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WO2016017680A1 - Nouveau polymère greffé, et procédé de fabrication de celui-ci - Google Patents

Nouveau polymère greffé, et procédé de fabrication de celui-ci Download PDF

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Publication number
WO2016017680A1
WO2016017680A1 PCT/JP2015/071478 JP2015071478W WO2016017680A1 WO 2016017680 A1 WO2016017680 A1 WO 2016017680A1 JP 2015071478 W JP2015071478 W JP 2015071478W WO 2016017680 A1 WO2016017680 A1 WO 2016017680A1
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Prior art keywords
group
epoxy
compound
graft polymer
amine
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PCT/JP2015/071478
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English (en)
Japanese (ja)
Inventor
畑中慎太郎
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Daicel Corp
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Daicel Corp
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/50—Amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides

Definitions

  • the present invention relates to a graft polymer and a method for producing the same.
  • This application claims the priority of Japanese Patent Application No. 2014-155844 for which it applied to Japan on July 31, 2014, and uses the content here.
  • a dispersant when dispersing pigments, a dispersant may be used for the purpose of improving dispersibility and storage stability and shortening the dispersion time.
  • a dispersant for example, a dispersant obtained by graft-polymerizing a carboxylic acid group-terminated polycaprolactone to polyethyleneimine is known (Patent Document 1).
  • dispersants are required to have dispersibility for a wide variety of pigments.
  • the dispersant having polyethyleneimine as the main chain described in Patent Document 1 has a structure in which polyethyleneimine is highly branched and has a three-dimensionally crowded structure, when adsorbing to the pigment, In some cases, the nitrogen atom of the imine cannot sufficiently act on the adsorption site, and a sufficient dispersion effect cannot be obtained depending on the pigment.
  • an object of the present invention is to provide a novel graft polymer that is excellent in dispersibility for a wide variety of pigments.
  • the present inventors have found that a graft polymer having a specific epoxy-amine adduct as a main chain and a polyester structure as a side chain is excellent in dispersibility to a pigment, and has completed the present invention.
  • the present invention provides a reaction between an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule as the main chain.
  • an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule as the main chain.
  • a graft polymer having the structure of an epoxy-amine adduct obtained by the above, and having a polyester structure as a side chain.
  • the amine compound (B) is represented by the following formula (b-1) [Wherein, R 2 and R 3 are the same or different and are each a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic hydrocarbon group. A divalent group in which the above and one or more cyclic aliphatic hydrocarbon groups are linked directly or via a linking group containing a hetero atom is shown. q represents 0 or an integer of 1 or more.
  • R 7 represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom.
  • t represents an integer of 0 to 10.
  • the epoxy compound (A) is a compound represented by the following formula (a).
  • X represents a single bond or a divalent group having one or more atoms.
  • the polyester structure in the side chain preferably has a carboxyl group-terminated polyester structure obtained by ring-opening polymerization of ⁇ -caprolactone.
  • the polyester structure in the side chain preferably has a carboxyl group-terminated polyester structure obtained by ring-opening copolymerization of ⁇ -caprolactone and ⁇ -valerolactone.
  • the present invention also provides a dispersant containing the graft polymer.
  • a method for producing a graft polymer is provided.
  • the present invention relates to the following.
  • [1] Obtained by a reaction between an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule as the main chain. Having the structure of an epoxy-amine adduct, A graft polymer having a polyester structure as a side chain.
  • the amine compound (B) is represented by the following formula (b-1) [Wherein, R 2 and R 3 are the same or different and are each a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic hydrocarbon group. A divalent group in which the above and one or more cyclic aliphatic hydrocarbon groups are linked directly or via a linking group containing a hetero atom is shown. q represents 0 or an integer of 1 or more.
  • R 7 represents a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent sulfur atom-containing group, a monovalent nitrogen atom-containing group, or a halogen atom.
  • t represents an integer of 0 to 10.
  • R 10 represents a linear, branched or cyclic divalent aliphatic hydrocarbon group, or one or more of a linear or branched aliphatic hydrocarbon group and one or more of a cyclic aliphatic hydrocarbon group. And a divalent group formed by linking with each other.
  • u represents an integer of 1 or more.
  • v represents an integer of 3 or more.
  • the amine compound (B) includes at least one amine compound selected from the group consisting of the amine compound (B1), the amine compound (B2), and the amine compound (B3). Graft polymer.
  • the compound represented by the formula (a) is at least one selected from the group consisting of compounds represented by the following formulas (a-1) to (a-10): Graft polymer.
  • l and m each represents an integer of 1 to 30;
  • R ′ represents an alkylene group having 1 to 8 carbon atoms; and
  • n1 to n6 each represents an integer of 1 to 30].
  • the polyester structure in the side chain has a carboxyl group-terminated polyester structure obtained by ring-opening polymerization of a lactone represented by the following formula (1): The graft polymer described.
  • R 11 represents an optionally substituted alkylene group having 1 to 10 carbon atoms.
  • a dispersant comprising the graft polymer according to any one of [1] to [22].
  • a pigment composition comprising the dispersant according to [23] and a pigment.
  • Epoxy-amine addition obtained by reaction of an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule The method for producing a graft polymer according to any one of [1] to [22], wherein the product is reacted with a carboxyl group-terminated polyester.
  • the graft polymer of the present invention has excellent dispersibility with respect to a wide variety of pigments by having the above configuration.
  • the graft polymer of the present invention has an epoxy-amine adduct structure as a main chain and a polyester structure as a side chain.
  • a graft polymer obtained by reacting an epoxy-amine adduct and a polyester having a carboxyl group at the terminal is preferable.
  • the side chain polyester structure in the graft polymer of the present invention is not particularly limited, but is preferably a structure of a polyester having a carboxyl group at the terminal (for example, a carboxyl group-terminated polyester described later), for example.
  • the graft polymer of the present invention may further have other side chains as long as the effects of the present invention are not impaired.
  • the epoxy-amine adduct includes an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule (sometimes simply referred to as “epoxy compound (A)”), and two or more in the molecule. It is an epoxy-amine adduct obtained by a reaction with an amine compound (B) having an amino group (sometimes referred to simply as “amine compound (B)”).
  • the above epoxy-amine adduct has two or more amino groups in the molecule obtained by reacting the alicyclic epoxy group of the epoxy compound (A) with the amino group of the amine compound (B).
  • An epoxy-amine adduct is preferred.
  • the term “amino group” simply means —NH 2 (unsubstituted amino group), and “—NH— group” refers to the unsubstituted amino group (—NH 2 ). It shall not be included.
  • Epoxy compound (A) The epoxy compound (A) as a raw material of the epoxy-amine adduct is a polyepoxy compound (alicyclic epoxy compound) having two or more alicyclic epoxy groups in the molecule.
  • An epoxy compound (A) can be used individually or in combination of 2 or more types.
  • the alicyclic epoxy group possessed by the epoxy compound (A) is an epoxy group composed of two adjacent carbon atoms constituting the alicyclic ring (aliphatic ring) and an oxygen atom.
  • the alicyclic epoxy group is not particularly limited. For example, it forms an aliphatic ring having 4 to 16 carbon atoms (aliphatic hydrocarbon ring) such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, or a cycloheptane ring. Examples thereof include an epoxy group composed of two adjacent carbon atoms and an oxygen atom.
  • the epoxy group (cyclohexene oxide group) comprised by two adjacent carbon atoms which comprise a cyclohexane ring, and an oxygen atom is preferable.
  • the number of alicyclic epoxy groups in the molecule of the epoxy compound (A) may be two or more, and is not particularly limited, but is preferably 2 to 6, more preferably 2 to 5, and still more preferably 2. Or three. When the number of alicyclic epoxy groups is more than 6, it is not desirable because a crosslinked structure is taken when synthesizing an amine adduct and tends to be highly viscous or hardened.
  • epoxy compound (A) a compound (epoxy compound) represented by the following formula (a) is particularly preferable.
  • X in the above formula (a) represents a single bond or a linking group (a divalent group having one or more atoms).
  • the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and the like. And a group in which two or more of the groups are linked.
  • Examples of the epoxy compound (A) in which X in the formula (a) is a single bond include 3,4,3 ′, 4′-diepoxybicyclohexane.
  • Examples of the divalent hydrocarbon group for X in the above formula (a) include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group.
  • Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
  • divalent alicyclic hydrocarbon group examples include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And bivalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.
  • Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond in X in the formula (a) is epoxidized include: Examples include linear or branched alkenylene groups having 2 to 8 carbon atoms such as vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, and octenylene group. It is done.
  • the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.
  • a linking group containing an oxygen atom is preferable.
  • divalent hydrocarbon group examples include those exemplified above.
  • R ′ in the following formula (a-5) represents an alkylene group having 1 to 8 carbon atoms.
  • a linear or branched alkylene group such as a group, a hexylene group, a heptylene group, and an octylene group.
  • n1 to n6 each represents an integer of 1 to 30.
  • epoxy compound (A) particularly from the viewpoint of reactivity with an amine compound, the compound represented by the above formula (a-1) [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate Trade name “Celoxide 2021P” (manufactured by Daicel Corporation) and the like] are preferable.
  • the amine compound (B) as a raw material of the epoxy-amine adduct is a polyamine compound having two or more amino groups (—NH 2 ; unsubstituted amino group) in the molecule.
  • the number of amino groups in the molecule of the amine compound (B) may be 2 or more (for example, 2 to 1000) from the viewpoint of dispersibility and polarity.
  • the amine compound (B) can be used alone or in combination of two or more.
  • pigments It is possible to design an optimum structure for the substrate and to improve dispersibility. For this reason, it is preferable to combine two or more amine compounds.
  • Examples of the amine compound (B) include a p-valent amine compound represented by the following formula (b).
  • P in the above formula (b) represents an integer of 2 or more.
  • p may be an integer of 2 or more, and is not particularly limited, but is preferably 2 to 6, more preferably 2 to 5, and still more preferably 2 or 3.
  • R 1 in the above formula (b) represents a p-valent organic group (organic residue) having a carbon atom at the binding site with the nitrogen atom shown in the formula.
  • R 1 include a linear or branched p-valent aliphatic hydrocarbon group; a cyclic p-valent aliphatic hydrocarbon group; a p-valent aromatic hydrocarbon group; and two or more of these groups And a p-valent group linked (bonded) directly or via a linking group (divalent group) containing a hetero atom.
  • linear or branched p-valent aliphatic hydrocarbon group examples include a linear or branched divalent aliphatic hydrocarbon group, a linear or branched trivalent aliphatic hydrocarbon group, and the like.
  • examples thereof include a hydrogen group, a linear or branched tetravalent aliphatic hydrocarbon group, and the like.
  • linear or branched divalent aliphatic hydrocarbon group examples include an alkylene group [eg, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, Linear or branched chain having 1 to 30 carbon atoms (C 1-30 ) such as nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, etc.
  • alkylene group eg, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, Linear or branched chain having 1 to 30 carbon atoms (C 1-30
  • An alkylene group (preferably a C 1-18 alkylene group)], an alkenylene group [an alkenylene group corresponding to the above alkylene group, for example, a linear or branched alkenylene group having 2 to 30 carbon atoms such as a vinylene group or an arylene group. (Preferably a C 2-18 alkenylene group) and the like.
  • alkane-triyl group eg, propane-triyl group, 1,1,1-trimethylpropane-triyl group, etc.
  • 30 linear or branched alkane-triyl groups (preferably a C 3-18 alkane-triyl group) and the like.
  • linear or branched tetravalent aliphatic hydrocarbon group examples include, for example, alkane-tetrayl group [for example, butane-tetrayl group, 2,2-dimethylpropane-tetrayl group and the like having 4 to 30 carbon atoms.
  • alkane-tetrayl group for example, butane-tetrayl group, 2,2-dimethylpropane-tetrayl group and the like having 4 to 30 carbon atoms.
  • a linear or branched alkane-tetrayl group preferably a C 4-18 alkane-tetrayl group
  • the linear or branched p-valent aliphatic hydrocarbon group may have various substituents (that is, the linear or branched p-valent aliphatic hydrocarbon group is And at least one of the hydrogen atoms it has may be substituted with various substituents).
  • substituents include a halogen atom, an oxo group, a hydroxy group, a substituted oxy group (for example, an alkoxy group, an aryloxy group, an aralkyloxy group, and an acyloxy group), a carboxy group, and a substituted oxycarbonyl group (alkoxycarbonyl group).
  • the hydroxy group or carboxy group may be protected with a protective group commonly used in the field of organic synthesis (for example, acyl group, alkoxycarbonyl group, organic silyl group, alkoxyalkyl group, oxacycloalkyl group, etc.).
  • Examples of the substituted or unsubstituted carbamoyl group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group and t-butyl group, or acetyl group and benzoyl group. And a carbamoyl group having an acyl group or an unsubstituted carbamoyl group.
  • substituted or unsubstituted amino group examples include an alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, acetyl group, benzoyl group, and the like. And an amino group having an acyl group such as a group, or an unsubstituted amino group.
  • the heterocyclic ring constituting the heterocyclic group includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring.
  • a heterocyclic ring include, for example, a heterocyclic ring containing an oxygen atom as a hetero atom (for example, a 3-membered ring such as an oxirane ring, a 4-membered ring such as an oxetane ring, a furan ring, a tetrahydrofuran ring, an oxazole ring, and ⁇ -butyrolactone.
  • 5-membered ring such as a ring
  • 6-membered ring such as 4-oxo-4H-pyran ring, tetrahydropyran ring, morpholine ring
  • condensed ring such as benzofuran ring, 4-oxo-4H-chromene ring, chroman ring, 3-oxa Bridged ring such as tricyclo [4.3.1.1 4,8 ] undecan-2-one ring, 3-oxatricyclo [4.2.1.0 4,8 ] nonan-2-one ring )
  • Hetero rings containing a sulfur atom as a hetero atom for example, 5-membered rings such as thiophene ring, thiazole ring and thiadiazole ring, 6-membered rings such as 4-oxo-4H-thiopyran ring, benzothiol
  • a condensed ring such as a thione ring
  • the heterocyclic group may be a heterocyclic group having a substituent, and the substituent may be, for example, the linear or branched p-valent aliphatic hydrocarbon group.
  • substituents eg, C 1-4 alkyl groups such as methyl and ethyl groups
  • alkenyl groups e.g, C 1-4 alkyl groups such as methyl and ethyl groups
  • alkenyl groups cycloalkyl groups
  • cycloalkenyl groups eg, phenyl groups, naphthyl groups, etc.
  • monovalent hydrocarbon groups eg, phenyl groups, naphthyl groups, etc.
  • the nitrogen atom constituting the heterocyclic ring in the heterocyclic group is a conventional protective group (for example, an alkoxy group, an alkoxycarbonyl group, an alkenyloxycarbonyl group, an aralkyloxycarbonyl group, an aralkyl group, an acyl group, an arylsulfonyl group). , An alkylsulfonyl group, etc.).
  • Examples of the cyclic p-valent aliphatic hydrocarbon group include a cyclic divalent aliphatic hydrocarbon group, a cyclic trivalent aliphatic hydrocarbon group, and a cyclic tetravalent aliphatic hydrocarbon group. .
  • cyclic divalent aliphatic hydrocarbon group examples include a cycloalkylene group [for example, a cycloalkylene group having 3 to 20 carbon atoms such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group ( Preferably a C 3-15 cycloalkylene group)], cycloalkenylene group [cycloalkenylene group corresponding to the above cycloalkylene group, for example, a cycloalkenylene group having 3 to 20 carbon atoms such as a cyclohexenylene group (preferably C 3 -15 cycloalkenylene groups)], cycloalkylidene groups [cycloalkylidene groups corresponding to the above cycloalkylene groups, such as cyclopentylidene groups, cyclohexylidene groups, etc., preferably C 3-20 cycloalkylidene
  • Examples of the cyclic trivalent aliphatic hydrocarbon group include a cycloalkane-triyl group and a polycyclic hydrocarbon-triyl group.
  • Examples of the cyclic tetravalent aliphatic hydrocarbon group include a cycloalkane-tetrayl group and a polycyclic hydrocarbon-tetrayl group.
  • the cyclic p-valent aliphatic hydrocarbon group may have a substituent. Examples of the substituent include the linear or branched p-valent aliphatic hydrocarbon group.
  • alkyl groups eg, C 1-4 alkyl groups such as methyl and ethyl groups
  • alkenyl groups e.g., methyl and ethyl groups
  • aryl groups e.g, phenyl and naphthyl groups
  • Examples of the p-valent aromatic hydrocarbon group include groups obtained by removing p hydrogen atoms from an aromatic hydrocarbon in terms of the structural formula.
  • Examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, 9-phenylanthracene, 9,10-diphenylanthracene, naphthacene, pyrene, perylene, biphenyl, binaphthyl, and bianthryl.
  • the p-valent aromatic hydrocarbon group may have a substituent. Examples of the substituent include the linear or branched p-valent aliphatic hydrocarbon group.
  • an alkyl group eg, a C 1-4 alkyl group such as a methyl group or an ethyl group
  • a monovalent hydrocarbon group such as an alkenyl group, a cycloalkyl group, or a cycloalkenyl group
  • linking group containing a hetero atom examples include —CO—, —O—, —CO—O—, —O—CO—O—, —CO—NH—, and —CO—NR.
  • an amine compound represented by the following formula (b-1) (amine compound (B1)), a compound represented by the following formula (b-2) (amine compound) (B2)), a compound represented by the following formula (b-3) (amine compound (B3)), a compound represented by the following formula (b-4) (amine compound (B4)), and the like. It is done. Especially, what contains at least 1 type of amine compound selected from the group which consists of an amine compound (B1), an amine compound (B2), and an amine compound (B3) is preferable.
  • R 2 and R 3 are the same or different and are a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic group.
  • Examples of the linear, branched, or branched divalent aliphatic hydrocarbon group include, for example, the substituted or unsubstituted linear, branched, or branched divalent fat exemplified as R 1.
  • Examples of the divalent group in which one or more of the above-mentioned linear or branched aliphatic hydrocarbon groups and one or more of the cyclic aliphatic hydrocarbon groups are directly bonded include, for example, the following formula (b- Examples include groups exemplified as groups formed by removing two amino groups at both ends from the structural formula represented by 3). Furthermore, as a coupling group containing a hetero atom, the group illustrated as a coupling group containing the hetero atom in R ⁇ 1 > is mentioned, for example.
  • R 2 is preferably a linear or branched divalent aliphatic hydrocarbon group, more preferably a linear or branched alkylene group having 2 to 6 carbon atoms, and still more preferably 2 carbon atoms. 4 to 4 linear or branched alkylene groups (for example, ethylene group, trimethylene group, propylene group, etc., particularly ethylene group).
  • R 3 is preferably a linear or branched divalent aliphatic hydrocarbon group, more preferably a linear or branched alkylene group having 2 to 6 carbon atoms, and still more preferably 2 carbon atoms. 4 to 4 linear or branched alkylene groups (for example, ethylene group, trimethylene group, propylene group, etc., particularly ethylene group).
  • R 3 each in brackets (multiple R 3) may be the same or different.
  • subjected q may be a random type, and may be a block type.
  • q (the number of repeating structural units in parentheses to which q is attached) represents 0 or an integer of 1 or more.
  • q is, for example, preferably 0 to 100, more preferably 0 to 70, still more preferably 1 to 30, even more preferably 1 to 8, and particularly preferably 2 to 5.
  • R 2 and R 3 in the above formula (b-1) may be the same or different. Among these, from the viewpoint that the carboxyl group-terminated polyester in the side chain is likely to be uniformly distributed, R 2 and R 3 in the above formula (b-1) are preferably the same.
  • the compounds represented by the above formula (b-1) include ethylenediamine (EDA) and diethylenetriamine from the viewpoint of reactivity between the epoxy compound (A) and the amine compound (B) and dispersibility of the graft polymer in the pigment.
  • EDA ethylenediamine
  • diethylenetriamine from the viewpoint of reactivity between the epoxy compound (A) and the amine compound (B) and dispersibility of the graft polymer in the pigment.
  • DETA triethylenetetramine
  • TEPA tetraethylenepentamine
  • a commercially available product can also be used as the compound represented by the above formula (b-1).
  • R 4 in the above formula (b-2) is a linear, branched or cyclic divalent aliphatic hydrocarbon group, or one or more of a linear or branched aliphatic hydrocarbon group and a cyclic group.
  • R 4 include the divalent groups exemplified as the above R 2 and R 3 .
  • R 4 is preferably a linear or branched divalent aliphatic hydrocarbon group, more preferably a linear or branched alkylene group having 2 to 6 carbon atoms, and still more preferably 2 carbon atoms. 4 to 4 linear or branched alkylene groups (for example, ethylene group, trimethylene group, propylene group, etc., especially propylene group).
  • R 5 in the above formula (b-2) is a linear, branched or cyclic divalent aliphatic hydrocarbon group or one or more linear or branched aliphatic hydrocarbon groups and a cyclic group.
  • R 5 include the divalent groups exemplified as the above R 2 and R 3 .
  • R 5 is preferably a linear or branched divalent aliphatic hydrocarbon group, more preferably a linear or branched alkylene group having 2 to 6 carbon atoms, and still more preferably 2 carbon atoms.
  • R 5 each in parentheses (multiple R 5) may be the same or different.
  • the addition form (polymerization form) of the structure in the parenthesis to which r is attached may be a random type or a block type.
  • R 4 and R 5 in the above formula (b-2) may be the same or different.
  • r (the number of repeating structural units in parentheses to which r is attached) represents an integer of 1 or more.
  • r is preferably 1 to 100, more preferably 1 to 70, and still more preferably 1 to 30.
  • the compound represented by the above formula (b-2) includes an amine terminal (both terminal amino acids) from the viewpoint of reactivity between the epoxy compound (A) and the amine compound (B) and dispersibility of the graft polymer in the pigment.
  • amine terminal both terminal amino acids
  • commercially available products for example, “JEFFAMINE” series, manufactured by HUNTSMAN Co., Ltd.
  • R 6 and R 8 in the above formula (b-3) are the same or different and each represents an alkylene group having 1 to 4 carbon atoms or an arylene group having 6 to 12 carbon atoms.
  • Specific examples of R 6 and R 8 include alkylene groups having 1 to 4 carbon atoms (eg, methylene group) and arylene groups having 6 to 12 carbon atoms (aromatic hydrocarbons) exemplified as R 1 in formula (b). A group in which two hydrogen atoms are removed from).
  • s (the number of repeating structural units in parentheses with s) represents 0 or 1.
  • R 7 in the above formula (b-3) represents a substituent on the cyclohexane ring shown in the formula, and is the same or different and is a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent sulfur atom.
  • R 7 include, for example, an alkyl group (eg, an alkyl group having 1 to 10 carbon atoms, particularly a methyl group), a halogen atom (a fluorine atom, a chlorine atom, etc.), a hydroxy group, a carboxy group, and an alkoxy group.
  • t represents the number of substituents (R 7 ) on the cyclohexane ring shown in the formula, and represents an integer of 0 to 10 (preferably an integer of 1 to 5).
  • R 7 may be the same or different.
  • examples of the group formed by removing two amino groups at both ends from the structural formula represented by the above formula (b-3) include 1,2-cyclohexylene-methylene group, 1, 3-cyclohexylene-methylene group, 1,4-cyclohexylene-methylene group, cyclohexylidene-methylene group, 1,2-cyclohexylene-ethylene group, 1,3-cyclohexylene-ethylene group, 1,4-cyclohexylene Silene-ethylene group, cyclohexylidene-ethylene group, methylene-1,5,5-trimethyl-1,3-cyclohexylene group (a divalent group formed by removing two amino groups from isophoronediamine), etc.
  • Cyclohexylene-alkylene group 1,2-cyclohexylene-phenylene group, 1,3-cyclohexylene-phenylene group, 1,4-cyclohexyl Cyclohexylene-arylene groups such as lenene-phenylene groups; alkylenes such as methylene-1,2-cyclohexylene-methylene groups, methylene-1,3-cyclohexylene-methylene groups, methylene-1,4-cyclohexylene-methylene groups -Cyclohexylene-alkylene group; alkylene-cyclohexylene-phenylene such as methylene-1,2-cyclohexylene-phenylene group, methylene-1,3-cyclohexylene-phenylene group, methylene-1,4-cyclohexylene-phenylene group Groups; arylene-cyclohexylene-arylene groups such as phenylene-1,2-cyclohexylene-phenylene group,
  • the compound represented by the above formula (b-3) is preferably isophoronediamine from the viewpoint of the reactivity between the epoxy compound (A) and the amine compound (B) and the dispersibility of the graft polymer in the pigment.
  • a commercially available product for example, trade name “Vestamine IPD” manufactured by Evonik Degussa Japan Co., Ltd.
  • Vestamine IPD manufactured by Evonik Degussa Japan Co., Ltd.
  • u (the number of repeating structural units in parentheses to which u is attached) represents an integer of 1 or more, preferably 1 to 100, more preferably 1 to 70, still more preferably 1 ⁇ 30.
  • v (the number of structures in parentheses to which v bonded to R 9 is attached) represents an integer of 3 or more, preferably 3 to 6, more preferably 3 to 5 More preferably, it is 3 or 4.
  • R 10 in the above formula (b-4) is a linear, branched or cyclic divalent aliphatic hydrocarbon group or one or more linear or branched aliphatic hydrocarbon groups and a cyclic group.
  • a divalent group formed by linking with one or more aliphatic hydrocarbon groups is exemplified, and examples thereof include the divalent groups exemplified as R 2 and R 3 described above.
  • R 9 represents a v-valent organic group having a carbon atom at the bonding site with the oxygen atom shown in the formula, and is the same as R 1 (for example, a linear or branched p-valence).
  • An aliphatic hydrocarbon group, a cyclic p-valent aliphatic hydrocarbon group, etc. is a linear, branched or cyclic divalent aliphatic hydrocarbon group or one or more linear or branched aliphatic hydrocarbon groups and a cyclic group.
  • the amine compound (B) from the viewpoint of the reactivity between the epoxy compound (A) and the amine compound (B) and the dispersibility of the graft polymer with respect to the pigment, the amine compound (B1), the amine compound (B2), and the amine compound ( It is preferably at least one amine compound selected from the group consisting of B3), and more preferably, from the viewpoint of further excellent dispersibility in the pigment, only the amine compound (B1), only the amine compound (B2), and the amine compound It is a combination of (B1) and an amine compound (B3), or a combination of an amine compound (B2) and an amine compound (B3).
  • the epoxy-amine adduct can be produced by reacting the epoxy compound (A) with the amine compound (B). More specifically, the epoxy-amine adduct is produced by reacting the alicyclic epoxy group of the epoxy compound (A) with the amino group of the amine compound (B).
  • the epoxy compound (A) and amine compound (B) as raw materials for the epoxy-amine adduct are from the viewpoint of the reactivity between the epoxy compound (A) and the amine compound (B) and the dispersibility of the graft polymer in the pigment.
  • Compound represented by formula (a) and amine compound (B1), compound represented by formula (a), amine compound (B1) and amine compound (B3), compound represented by formula (a) and amine compound (B2), the compound represented by the formula (a), the amine compound (B2), and the amine compound (B3) are preferable.
  • an epoxy compound (A) other than the compound represented by the formula (a) and an amine compound other than the amine compounds (B1) (B2) (B3) may be used in combination.
  • the epoxy equivalent for example, the equivalent of an alicyclic epoxy group
  • the ratio (equivalent of amino group) is not particularly limited, but is preferably 0.3 to 3, more preferably 0.5 to 2, more preferably 0.7 to 1.5, particularly preferably 0.9 to 1.1.
  • the compound represented by the formula (a) in the total amount (100% by weight) of the epoxy compound (A).
  • the proportion of the compound is not particularly limited, but is preferably 80% by weight or more, more preferably 90% by weight or more, and still more preferably 98 to 100% by weight.
  • the proportion of the amine compound (B1) in the total amount (100% by weight) of the amine compound (B) is particularly limited. However, it is preferably 10% by weight or more (for example, 10 to 100% by weight), more preferably 20 to 100% by weight, still more preferably 45 to 90% by weight, and particularly preferably 50 to 70% by weight.
  • the ratio of the amine compound (B1) within the above range, the dispersibility can be further improved.
  • the proportion of the amine compound (B2) in the total amount (100% by weight) of the amine compound (B) is particularly limited. However, it is preferably 10% by weight or more (for example, 10 to 100% by weight), more preferably 20 to 100% by weight, still more preferably 30 to 90% by weight, and particularly preferably 40 to 70% by weight.
  • the ratio of the amine compound (B2) within the above range, flexibility can be improved.
  • the proportion of the amine compound (B3) in the total amount (100% by weight) of the amine compound (B) is particularly limited. However, it is preferably 10 to 70% by weight, more preferably 20 to 60% by weight, still more preferably 30 to 55% by weight. Heat resistance can be improved by making the ratio of an amine compound (B3) into the said range.
  • reaction of epoxy compound (A) and amine compound (B) can be allowed to proceed in the presence of a solvent, or can be allowed to proceed in the absence of a solvent (that is, without solvent).
  • a solvent that is, without solvent
  • the solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; chloroform, dichloromethane.
  • Halogenated hydrocarbons such as 1,2-dichloroethane; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate and the like Esters; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Nitriles such as acetonitrile, propionitrile and benzonitrile; Methanol, ethanol and isopropyl alcohol Alcohols such as butanol; and dimethyl sulfoxide.
  • the said solvent can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the amount of solvent used in the above reaction is not particularly limited and can be set as appropriate.
  • the reaction of the epoxy compound (A) and the amine compound (B) can be caused to proceed by, for example, the following method [1], the following [2], or the following [3].
  • the method for causing the reaction to proceed is not limited to the following methods [1] to [3].
  • [2] A method in which the amine compound (B) is sequentially added to a reaction vessel in which the epoxy compound (A) is charged and heated to the reaction temperature as necessary, and both are reacted.
  • [3] A method in which the epoxy compound (A) is sequentially added to a reaction vessel in which the amine compound (B) is charged and heated to the reaction temperature as necessary, and both are reacted.
  • the “sequential addition” means continuous addition (a mode of adding over a certain period of time) or intermittent addition (a mode of split addition in multiple times).
  • the method according to the above [2] is preferable because the reaction heat can be easily controlled and an epoxy-amine adduct having a high molecular weight and a high glass transition temperature can be easily formed.
  • the method [3] is preferred.
  • the epoxy-amine adduct having a lower molecular weight may be advantageous depending on the application. In such a case, the reaction is preferably carried out by the method [1] above.
  • the rate at which the amine compound (B) is added in the method [2] is not particularly limited.
  • the rate at which the epoxy compound (A) is added in the method [3] is not particularly limited.
  • the total amount of the epoxy compound (A) to be added is 100 parts by weight, 0.1 to 20 parts by weight. It can set suitably from the range of a part / minute.
  • the amine compound (B) or epoxy compound (A) to be added can be added as it is, or can be added in the state of a solution or dispersion dissolved or dispersed in a solvent.
  • each amine compound (B) when using 2 or more types of amine compounds (B), in the method of said [2], it may be dripped in the state which mixed each amine compound (B), and it is dripped in the state (each) which is not mixed. May be. In the latter case, each amine compound (B) can be dropped simultaneously or sequentially. The same applies to the dropping in the case of using two or more epoxy compounds (A) in the method [3].
  • the temperature (reaction temperature) in the above reaction is not particularly limited, but is preferably 30 to 280 ° C, more preferably 80 to 260 ° C, still more preferably 120 to 250 ° C.
  • the reaction temperature may always be constant (substantially constant), or may be changed stepwise or continuously.
  • the reaction time in the above reaction is not particularly limited, but is preferably 0.2 to 20 hours, more preferably 0.5 to 10 hours, and further preferably 2 to 8 hours.
  • the reaction time is preferably 0.2 to 20 hours, more preferably 0.5 to 10 hours, and further preferably 2 to 8 hours.
  • the above reaction can be carried out under normal pressure, under pressure or under reduced pressure.
  • the pressure during the reaction may always be constant (substantially constant), or may be changed stepwise or continuously.
  • the atmosphere in which the above reaction is performed is not particularly limited, and the reaction can be performed in any atmosphere such as an inert gas (for example, nitrogen, argon, etc.) or air.
  • the above reaction is not particularly limited and can be carried out by any of a batch method (batch method), a semi-batch method, and a continuous flow method.
  • reaction of epoxy compound (A) and amine compound (B) gives an epoxy-amine adduct.
  • reaction of epoxy compound (A) and amine compound (B) gives an epoxy-amine adduct.
  • the resulting epoxy-amine adduct is obtained by, for example, known or conventional separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these. It is possible to separate and purify by, for example.
  • the number of amino groups (—NH 2 ; unsubstituted amino group) possessed by the epoxy-amine adduct is preferably 2 or more, more preferably 2 to 10, further preferably 2 to 4, particularly preferably 2 Or three.
  • the epoxy-amine adduct preferably has substantially no epoxy group (particularly an alicyclic epoxy group derived from the epoxy compound (A)).
  • the position of the amino group (—NH 2 ; unsubstituted amino group) in the epoxy-amine adduct is not particularly limited, but the end of the molecular chain of the epoxy-amine adduct (particularly the linear epoxy-amine adduct) In such a case, it is preferable to locate at both ends of the molecular chain of the epoxy-amine adduct.
  • the epoxy-amine adduct is generated by the reaction between the alicyclic epoxy group of the epoxy compound (A) and the amino group (—NH 2 ; unsubstituted amino group) of the amine compound (B). .
  • the epoxy-amine adduct is an —NH— group (substituted amino group) formed by the reaction of the alicyclic epoxy group and an amino group (in addition, when the amine compound (B1) is used, the amine compound (B1 )) -NH- group (when q is 1 or more)) and the cycloaliphatic epoxy group of the epoxy compound (A) are presumed to be poor in reactivity, but usually -NH- The group remains unreacted.
  • the number of —NH— groups in the molecule of the epoxy-amine adduct is not particularly limited, but is preferably 1 to 200, more preferably 1 to 150, and still more preferably 2 to 100. If the epoxy-amine adduct does not have a —NH— group, the reactivity with the carboxyl group-terminated polyester may be reduced.
  • the number of —NH— groups in the epoxy-amine adduct is, for example, the epoxy constituting the epoxy-amine adduct using a molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC). It is possible to calculate by obtaining the number of the compound (A) and the amine compound (B).
  • the compound obtained by the reaction between the epoxy compound having a glycidyl group and the amine compound (B) includes a reaction between the —NH— group and the glycidyl group generated by the reaction between the glycidyl group and the amino group (unsubstituted amino group).
  • the —NH— group does not substantially remain because of its very high properties.
  • the number average molecular weight of the epoxy-amine adduct is not particularly limited, but is preferably 200 to 40000, more preferably 300 to 30000, and still more preferably 400 to 20000.
  • the number average molecular weight is preferably 200 to 40000, more preferably 300 to 30000, and still more preferably 400 to 20000.
  • the number average molecular weight can be calculated using the molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC) method.
  • the glass transition temperature (Tg) of the epoxy-amine adduct is not particularly limited, but is preferably ⁇ 50 to 200 ° C., more preferably ⁇ 40 to 190 ° C., still more preferably ⁇ 30 to 180 ° C., and particularly preferably 20 ⁇ 180 ° C. When the glass transition temperature is in the above range, the dispersibility of the graft polymer with respect to the pigment tends to be further improved.
  • the Tg of the epoxy-amine adduct can be measured, for example, by differential scanning calorimetry (DSC) or dynamic viscoelasticity measurement. More specifically, it can be measured by the method disclosed in the examples.
  • the epoxy-amine adduct has a structural unit (structural unit) derived from the epoxy compound (A) and a structural unit derived from the amine compound (B).
  • a structural unit represented by the following formula (I) structural unit; structural unit derived from the compound represented by formula (a)
  • a structural unit represented by the following formula (II) (amine)
  • the addition form (polymerization form) of the epoxy compound (A) and the amine compound (B) may be any form of alternating type, random type, and block type.
  • each cyclohexane ring of the structural unit represented by formula (I) The bonding position of the nitrogen atom (—NH—) of the structural unit derived from the amine compound (B) bonded to is the 3-position carbon atom or 4-position carbon atom of the cyclohexane ring.
  • the nitrogen atom is bonded to the 3-position carbon atom
  • the hydroxy group (—OH) bonded to the cyclohexane ring in the formula (I) is bonded to the 4-position carbon atom.
  • the bonding position of the nitrogen atom is the carbon atom at the 4-position of the cyclohexane ring
  • the bonding position of the hydroxy group (—OH) bonded to the cyclohexane ring in the formula (I) is the carbon atom at the 3-position.
  • the bonding positions of the nitrogen atoms (or the bonding positions of hydroxy groups) in a plurality of (two or more) cyclohexane rings in the formula (I) may be the same or different.
  • the above-mentioned position number is attached
  • generated by ring-opening polymerization of the lactone represented by following formula (1), and has a carboxyl group at the terminal is mentioned, for example.
  • the carboxyl group-terminated polyester preferably has a carboxyl group only at one end of the polyester chain.
  • the said lactone compound can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the terminal carboxyl group (at least one of the terminal carboxyl groups) can react with the amino group or hydroxyl group of the epoxy-amine adduct (for example, addition reaction, graft polymerization, etc.).
  • R 11 in the above formula (1) is an optionally substituted alkylene group having 1 to 10 carbon atoms (straight chain alkylene group, preferably a straight chain alkylene group having 2 to 5 carbon atoms (ethylene group, n-propylene group). N-butylene group, n-hexylene group)).
  • the substituent in the alkylene group having 1 to 10 carbon atoms in R 11 is not particularly limited.
  • an alkyl group for example, an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group is preferable.
  • the lactone compound represented by the above formula (1) is not particularly limited.
  • ⁇ -caprolactone, ⁇ -valerolactone, ⁇ -methyl- ⁇ -valerolactone, ⁇ -propiolactone, ⁇ -butyrolactone, 2 -Methyl caprolactone, 4-methyl caprolactone and the like in addition to being industrially easily available, the reactivity for obtaining a ring-opening polymer is excellent, and from the viewpoint of compatibility with a substrate, ⁇ -caprolactone, ⁇ -valerolactone, or a combination thereof Is preferred.
  • the graft polymer of the present invention has, as a side chain polyester structure, a carboxyl group-terminated polyester obtained by ring-opening polymerization of ⁇ -caprolactone or ⁇ -valerolactone, or ⁇ -caprolactone and ⁇ -valerolactone. It preferably has a structure of a carboxyl group-terminated polyester obtained by polymerization.
  • polyester which has a structural unit represented by following formula (2), and has a carboxyl group at the terminal is mentioned.
  • w1 (the number of repeating structural units in parentheses to which w1 is attached) represents an integer of 1 or more, preferably 1 to 100, more preferably 1 to 70, still more preferably 1 to 30 It is.
  • R 11 in the formula (2) is may be the same as those R 11 in the formula (1).
  • an alkylene group having 1 to 10 carbon atoms (preferably carbon having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group) which may have an alkyl group having 1 to 10 carbon atoms as a substituent.
  • a linear alkylene group of 2 to 5 is preferred.
  • R 11 plural R 11 in each parenthesis may be the same or different.
  • subjected to w1 may be a random type, and may be a block type.
  • the method for synthesizing the carboxyl group-terminated polyester is not particularly limited, but (i) an addition reaction for adding a lactone to a monocarboxylic acid, (ii) an addition reaction for adding a lactone to a hydroxycarboxylic acid, (iii) a monocarboxylic acid, A condensation reaction in which the three components of hydroxycarboxylic acid and lactone are condensed; (iv) a condensation reaction in which the dicarboxylic acid and diol component are condensed with lactone, hydroxycarboxylic acid, monocarboxylic acid, etc .; Examples thereof include a condensation reaction in which a polyvalent carboxylic acid or an acid anhydride thereof, a polyhydric alcohol, a lactone, a hydroxycarboxylic acid or the like is used for condensation. Among these, from the viewpoint that a carboxyl group-terminated polyester having a molecular weight as designed is easily obtained, the synthesis method (i) or (ii) is prefer
  • the monocarboxylic acid used for the synthesis of the carboxyl group-terminated polyester is not particularly limited, but is an aliphatic carboxylic acid such as acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, lauric acid, stearic acid, and methoxyacetic acid. And aromatic carboxylic acids such as abietic acid and phenylacetic acid. Among these, lauric acid is preferable from the viewpoint of industrial availability and dispersibility of the graft polymer with respect to the pigment.
  • the said monocarboxylic acid can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the hydroxycarboxylic acid used for the synthesis of the carboxyl group-terminated polyester is not particularly limited, and examples thereof include saturated or unsaturated aliphatic hydroxycarboxylic acids and aromatic hydroxycarboxylic acids. Specifically, ricinoleic acid, 12-hydroxystearic acid, castor oil fatty acid (castor oil fatty acid condensate), hydrogenated castor oil fatty acid, ⁇ -hydroxyvaleric acid, ⁇ -hydroxycaproic acid, p-hydroxyethyloxycarboxylic acid, 2- Hydroxynaphthalene-3-carboxylic acid, 2-hydroxynaphthalene-6-carboxylic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolvaleric acid, 2,2-dimethylolpentanoic acid, malic acid, tartaric acid, lactic acid Glycolic acid, gluconic acid, hydroxypivalic acid, 11-oxyhexadecanoic acid, 2-oxidedecano
  • ricinoleic acid, castor oil fatty acid or a condensate thereof is preferable from the viewpoint of industrial availability and dispersibility of the graft polymer with respect to the pigment.
  • the said hydroxy monocarboxylic acid can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • polyhydric carboxylic acid or its acid anhydride used for the synthesis combination of the said carboxyl group terminal polyester, Maleic acid, succinic acid, glutaric acid, fumaric acid, adipic acid, sebacic acid, azelaic acid , Dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, trimellitic acid, methyltetrahydrophthalic acid, or anhydrides thereof.
  • the above-mentioned divalent or higher polyvalent carboxylic acid or acid anhydride thereof can be used alone or in combination of two or more.
  • the polyhydric alcohol used for the synthesis of the carboxyl group-terminated polyester is not particularly limited, and examples thereof include linear or branched polyhydric aliphatic alcohols, alicyclic polyhydric alcohols, and aromatic polyhydric alcohols. . Specifically, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, 3-methylpentanediol, 1, Examples thereof include 5-pentanediol, 1,6-hexanediol, trimethylolpropane, cyclohexanedimethanol, 1,4-dibenzyl alcohol and the like.
  • the said polyhydric alcohol can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the carboxyl group-terminated polyester it is preferable to use a catalyst (esterification catalyst) and / or a reaction solvent from the viewpoint of increasing the reaction rate and improving the heat exchange ability. Moreover, it is preferable to synthesize
  • the esterification catalyst used for the synthesis of the carboxyl group-terminated polyester is not particularly limited. Examples thereof include tin compounds such as stannous, tetrabutyl titanate, tetraethyl titanate, and tetrapropyl titanate. Among these, tetrabutyl titanate is preferable from the viewpoint of cost and productivity.
  • the said esterification catalyst can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the amount of the esterification catalyst used (the total amount when two or more esterification catalysts are used) is not particularly limited, but is preferably 0.1 to 3000 ppm based on the total amount of the reaction raw materials.
  • the amount of the esterification catalyst used is 0.1 ppm or more, the ring-opening polymerization rate of the lactone is increased and the productivity is improved.
  • coloring of carboxyl group-terminated polyester can be suppressed by setting it as 3000 ppm or less.
  • reaction solvent used for the synthesis of the carboxyl group-terminated polyester examples include dehydrating solvents such as toluene and xylene.
  • the temperature at the time of synthesizing the carboxyl group-terminated polyester can be appropriately selected depending on the type of raw material, molar ratio, type and amount of catalyst, type and amount of solvent, etc., for example, 120 to 220 ° C (preferably 160 to 210 ° C) Is mentioned.
  • 120 to 220 ° C preferably 160 to 210 ° C
  • the reaction rate is increased.
  • side reactions for example, decomposition of a lactone polymer into a lactone monomer, generation of a cyclic lactone dimer, etc.
  • coloring of the carboxyl group-terminated polyester can be suppressed.
  • the carboxyl group-terminated polyester can be synthesized, for example, by charging the above raw materials into a reactor equipped with a dehydrating tube and a condenser and reacting them under an inert gas stream such as nitrogen gas.
  • an inert gas stream such as nitrogen gas.
  • the reaction solvent may be removed by an operation such as distillation or may be used as it is for the reaction with the epoxy-amine adduct.
  • the acid value of the carboxyl group-terminated polyester is not particularly limited, but is preferably 1 to 200, for example.
  • the viscosity of the carboxyl group-terminated polyester can be adjusted to an appropriate range.
  • the oxidation is 200 or less, the molecular weight of the carboxyl group-terminated polyester is in an appropriate range, a repellent layer is easily formed around the pigment, and the dispersibility to the pigment is improved.
  • the acid value refers to the acid value measured according to JIS K-1557.
  • the weight average molecular weight of the carboxyl group-terminated polyester is not particularly limited, but is preferably 100 to 5,000.
  • a sufficient three-dimensional repellent layer is formed around the pigment to improve dispersibility, and compatibility with pigments such as paints and ink vehicles is improved.
  • the said weight average molecular weight says the value measured by NMR method.
  • the graft polymer of the present invention is, for example, a reaction between the epoxy-amine adduct obtained by the reaction of the epoxy compound (A) and the amine compound (B) with a polyester (for example, the carboxyl group-terminated polyester) (for example, , Graft polymerization). More specifically, for example, derived from the —OH group in the structural unit derived from the epoxy compound (A) (for example, —OH group in the formula (I)) or the amine compound (B) of the epoxy-amine adduct.
  • a —NH— group for example, —NH— group in the formulas (II), (III), and (IV)
  • a carboxyl group-terminated polyester eg, a terminal carboxyl group
  • the epoxy in the total amount of raw materials for reaction (total amount of raw materials including the epoxy-amine adduct and the carboxyl group-terminated polyester) (100% by weight)
  • the proportion of the amine adduct is not particularly limited, but is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, and still more preferably 10 to 30% by weight.
  • the reaction efficiency between the epoxy-amine adduct and the carboxyl group-terminated polyester is improved.
  • the total amount (total amount) of all epoxy-amine adducts is preferably within the above range.
  • the carboxyl in the total amount of raw materials for reaction (total amount of raw materials including the epoxy-amine adduct and the carboxyl group-terminated polyester) (100% by weight)
  • the proportion of the base terminal polyester is not particularly limited, but is preferably 50 to 99% by weight, more preferably 60 to 95% by weight, and still more preferably 70 to 90% by weight.
  • the ratio of the carboxyl group-terminated polyester to the epoxy-amine adduct is not particularly limited. Is preferably 1.01 to 10.00, more preferably 1.50 to 8.00, and still more preferably 2.00 to 6.00. By setting the ratio within the above range. The reaction efficiency between the epoxy-amine adduct and the carboxyl group-terminated polyester is improved.
  • the reaction between the epoxy-amine adduct and the carboxyl group-terminated polyester can be allowed to proceed in the presence of a solvent, or can be allowed to proceed in the absence of a solvent (ie, without solvent).
  • a solvent ie, without solvent
  • the solvent illustrated by reaction with the above-mentioned epoxy compound (A) and amine compound (B) is mentioned.
  • the said solvent can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the usage-amount of the said solvent is not specifically limited, It can set suitably.
  • a polymerization initiator for the reaction between the epoxy-amine adduct and the carboxyl group-terminated polyester, for example, a polymerization initiator, a catalyst, a solvent, an antioxidant or the like may be used.
  • the reaction between the epoxy-amine adduct and the carboxyl group-terminated polyester can be carried out by a known or conventional method, and is not particularly limited.
  • the reaction between the epoxy-amine adduct and the carboxyl group-terminated polyester is performed.
  • the reaction can be carried out by batch charging into the container, or either one of the epoxy-amine adduct and the carboxyl group-terminated polyester is charged into the reaction container, and the other is added (for example, the above-mentioned sequential addition) to react. You can also.
  • reaction temperature in the above reaction is not particularly limited, but can be appropriately selected from the range of, for example, 0 to 200 ° C. (for example, 15 to 150 ° C.).
  • reaction time is not particularly limited, but can be appropriately selected from the range of, for example, 0.2 to 20 hours (eg, 1 to 10 hours).
  • the above reaction can be carried out under normal pressure, under pressure or under reduced pressure.
  • the atmosphere for carrying out the reaction is not particularly limited, but can be carried out in any atmosphere such as in an inert gas (for example, nitrogen, argon, etc.) or in the air.
  • the above reaction may be performed with stirring or may not be performed.
  • the above reaction is not particularly limited and can be carried out by any of a batch method (batch method), a semi-batch method, and a continuous flow method.
  • the graft polymer of the present invention is separated by known or conventional separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these. It is possible to purify.
  • amino groups in the epoxy-amine adduct are eliminated by reaction with polyester (for example, carboxyl-terminated polyester).
  • polyester for example, carboxyl-terminated polyester.
  • the graft polymer of the present invention may have an amino group (may be an amino group-containing graft polymer) or may not have an amino group.
  • the graft polymer of the present invention may have a secondary amino group (for example, —NH— group, etc.) in the main chain (for example, in the structure of an epoxy-amine adduct).
  • the number of secondary amino groups is not particularly limited, and examples thereof include 1 to 1000 (preferably 2 to 800, more preferably 5 to 500, still more preferably 10 to 300).
  • the graft polymer of the present invention has a polyester structure as a side chain.
  • the structure of each side chain may be the same or different.
  • the polyester structure of the side chain is not particularly limited, but the structure of the carboxyl group-terminated polyester is preferable. Among these, a polyester structure represented by the following formula (3) or (4) is preferable.
  • R 11 in the formula (3) and (4), and R 11 in the formula (1) the same group.
  • an alkylene group having 1 to 10 carbon atoms (preferably having a carbon number of 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group) may be used as a substituent. 2-5 linear alkylene groups) are preferred.
  • R 11 in the above formulas (3) and (4) may be the same or different.
  • R 11 in the formula (3) and (4) may be different or may be the same as R 11 in the formula (1) and / or (2).
  • R 12 in the above formulas (3) and (4) include groups derived from the monocarboxylic acid, the hydroxycarboxylic acid or the polyvalent carboxylic acid used for the synthesis of the carboxyl group-terminated polyester.
  • R 12 in the above formulas (3) and (4) may be the same or different.
  • w2 (the number of repeating structural units in parentheses to which w2 is attached) and w3 in the above formula (4) (the number of repeating structural units in parentheses to which w3 is attached) are 1 or more. And is preferably 1 to 100, more preferably 1 to 70, and still more preferably 1 to 30.
  • R 11 (plural R 11 ) in each parenthesis may be the same or different.
  • w2 and w3 may be the same or different.
  • subjected to w2 or w3 may be a random type, and may be a block type.
  • the use of the graft polymer of the present invention is not particularly limited, it can be used as a pigment dispersant or other inorganic filler dispersant.
  • the graft polymer of the present invention comprises a reaction between an epoxy compound (A) having a main chain having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule. Because of the structure of the epoxy-amine adduct obtained by the above, the structure of the main chain can be changed variously depending on the type of epoxy compound or amine compound, the degree of freedom of the structure of the main chain is improved, and the graft polymer as a whole The dispersibility of the pigment is improved.
  • the structural unit part derived from the epoxy compound (A) in the main chain and the structural unit part derived from the amine compound (B) have different properties, so that the dispersibility of the graft polymer as a whole can be improved. It is thought that it will be further improved.
  • the graft polymer of this invention can change the structure of the amine adduct part in a principal chain, if an amine compound (B) is changed (for example, if the combination, a ratio, etc. of an amine compound (B) are changed). It is considered that it is easy to adjust wettability and adhesion to various base materials.
  • a three-dimensional repellent layer is formed around the pigment to further improve dispersibility.
  • the graft polymer of the present invention is excellent in storage stability and can form a dispersed state in a short time.
  • the dispersant of the present invention contains the graft polymer of the present invention.
  • the dispersant of the present invention may be only the graft polymer of the present invention, or may contain other dispersible compounds. Especially, it is preferable that it is only the graft polymer of this invention from a viewpoint that it is excellent in the dispersibility with respect to a pigment.
  • Examples of the other dispersible compounds include, but are not limited to, anionic compounds such as sulfates, sulfonates, and phosphates, cationic compounds such as aliphatic amine salts, nonionic compounds, and polymer compounds. It is done.
  • the ratio of the graft polymer of the present invention in the dispersant of the present invention is not particularly limited, but is preferably 30 to 100% by weight, more preferably 40 to 95% by weight, based on the total amount of the dispersant (100% by weight). More preferably, it is 50 to 90% by weight.
  • the dispersant of the present invention may further contain a solvent, a leveling agent, an antifoaming agent, a surfactant, a flame retardant, an antioxidant, an antiseptic, and the like.
  • Pigment composition By blending (mixing) the dispersant of the present invention and the pigment, a pigment composition (pigment dispersion composition) is obtained. That is, the pigment composition contains at least the graft polymer of the present invention and the pigment. The pigment composition may contain a dispersant other than the dispersant of the present invention.
  • the above pigments are not particularly limited, but include inorganic pigments such as titanium oxide, zinc oxide, cadmium sulfide, yellow iron oxide, red pepper, yellow lead, carbon black, phthalocyanines, insoluble azo pigments, azo lake pigments, condensed polycyclic systems. Pigments (slen, indigo, perylene, perinone, phthalone, dioxazine, quinacridone, isoindolinone, and diketopyrrolopyrrole pigments).
  • inorganic pigments such as titanium oxide, zinc oxide, cadmium sulfide, yellow iron oxide, red pepper, yellow lead, carbon black, phthalocyanines, insoluble azo pigments, azo lake pigments, condensed polycyclic systems. Pigments (slen, indigo, perylene, perinone, phthalone, dioxazine, quinacridone, isoindolinone, and diketopyrrolopyrrole pigments).
  • the pigment composition may contain a coating resin, a solvent, a leveling agent, an antifoaming agent, a surfactant, a flame retardant, an antioxidant, an antiseptic, and the like.
  • a coating resin a solvent, a leveling agent, an antifoaming agent, a surfactant, a flame retardant, an antioxidant, an antiseptic, and the like.
  • an alkyd resin, oil free alkyd resin, an acrylic resin, a urethane resin, etc. are mentioned.
  • the content of the graft polymer of the present invention in the pigment composition is not particularly limited, but is preferably 1 to 50% by weight, more preferably 2 to 40% by weight with respect to the total amount of the pigment composition (100% by weight). More preferably, it is 3 to 30% by weight.
  • the method for producing the pigment composition is not particularly limited, but can be produced by stirring and mixing the components such as the graft polymer and the pigment of the present invention at a predetermined ratio.
  • the graft polymer of the present invention reacts with the pigment, the graft polymer hardly aggregates or crystallizes in the composition.
  • the graft polymer of the present invention exhibits excellent dispersibility (dispersion effect) for a wide variety of pigments.
  • the graft polymer of the present invention and the composition containing the same are, for example, a filter for fine color separation such as a liquid crystal panel, a thin film transistor side substrate of a liquid crystal panel, etc.
  • a composition for a liquid crystal panel that can be used for: a composition for forming a black matrix in an optical color filter (a composition for forming a black matrix); a coloring composition for forming a color filter; and an oily black pigment writing instrument ink Obtained oily black content dispersion for writing instrument ink; Pigment dispersion containing colored pigment or carbon black (eg, pigment dispersant for paint); Dispersion containing carbon black and black photosensitive composition (eg, photocuring) Black photosensitive composition used for adhesive coatings, photo-curable adhesives, photoresists for printed boards and printed wiring boards, etc.) Active energy ray curable inkjet ink using carbon black; non-aqueous inkjet ink (non-aqueous ink composition); conductive material dispersion (for example, electrode paste in batteries and the like, conductive material dispersion for conductive material-coated active material) Electrophoretic dispersion liquid containing black electrophoretic particles (for example, image display medium, electrophoretic dispersion liquid for image
  • graft polymer of the present invention By using the graft polymer of the present invention and the composition containing the same in these embodiments and applications, for example, color filters, electrode substrates, liquid crystal display devices (liquid crystal panels), oil-based black pigment writing instrument inks, writing instruments, paints (for example, , Solid paint, metallic paint), photocurable paint, photocurable adhesive, printing board, printed wiring board, inkjet ink (for example, active energy ray curable inkjet ink, non-aqueous inkjet ink), electrode paste, conductive material Coated active material, battery (for example, lithium ion battery) image display medium and image display device (for example, electronic paper) using black electrophoretic particles, plastic material, printing ink, thermal transfer ink, light shielding film, electrocapillary display device, electro Wetting display device, electrochromic display device, optical element ( Eg to optical shutters, optical pickup device, the various articles of a liquid optical lens) or the like is obtained.
  • the content of the content is flowable (130 to 150 ° C.), and then poured out from the reaction vessel onto release paper, further cooled and solidified, and then pulverized to give an epoxy-amine 990 g of adduct 1 (amine adduct 1, main chain 1) was obtained.
  • the mixture was reacted by stirring at 200 ° C. for 3 hours and further at 220 ° C. for 2 hours to obtain an epoxy-amine adduct.
  • the content of the content is flowable (130 to 150 ° C.), and then poured out from the reaction vessel onto release paper, further cooled and solidified, and then pulverized to give an epoxy-amine 1000 g of adduct 2 (amine adduct 2, main chain 2) was obtained.
  • the content of the content is flowable (130 to 150 ° C.), and then poured out from the reaction vessel onto release paper, further cooled and solidified, and then pulverized to give an epoxy-amine 790 g of adduct 3 (amine adduct 3, main chain 3) was obtained.
  • the content of the content is flowable (130 to 150 ° C.), and then poured out from the reaction vessel onto release paper, further cooled and solidified, and then pulverized to give an epoxy-amine 530 g of adduct 4 (amine adduct 4, main chain 4) was obtained.
  • Example 1 Into a 1000 mL reactor equipped with a condenser, a nitrogen introducing tube, a stirrer and a thermometer, 856 parts of carboxyl group-terminated polyester 1 (side chain 1) were charged, and then 144 parts of epoxy-amine adduct 1 were charged and reacted at 120 ° C. It was. The reaction was stopped 8 hours after the start of the reaction to obtain a graft polymer.
  • Example 2 With the composition shown in Table 1, a graft polymer was prepared by the same procedure as in Example 1.
  • the acid value was measured according to JIS K-1557.
  • Pigment dispersibility [Preparation of pigment paste with pigment dispersant]
  • a pigment and a solvent are blended in the blending amounts shown in Table 2, and glass beads are further added.
  • the glass beads were removed by filtration to obtain a pigment dispersion paste in which the pigment was dispersed with a pigment dispersant (graft polymer).
  • liquidity of the pigment dispersion paste was visually evaluated on the following references
  • the evaluation results are shown in Table 2.
  • the numerical value in Table 2 shows a weight part. Observe the filtration state and the viscosity of the filtrate when preparing the pigment dispersion paste. If the glass beads can be filtered and the fluidity is good, the dispersion is good. It was evaluated.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Resins (AREA)

Abstract

Le polymère greffé de l'invention est caractéristique en ce qu'il possède, en tant que chaîne principale, la structure d'un produit d'addition époxy-amine qui peut être obtenu par réaction d'un composé époxy (A) possédant au moins deux groupes époxy alicyclique par molécule, et d'un composé amine (B) possédant au moins deux groupes amino alicyclique par molécule; ce polymère greffé de l'invention est aussi caractéristique en ce qu'il possède, en tant que chaîne latérale, une structure polyester. Le polymère greffé de l'invention est excellent en termes de propriétés de dispersion vis-à-vis d'un grand nombre de pigments différents.
PCT/JP2015/071478 2014-07-31 2015-07-29 Nouveau polymère greffé, et procédé de fabrication de celui-ci Ceased WO2016017680A1 (fr)

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Citations (12)

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JPS57164116A (en) * 1981-04-03 1982-10-08 Daicel Chem Ind Ltd Modified epoxy resin
JPS5821416A (ja) * 1981-07-31 1983-02-08 Daicel Chem Ind Ltd 新規コ−テイング用樹脂の製造法
JPS5832628A (ja) * 1981-08-20 1983-02-25 Daicel Chem Ind Ltd エポキシ樹脂硬化性組成物
JPS60155223A (ja) * 1983-12-22 1985-08-15 アモコ、コーポレーション 熱可塑性変性エポキシ組成物
JPS61233068A (ja) * 1985-04-10 1986-10-17 Nippon Oil & Fats Co Ltd カチオン電着塗料用樹脂の製造方法
JPS63189420A (ja) * 1987-01-30 1988-08-05 Nippon Paint Co Ltd 両性イオン型変性エポキシ樹脂
JPS63189419A (ja) * 1987-01-30 1988-08-05 Nippon Paint Co Ltd アニオン型変性エポキシ樹脂
JPH01225619A (ja) * 1988-03-07 1989-09-08 Mitsui Petrochem Ind Ltd 変性エポキシ樹脂の製造方法
JPH0291169A (ja) * 1988-09-29 1990-03-30 Kansai Paint Co Ltd 被覆用樹脂組成物
JPH03126954A (ja) * 1989-10-12 1991-05-30 Ricoh Co Ltd 乾式電子写真用トナー
JP2000290584A (ja) * 1999-02-05 2000-10-17 Kansai Paint Co Ltd 被覆用樹脂組成物
JP2003012764A (ja) * 2001-06-28 2003-01-15 Kansai Paint Co Ltd カチオン性樹脂の製造方法及びカチオン電着塗料

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57164116A (en) * 1981-04-03 1982-10-08 Daicel Chem Ind Ltd Modified epoxy resin
JPS5821416A (ja) * 1981-07-31 1983-02-08 Daicel Chem Ind Ltd 新規コ−テイング用樹脂の製造法
JPS5832628A (ja) * 1981-08-20 1983-02-25 Daicel Chem Ind Ltd エポキシ樹脂硬化性組成物
JPS60155223A (ja) * 1983-12-22 1985-08-15 アモコ、コーポレーション 熱可塑性変性エポキシ組成物
JPS61233068A (ja) * 1985-04-10 1986-10-17 Nippon Oil & Fats Co Ltd カチオン電着塗料用樹脂の製造方法
JPS63189420A (ja) * 1987-01-30 1988-08-05 Nippon Paint Co Ltd 両性イオン型変性エポキシ樹脂
JPS63189419A (ja) * 1987-01-30 1988-08-05 Nippon Paint Co Ltd アニオン型変性エポキシ樹脂
JPH01225619A (ja) * 1988-03-07 1989-09-08 Mitsui Petrochem Ind Ltd 変性エポキシ樹脂の製造方法
JPH0291169A (ja) * 1988-09-29 1990-03-30 Kansai Paint Co Ltd 被覆用樹脂組成物
JPH03126954A (ja) * 1989-10-12 1991-05-30 Ricoh Co Ltd 乾式電子写真用トナー
JP2000290584A (ja) * 1999-02-05 2000-10-17 Kansai Paint Co Ltd 被覆用樹脂組成物
JP2003012764A (ja) * 2001-06-28 2003-01-15 Kansai Paint Co Ltd カチオン性樹脂の製造方法及びカチオン電着塗料

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JULIA THEIS ET AL.: "Formation of epoxide-amine oligo-adducts as OH- functionalized initiators for the ring-opening polymerization of epsilon-caprolactone", BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY, vol. 6, 2010, pages 938 - 944 *

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