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
  • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
  • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D17/00—Pigment pastes, e.g. for mixing in paints
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents

Definitions

• the present invention relates to a method for producing a novel block copolymer useful as a pigment dispersant and a copolymer precursor.
• At least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base, a repeating unit containing an acidic group, and a unit derived from an alkyl (meth) acrylate Random copolymers containing are known. Since these polymers have various properties based on their unique structures, development is being studied in various fields.
• Patent Document 1 discloses a pigment composition containing a pigment, an acidic functional group-containing organic dye derivative, an alkali-soluble resin, and an organic solvent, and having an amino group and / or its quaternary ammonium group. Describes a pigment composition having a basic equivalent weight of 3000 to 20000 g / eq and an acid value of 30 to 200 mg KOH / g. Specifically, as alkali-soluble resins, random copolymers of n-butyl methacrylate, methyl methacrylate, methacrylic acid and dimethylaminoethyl methacrylate are described.
• Patent Documents 2 and 3 focusing on the fact that the random copolymer has the property of an amphoteric polymer that is positively or negatively charged by treatment with an acid or a base, the random copolymer is electrophoresed. It is used as a sex composition.
• the random copolymer is used as a binder for silyl isocyanate.
• Patent Document 5 a powder coating composition is obtained by causing a crosslinking reaction between a carboxyl group and an epoxy group of the random copolymer, and further using an amino group of the random copolymer as a catalyst for the crosslinking reaction. It is used as.
• JP 2007-84659 A JP-A-6-289609 JP-A-5-295305 Japanese Patent Laid-Open No. 4-62880 Japanese Patent Laid-Open No. 61-6866
• the use of copolymers has been diversified, and copolymers having various properties have been demanded.
• pigment particles are finely divided to at least the wavelength of visible light or less due to the increasing demand for high visible light transmittance and high contrast.
• the specific surface area of the pigment particles is larger than usual, so that the conventionally used copolymers for pigment dispersants have insufficient initial pigment dispersibility and dispersion stability over time. It was.
• higher performance is required in addition to dispersion performance, and conventional copolymers have not been able to obtain sufficient performance. Therefore, the present invention has an object to provide a method for producing a copolymer and a copolymer precursor, which have good initial pigment dispersibility and dispersion stability with time, and also have higher performance than dispersion performance.
• the present inventors have obtained at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base.
• a block copolymer containing (B1) and having a copolymerization ratio of the repeating unit represented by the formula (II) of 90% by mass or more in the block chain (B1) can solve the above problems, and
• the block copolymer has a repeating unit represented by the formula (I) in which the acidic group of the repeating unit containing the acidic group represented by the formula (III) is protected. It found that can be produced by heating the body, and have completed the present invention.
• the present invention (1) a block chain (A) comprising at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base; and the formula (I)
• R 1 , R 2 and R 3 each independently represents a hydrogen atom or a C1-C3 alkyl group.
• X represents a single bond or a C1-C10 alkylene group, —C ( ⁇ O) OR 1a A group selected from the group consisting of —, —C ( ⁇ O) NHR 1a —, —OC ( ⁇ O) R 1a — and —R 2a —OC ( ⁇ O) —R 1a — (R 1a and R 2a are Each independently represents a C1-C10 alkylene group or a C1-C10 alkylene-O—C1-C10 alkylene group.), R 4 represents a hydrogen atom, a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group.
• R 5 represents a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group, or a C6-C10 aryl group).
• R 10 , R 11 and R 12 each independently represents a hydrogen atom or a C1-C3 alkyl group.
• Y represents a C1-C10 alkylene group, —C ( ⁇ O) OR 1b —, — A group selected from the group consisting of C ( ⁇ O) NHR 1b —, —OC ( ⁇ O) R 1b — and —R 2b —OC ( ⁇ O) —R 1b —
• R 1b and R 2b are each independently Represents a C1 to C10 alkylene group or a C1 to C10 alkylene-O—C1 to C10 alkylene group
• R 13 and R 14 each independently represents a C1 to C6 alkyl group or a C6 to C10 aryl group.
• R 15 , R 16 and R 17 each independently represents a hydrogen atom or a C1-C3 alkyl group.
• Y 1 represents a C1-C10 alkylene group, —C ( ⁇ O) OR 1c —, Groups selected from the group consisting of —C ( ⁇ O) NHR 1c —, —OC ( ⁇ O) R 1c —, and —R 2c —OC ( ⁇ O) —R 1c —
• R 1c and R 2c are each independently Represents a C1 to C10 alkylene group or a C1 to C10 alkylene-O—C1 to C10 alkylene group
• R 18 , R 19 and R 20 each independently represents a C1 to C6 alkyl group, or .Z representing a C6 ⁇ C10 aryl C1 ⁇ C6 alkyl group -.
• the present invention relates to the method for producing a block copolymer according to any one of (1) to (3), which is carried out in a mixed solvent of an organic solvent and water.
• the present invention also provides: (5) a block chain (A) containing at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base; and the formula (I)
• R 1 , R 2 and R 3 each independently represents a hydrogen atom or a C1-C3 alkyl group.
• X represents a single bond or a C1-C10 alkylene group, —C ( ⁇ O) OR 1a A group selected from the group consisting of —, —C ( ⁇ O) NHR 1a —, —OC ( ⁇ O) R 1a — and —R 2a —OC ( ⁇ O) —R 1a — (R 1a and R 2a are Each independently represents a C1-C10 alkylene group or a C1-C10 alkylene-O—C1-C10 alkylene group.), R 4 represents a hydrogen atom, a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group.
• R 5 represents a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group, or a C6-C10 aryl group).
• the repeating unit containing a tertiary amino group has the formula (IV)
• R 10 , R 11 and R 12 each independently represents a hydrogen atom or a C1-C3 alkyl group.
• Y represents a C1-C10 alkylene group, —C ( ⁇ O) OR 1b —, — A group selected from the group consisting of C ( ⁇ O) NHR 1b —, —OC ( ⁇ O) R 1b — and —R 2b —OC ( ⁇ O) —R 1b —
• R 1b and R 2b are each independently Represents a C1 to C10 alkylene group or a C1 to C10 alkylene-O—C1 to C10 alkylene group
• R 13 and R 14 each independently represents a C1 to C6 alkyl group or a C6 to C10 aryl group.
• R 15 , R 16 and R 17 each independently represents a hydrogen atom or a C1-C3 alkyl group.
• Y 1 represents a C1-C10 alkylene group, —C ( ⁇ O) OR 1c —, Groups selected from the group consisting of —C ( ⁇ O) NHR 1c —, —OC ( ⁇ O) R 1c —, and —R 2c —OC ( ⁇ O) —R 1c —
• R 1c and R 2c are each independently Represents a C1 to C10 alkylene group or a C1 to C10 alkylene-O—C1 to C10 alkylene group
• R 18 , R 19 and R 20 each independently represents a C1 to C6 alkyl group, or .Z representing a C6 ⁇ C10 aryl C1 ⁇ C6 alkyl group - relates precursor copolymers described in (5) to a repeating unit represented by the representative) a counter ion..
• the copolymer precursor used in the present invention contains at least one of the following block chain (A) and block chain (B).
• Block chain (A) Block chain containing at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base
• Block (B) protected The block chain containing the repeating unit containing an acidic group and the repeating unit represented by the formula (II)
• the copolymer precursor used in the present invention includes the block chain (A) and the block chain (B). In addition, other block chains may be contained.
• Block chain (A) In the block chain (A), the repeating unit containing a tertiary amino group and the repeating unit containing a quaternary ammonium base are those having the cationic functional group in the side chain of the repeating unit, There is no particular limitation. Specifically, the block chain (A) is a repeating unit containing a tertiary amino group, or a repeating unit containing a tertiary amino group, a block chain consisting of only one type of repeating unit containing a quaternary ammonium base.
• a block chain composed of two or more repeating units containing a quaternary ammonium base a block chain composed of at least one repeating unit containing a tertiary amino group and at least one repeating unit containing a quaternary ammonium base.
• block chains of these and repeating units derived from other copolymerizable monomers may be in any form such as random, alternating, or block.
• the repeating unit containing a tertiary amino group is not particularly limited as long as it contains a tertiary amino group, and examples thereof include a repeating unit represented by the following general formula (IV).
• R 10 , R 11 and R 12 are each independently a hydrogen atom or a C1-C3 alkyl group.
• Y represents a C1-C10 alkylene group, —C ( ⁇ O) OR 1b —, —C ( ⁇ O) NHR 1b —, —OC ( ⁇ O) R 1b — and —R 2b —OC ( ⁇ O) —R A group selected from the group consisting of 1b — (R 1b and R 2b each independently represents a C1 to C10 alkylene group or a C1 to C10 alkylene-O—C1 to C10 alkylene group).
• R 13 and R 14 are each independently a C1-C6 alkyl group or a C6-C10 aryl C1-C6 alkyl group.
• the C1-C3 alkyl group and the C1-C6 alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, s-butyl, i-butyl, t-butyl, n-pentyl, n -Hexyl and the like are exemplified.
• Examples of the C1-C10 alkylene group include a methylene chain, an ethylene chain, a propylene chain, a methylethylene chain, a butylene chain, a 1,2-dimethylethylene chain, a pentylene chain, a 1-methylbutylene chain, a 2-methylbutylene chain, and a hexylene chain. Is exemplified.
• C6-C10 aryl C1-C6 alkyl groups include benzyl, phenethyl, 3-phenyl-n-propyl, 1-phenyl-n-hexyl, naphthalen-1-ylmethyl, naphthalen-2-ylethyl, 1-naphthalene-2 Examples include -yl-n-propyl, inden-1-ylmethyl and the like.
• dimethylaminoethyl (meth) acrylate dimethylaminopropyl (meth) acrylate, dimethylaminobutyl (meth) acrylate, diethylaminoethyl (meth) acrylate, diethylamino
• examples include propyl (meth) acrylate and diethylaminobutyl (meth) acrylate.
• the repeating unit containing a quaternary ammonium base is not particularly limited as long as it contains a quaternary ammonium base, and examples thereof include a repeating unit represented by the following general formula (V).
• R 15 , R 16 and R 17 are each independently a hydrogen atom or a C1-C3 alkyl group.
• Y 1 represents a C1-C10 alkylene group, —C ( ⁇ O) OR 1c —, —C ( ⁇ O) NHR 1c —, —OC ( ⁇ O) R 1c — and —R 2c —OC ( ⁇ O) —
• R 18 , R 19 and R 20 are each independently a C1-C6 alkyl group or a C6-C10 aryl C1-C6 alkyl group.
• Z ⁇ represents a counter ion such as a halide ion, an alkyl halide ion, an alkyl carboxylate ion, a nitroxide ion, an alkyl sulfate ion, a sulfonate ion, a phosphate ion or an alkyl phosphate ion.
• the C1-C3 alkyl group, the C1-C6 alkyl group, the C1-C10 alkylene group, and the C6-C10 aryl C1-C6 alkyl group are represented by the formula (IV) of the repeating unit containing the tertiary amino group. The thing similar to what is in can be illustrated.
• repeating units that can be contained examples include repeating units derived from (meth) acrylic acid monomers, aromatic vinyl monomers, conjugated diene monomers, and the like. Examples of the (meth) acrylic acid-based monomer, aromatic vinyl-based monomer, and conjugated diene-based monomer that are the raw materials for the repeating unit include the following.
• (Meth) acrylic acid monomers include (meth) acrylic acid; methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, (meth ) N-butyl acrylate, i-butyl (meth) acrylate, s-butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth ) (Meth) acrylic acid ester compounds such as 2-ethylhexyl acrylate, 1-ethylcyclohexyl (meth) acrylate, benzyl (meth) acrylate; 2-methoxyethyl (meth) acrylate, methoxypolyethylene glycol (ethylene glycol) The number of units is 2 to 100) (meth)
• Aromatic vinyl monomers include styrene, o-methylstyrene, p-methylstyrene, pt-butylstyrene, ⁇ -methylstyrene, pt-butoxystyrene, mt-butoxystyrene, p- (1 -Ethoxyethoxy) styrene, 2,4-dimethylstyrene, vinylaniline, vinylbenzoic acid, vinylnaphthalene, vinylanthracene, 2-vinylpyridine, 4-vinylpyridine, 2-vinylquinoline, 4-vinylquinoline, 2-vinylthiophene And heteroaryl compounds such as 4-vinylthiophene.
• Conjugated diene monomers include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 2,3 -Dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-octadiene 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene, 1,3-tri Examples thereof include cyclodecadiene, myrcene, chloroprene, and the like. These can be used alone or in combination
• Block chain (B) is a block chain containing at least one repeating unit containing a protected acidic group and at least one repeating unit represented by the formula (II).
• the copolymerization ratio of at least one repeating unit represented by the formula (II) is 90% by mass or more, preferably 91% by mass to 99% by mass.
• the repeating unit containing a protected acidic group in the block chain (B) is a repeating unit represented by the formula (I).
• R 1 , R 2 and R 3 are each independently a hydrogen atom or a C1-C3 alkyl group.
• X is a single bond or a C1-C10 alkylene group, —C ( ⁇ O) OR 1a —, —C ( ⁇ O) NHR 1a —, —OC ( ⁇ O) R 1a — and —R 2a —OC ( ⁇ O ) —R 1a — is a group selected from the group consisting of —R 1a — (R 1a and R 2a are each independently a C1-C10 alkylene group or a C1-C10 alkylene-O—C1-C10 alkylene group), and R 4 is a hydrogen atom, a C1-C6 alkyl group, a C6-C10 aryl C1-C6 alkyl group, or a C6-C10 aryl group, and R 5 is a C1-C6 alkyl group, a C6
• Examples of monomers used as a raw material for the repeating unit represented by the formula (I) include acrylic acid methoxymethyl ester, acrylic acid ethoxymethyl ester, acrylic acid 1-ethoxy-ethyl ester, acrylic acid 1-methoxy-ethyl ester, and acrylic acid.
• acrylic acid 1-ethoxy-ethyl ester and 2-methyl-acrylic acid 1-ethoxy-ethyl ester are preferred. These can be used alone or in admixture of two or more.
• the repeating unit containing a protected acidic group can be converted to a repeating unit containing an acidic group described below by deprotecting the protective group by the production method of the present invention.
• the block chain (B) further contains at least one repeating unit represented by the following formula (II).
• R 6 , R 7 and R 8 represent a hydrogen atom or a C1-C3 alkyl group
• R 9 represents an aliphatic hydrocarbon group or an alicyclic hydrocarbon group.
• examples of the C1-C3 alkyl group for R 6 , R 7 , and R 8 include those similar to those in formula (IV) of the repeating unit having a tertiary amino group.
• the aliphatic hydrocarbon group for R 9 may be either saturated or unsaturated, and includes a C1 to C20 alkyl group, a C2 to C20 alkenyl group, and a C2 to C20 alkynyl group.
• Examples of the C1 to C20 alkyl group include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, 2-methylbutyl, n- Hexyl, isohexyl, 3-methylpentyl, ethylbutyl, n-heptyl, 2-methylhexyl, n-octyl, isooctyl, tert-octyl, 2-ethylhexyl, 3-methylheptyl, n-nonyl, isononyl, Examples include 1-methyloctyl, ethylheptyl, n-decyl, 1-methylnonyl, n-undecyl, 1,1-dimethylnonyl, n
• C1-C6 alkyl group is preferred.
• Examples of the C2-C20 alkenyl group include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5- Examples include hexenyl, heptenyl, octenyl, decenyl group, pentadecenyl, eicocenyl group, tricocenyl and the like.
• C2-C6 alkenyl group is preferable.
• the C2-C20 alkynyl group include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-methyl-2-propynyl, 1- Pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 2-methyl-2-butynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, Examples include 1-heptynyl, 1-octynyl, 1-decynyl, 1-pentadecynyl, 1-eicosinyl, 1-tricosinyl and the like.
• it is a C2 to
• an alicyclic hydrocarbon group means a saturated or unsaturated hydrocarbon group having a monocyclic or polycyclic ring structure in any part of the group, and is a C3-C20 cycloalkyl group.
• Alkyl group, C4-C20 alkyl-substituted cycloalkyl group, C4-C20 cycloalkylalkyl group, C3-C20 cycloalkenyl group, C4-C20 alkyl-substituted cycloalkenyl group, C4-C20 cycloalkenylalkyl group, C7 Includes a C20 bridged ring hydrocarbon group and the like.
• Examples of the C3-C20 cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl and the like.
• a C3-C8 cycloalkyl group is preferred.
• Examples of the C4-C20 alkyl-substituted cycloalkyl group include 1-methylcyclopropyl, 2-ethylcyclopropyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 4-ethylcyclohexyl, 3-ethylcyclohexyl, 2-ethylcyclohexyl, And methylcyclooctyl.
• it is a C4 to C10 alkyl-substituted cycloalkyl group.
• the C3-C20 cycloalkylalkyl group include cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cycloheptylethyl, cyclooctylethyl and the like.
• it is a C4-C10 cycloalkylalkyl group.
• Examples of the C3-C20 cycloalkenyl group include cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclopentadienyl and the like. Preferably, it is a C3-C8 cycloalkenyl group.
• Examples of the C4-C20 alkyl-substituted cycloalkenyl group include 3-ethylcyclopentenyl, hexenyl 4-methylcyclohexenyl, 4-ethylcyclohexenyl, and the like.
• it is a C4-C10 alkyl-substituted cycloalkenyl group.
• the C4 to C20 cycloalkenylalkyl group include cyclopropenylmethyl, cyclobutenylmethyl, cyclopentenylethyl, cyclohexenylethyl and the like.
• it is a C4 to C10 cycloalkenylalkyl group.
• Examples of the C7 to C20 bridged ring hydrocarbon group include tricyclo [5.2.1.0 2,6 ] decan-8-yl group, adamantyl group, dicyclopentenyl group, isobornyl group and the like.
• repeating units that can be contained examples include repeating units derived from aromatic vinyl monomers, conjugated diene monomers, and the like.
• Aromatic vinyl monomers include styrene, o-methylstyrene, p-methylstyrene, pt-butylstyrene, ⁇ -methylstyrene, pt-butoxystyrene, mt-butoxystyrene, p- (1 -Ethoxyethoxy) styrene, 2,4-dimethylstyrene, vinylaniline, vinylbenzoic acid, vinylnaphthalene, vinylanthracene, 2-vinylpyridine, 4-vinylpyridine, 2-vinylquinoline, 4-vinylquinoline, 2-vinylthiophene And heteroaryl compounds such as 4-vinylthiophene. These can be used singly or in combination of two or more.
• Conjugated diene monomers include 1,3-butadiene, isoprene, 2-ethyl-1,3-butadiene, 2-t-butyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 2,3 -Dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 3-methyl-1,3-pentadiene, 1,3-hexadiene, 2-methyl-1,3-octadiene 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, 1,3-cyclopentadiene, 1,3-cyclohexadiene, 1,3-cyclooctadiene, 1,3-tri Examples thereof include cyclodecadiene, myrcene, chloroprene, and the like. These can be used alone or in combination of two or more.
• the copolymer precursor used in the present invention may have other block chains in addition to the block chains (A) and (B).
• Examples of such a block chain include a block chain containing a repeating unit derived from a (meth) acrylic acid monomer, an aromatic vinyl monomer, a conjugated diene monomer, and the like. Any form such as random copolymerization, alternating copolymerization, and block copolymerization may be used. Examples of the (meth) acrylic acid monomer, aromatic vinyl monomer, conjugated diene monomer, and the like are exemplified.
• the ratio of the block chain (A) to the block chain (B) in the copolymer of the present invention is not particularly limited, but is 10 to 40:90 to 60, preferably 15 to 35 to 85 in terms of% by weight. ⁇ 65. Further, the weight average molecular weight measured using GPC is 2,000 to 50,000, and the copolymer precursor is particularly preferably 4,000 to 15,000. The ratio of the weight average molecular weight to the number average molecular weight, measured using GPC, is 1.0 to 2.0, preferably 1.0 to 1.5.
• the method for producing the copolymer precursor used in the present invention is not particularly limited and can be produced by a known method. It can be polymerized to form a block copolymer.
• Examples of the living polymerization include living radical polymerization and living anion polymerization, among which living anion polymerization is more preferable.
• another block monomer may be continuously polymerized to form a block copolymer, Each block of A) and the block chain (B) may be reacted separately to produce a block, and then each block may be combined.
• Living anionic polymerization is preferable because the composition and molecular weight can be strictly controlled.
• the reaction can be carried out in the same manner as living anion polymerization, or after polymerizing a certain block of monomer and before polymerizing the next monomer, the polymer is once purified, It is also possible to polymerize the next monomer after removing the remainder of the monomer in the reaction.
• the monomers of each block do not mix with each other, it is preferable to purify the polymer.
• a desired monomer can be dropped and polymerized in a solvent to which an additive and a polymerization initiator are added.
• the monomers of each block are sequentially added dropwise so as to have a desired sequence and reacted.
• the dropping of the monomer of the next block is started after completion of the polymerization reaction of the previous block.
• the progress of the polymerization reaction can be confirmed by detecting the remaining amount of the monomer by gas chromatography or liquid chromatography.
• the dropping of the monomer of the next block can be started after stirring for 1 minute to 1 hour.
• the anionic polymerization initiator used for the polymerization of the monomer is not particularly limited as long as it is a nucleophile and has a function of initiating the polymerization of the anionic polymerizable monomer.
• alkali metal organic Alkali metal compounds and the like can be used.
• the alkali metal include lithium, sodium, potassium, cesium and the like.
• the organic alkali metal compound include alkylated products, allylated products, and arylated products of the above alkali metals, and alkyllithium is particularly preferable.
• anionic polymerization initiators can be used alone or in combination of two or more.
• the amount of the anionic polymerization initiator used is usually from 0.0001 to 0.2 equivalent, preferably from 0.0005 to 0.1 equivalent, based on the whole anionic polymerizable monomer to be used. By using an anionic polymerization initiator in this range, the target polymer can be produced with high yield.
• the polymerization temperature is not particularly limited as long as the side reaction such as transfer reaction or termination reaction does not occur and the monomer is consumed and the polymerization is completed, but the polymerization temperature is not lower than ⁇ 100 ° C. but not higher than the solvent boiling point. preferable.
• the concentration of the monomer with respect to the polymerization solvent is not particularly limited, but is usually 1 to 40% by weight, and preferably 10 to 30% by weight.
• the polymerization solvent used in the production method of the present invention is not particularly limited as long as it does not participate in the polymerization reaction and is compatible with the polymer, and specifically includes diethyl ether, tetrahydrofuran (THF), dioxane.
• Polar compounds such as ether compounds such as trioxane, tertiary amines such as tetramethylethylenediamine and hexamethylphosphoric triamide, and non-aliphatic, aromatic or alicyclic hydrocarbon compounds such as hexane and toluene
• a polar solvent or a low polarity solvent can be illustrated. These solvents can be used alone or as a mixed solvent of two or more.
• polymerization can be accurately controlled even when a nonpolar solvent or a low polarity solvent is used in combination with a polar solvent.
• the nonpolar solvent or the low polarity solvent is based on the whole solvent. 5 vol% or more can be used, 20 vol% or more may be used, and 50 vol% or more may be used.
• a dialkyl zinc such as diethyl zinc, a dialkyl magnesium such as dibutyl magnesium, or an organic metal such as triethylaluminum can be used as a polymerization stabilizer, a monomer or a solvent purifier, if necessary.
• an additive such as an alkali metal salt or an alkaline earth metal salt can be added at the start of polymerization or during polymerization as required. Specific examples of such additives include mineral salts and halides such as sodium, potassium, barium and magnesium sulfates, nitrates and borates.
• lithium And barium chloride, bromide, iodide, lithium borate, magnesium nitrate, sodium chloride, potassium chloride and the like lithium halides such as lithium chloride, lithium bromide, lithium iodide, and lithium fluoride are preferable, and lithium chloride is particularly preferable. It is generally difficult to polymerize a monomer containing a quaternary ammonium base by living anionic polymerization.
• Quaternizing agents include benzyl chloride, benzyl bromide, benzyl iodide and the like, alkyl halides such as methyl chloride, ethyl chloride, methyl bromide, methyl iodide, dimethyl sulfate, diethyl sulfate, di-n-sulfate. Common alkylating agents such as propyl can be mentioned.
• Block copolymer The block copolymer produced in the present invention contains at least one of the following block chains (A) and block chains (B1).
• Block chain (A) Block chain containing at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base
• Block chain (B1) an acidic group
• the copolymer of the present invention contains other block chains in addition to the block chain (A) and the block chain (B1). You may do it.
• Block chain (A) The block chain (A) in the block copolymer is the same as the block chain (A) in the copolymer precursor.
• Block chain (B1) The block chain (B1) is a copolymer containing at least one repeating unit containing an acidic group and at least one repeating unit represented by the formula (II).
• the copolymerization ratio of at least one repeating unit represented by the formula (II) is 90% by mass or more, preferably 91% by mass to 99% by mass.
• Copolymers include random, alternating, block, etc. copolymers.
• the repeating unit containing an acidic group in the block chain (B1) is a repeating unit represented by the formula (III).
• R 1 , R 2 , R 3 and X have the same meaning as in the repeating unit containing a protected acidic group represented by formula (I).
• the repeating unit represented by the formula (III) can be obtained by deprotecting the protecting group of the protected acidic group represented by the formula (I) by the production method of the present invention.
• the repeating unit represented by the formula (II) in the block chain (B1) is the same as the repeating unit represented by the formula (II) in the copolymer precursor.
• the other repeating unit that can be contained in the block chain (B1) is the same as the other repeating unit that can be contained in the block chain (B) in the copolymer precursor.
• the copolymer used in the present invention may have a block chain made of another polymer in addition to the block chains (A) and (B1). Such a block chain is the same as the block chain other than the block chains (A) and (B) in the copolymer precursor.
• the ratio of the block chain (A) to the block chain (B1) in the copolymer used in the present invention is not particularly limited, but is 10 to 40:90 to 60, preferably 15 to 15% by weight. 35 to 85-65.
• the content of the repeating unit having an acidic group in the copolymer is 0.5 to 20% by weight, preferably 1 to 15% by weight.
• the weight average molecular weight measured using GPC is 2,000 to 50,000, and the dispersant is preferably 2,000 to 20,000, more preferably 4,000 to 15,000. .
• the ratio of the weight average molecular weight to the number average molecular weight, measured using GPC is 1.0 to 2.0, and the dispersant is particularly preferably 1.0 to 1.5.
• the block copolymer of this invention can be obtained by heating the said copolymer precursor.
• the protecting group protecting the acidic group in the copolymer precursor is deprotected.
• the heating temperature varies depending on the structure of the protecting group protecting the acidic group, but is not particularly limited as long as the deprotection reaction proceeds rapidly. Usually, it is preferably carried out at 80 ° C. to 200 ° C., more preferably 100 ° C. to 160 ° C.
• the copolymer precursor may be heated as it is, or may be heated in a state where the copolymer precursor is dissolved in a solvent.
• solvents examples include water; glycol ether ester solvents such as ethyl cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether acetate; ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether, Glycol mono- or diether solvents such as propylene glycol monoethyl ether and diethylene glycol dimethyl ether; aromatic hydrocarbon solvents such as toluene and monochlorobenzene; ethanol, isopropanol, n-butanol, 1-methoxy-2-propanol (PGME), etc.
• glycol ether ester solvents such as ethyl cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate (PGMEA) and propylene glycol monoethyl ether
• Alcohol solvents such as ethyl lactate, butyl acetate and ethyl pyruvate; and these A mixed solvent consisting of seeds or more; and the like.
• glycol ether ester solvents mixed solvents of glycol ether ester solvents and alcohol solvents, and mixed solvents of glycol ether ester solvents and water are preferred.
• a mixed solvent of a glycol ether ester solvent and an alcohol solvent a mixed solvent of a glycol ether ester solvent and water is preferable, and a mixture of a glycol ether ester solvent and water is preferable.
• a mixed solvent is particularly preferred.
• a mixed solvent of glycol ether ester solvent and water is preferable, and a mixed solvent of PGMEA and water is particularly preferable.
• the mixing ratio is not particularly limited as long as the copolymer precursor can be dissolved, but usually 95/5 wt% to 0.1 / 99.9. % By weight is preferable, and 50/50 to 0.1 / 99.9% by weight is more preferable.
• the mixing ratio is not particularly limited as long as the copolymer precursor can be dissolved, but it is usually preferably 95/5 to 50/50% by weight, It is more preferably 90/10 to 60/40% by weight, and particularly preferably 90/10 to 70/30% by weight.
• the heating temperature varies depending on the structure of the protecting group protecting the acidic group and the reaction solvent, but is not particularly limited as long as the deprotection reaction proceeds rapidly.
• a glycol ether ester solvent it is usually preferably carried out at 80 ° C. to 200 ° C., more preferably 100 ° C. to 170 ° C.
• a mixed solvent of a glycol ether ester solvent and an alcohol solvent it is preferably carried out at 100 to 140 ° C., more preferably 110 to 140 ° C.
• a mixed solvent of a glycol ether ester solvent and water it is preferably carried out at 70 ° C. to 120 ° C., more preferably 90 ° C. to 120 ° C. From the viewpoint of reducing the coloration of the polymer solution produced by the deprotection reaction, it is preferable to lower the heating temperature.
• Example 1 Polymerization process
• THF tetrahydrofuran
• lithium chloride 4.54% by weight concentration THF solution
• diphenylethylene 0.45 part of diphenylethylene
• EEMA 1-ethoxyethyl methacrylate
• nBMA n-butyl methacrylate
• MMA methyl methacrylate
• DMMA 2- (dimethylamino) ethyl methacrylate
• GPC gel permeation chromatography
• PMMA polymethyl methacrylate
• a block chain (A) comprising at least one repeating unit selected from the group consisting of a repeating unit containing a tertiary amino group and a repeating unit containing a quaternary ammonium base, and the formula (III) Containing a repeating unit containing an acidic group represented by formula (II) and a block chain (B1) containing a repeating unit represented by formula (II), wherein the copolymerization ratio of the repeating unit represented by formula (II) is blocked
• a block copolymer that is 90% by mass or more in the chain (B1) can be produced.
• Those block copolymers are particularly useful as pigment dispersants for color liquid crystals.

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