富山大学 防微粒吸附聚合物
JP2022003133A (ja) * 2019-08-26 2022-01-11 国立大学法人富山大学 微粒子吸着防止ポリマー
CN114402004A (zh) * 2019-08-26 2022-04-26 国立大学法人富山大学 防微粒吸附聚合物
JP7083467B2 (ja) 2019-08-26 2022-06-13 国立大学法人富山大学 微粒子吸着防止ポリマー
KR20210043707A (ko) 2019-09-06 2021-04-21 미쯔비시 케미컬 주식회사 감광성 착색 조성물, 경화물, 화상 표시 장치, 및 화상 표시 장치용의 안료 분산액
KR20220027257A (ko) 2019-09-06 2022-03-07 미쯔비시 케미컬 주식회사 화상 표시 장치용의 안료 분산액
JP2021063180A (ja) * 2019-10-15 2021-04-22 大塚化学株式会社 分散剤組成物、着色組成物およびカラーフィルタ
JP7348804B2 (ja) 2019-10-15 2023-09-21 大塚化学株式会社 分散剤組成物、着色組成物およびカラーフィルタ
JP7126169B2 (ja) 2019-11-12 2022-08-26 大日精化工業株式会社 顔料分散液
JP2021075660A (ja) * 2019-11-12 2021-05-20 大日精化工業株式会社 顔料分散液

Also Published As

Publication number Publication date
JPWO2018079659A1 (ja) 2018-10-25
JP6316531B1 (ja) 2018-04-25
KR20180067567A (ko) 2018-06-20
CN108431064A (zh) 2018-08-21
TWI670286B (zh) 2019-09-01
CN108431064B (zh) 2021-03-12
KR102032076B1 (ko) 2019-10-14
TW201829504A (zh) 2018-08-16

Similar Documents

Publication Publication Date Title
JP6316531B1 (ja) ブロック共重合体、分散剤および顔料分散組成物
JP5734821B2 (ja) ブロック共重合体、分散剤及び顔料分散組成物
JP6567905B2 (ja) ブロック共重合体、分散剤及び顔料分散組成物
JP6605783B1 (ja) 分散剤組成物、着色組成物およびカラーフィルタ
JP7348998B2 (ja) ブロック共重合体を含有する重合生成物
JP7235474B2 (ja) 着色組成物、および、カラーフィルタ
JP7235475B2 (ja) 着色組成物、および、カラーフィルタ
JP7217680B2 (ja) ブロック共重合体、分散剤、着色組成物およびカラーフィルタ
JP7299894B2 (ja) 分散剤組成物、着色組成物、および、カラーフィルタ
JP6758166B2 (ja) 着色感放射線性組成物およびカラーフィルタ
JP7299895B2 (ja) 分散剤組成物、着色組成物、および、カラーフィルタ
JP7038493B2 (ja) ブロック共重合体、分散剤、着色組成物およびカラーフィルタ
JP7324623B2 (ja) ブロック共重合体、分散剤、着色組成物、および、カラーフィルタ
JP6797483B2 (ja) ブロック共重合体、分散剤、着色組成物およびカラーフィルタ
WO2024116876A1 (fr) Copolymère bloc, dispersant et composition colorante
TW202407065A (zh) 含有雙噁嗪類顏料的著色組合物及彩色濾光片
WO2024116875A1 (fr) Copolymère bloc, agent de dispersion et composition colorée
JP2024024585A (ja) ジオキサジン系顔料含有着色組成物およびカラーフィルタ

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 2018505485

Country of ref document: JP

ENP Entry into the national phase

Ref document number: 20187012560

Country of ref document: KR

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17864413

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17864413

Country of ref document: EP

Kind code of ref document: A1