TW201609854A - Novel graft polymer and method for producing same - Google Patents

Abstract

This graft polymer is characterized by having an epoxy-amine adduct structure that can be obtained by reacting an epoxy compound (A) having, as a main chain, two or more alicyclic epoxy groups within the molecule, and an amine compound (B) having two or more amino groups within the molecule, and having, as a side chain, a polyester structure, the graft polymer having excellent dispersibility in a wide range of different pigments.

Description

Novel graft polymer and method of producing the same

This invention relates to graft polymers and methods for their manufacture. This case was filed in Japan on July 31, 2014, and claims the priority of Japanese Patent No. 2014-155844, and its contents are hereby incorporated.

In the field of paints, inks, and the like, when a pigment is dispersed, a dispersant may be used for the purpose of improving dispersibility, storage stability, and shortening of dispersion time. As such a dispersing agent, for example, a dispersing agent in which a carboxyl terminal polycaprolactone is graft-polymerized to polyethyleneimine is known (Patent Document 1).

Advanced technical literature Patent literature

Patent Document 1 Japanese Patent Publication No. 8-507960

In recent years, dispersants have been required to have dispersibility for a wide variety of pigments. However, the dispersing agent containing polyethyleneimine as the main chain described in Patent Document 1 has a highly branched structure and is a three-dimensionally crowded structure. Therefore, in the adsorption site of the pigment when adsorbed to the pigment, The nitrogen atom of the amine does not sufficiently function, and depending on the type of the pigment, a sufficient dispersion effect cannot be obtained.

It is therefore an object of the present invention to provide a novel graft polymer which 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 has good dispersibility for a pigment, and has completed the present invention.

That is, the present invention provides a graft polymer characterized by having an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule, and an amine having two or more amine groups in the molecule. The epoxy-amine adduct obtained by the reaction of the compound (B) has a structure as a main chain and a polyester structure as a side chain.

The amine compound (B) preferably contains a compound selected from the group consisting of the following formula (b-1)

[wherein R ² and R ³ are the same or different and each of a straight chain, a branched chain, or a cyclic divalent aliphatic hydrocarbon group, or a linear or branched chain aliphatic hydrocarbon group; One or more kinds of aliphatic hydrocarbon groups are a divalent group which is bonded directly or via a linking group containing a hetero atom. q represents an integer of 0 or more].

The amine compound (B1) represented by the following formula (b-2)

[wherein R ⁴ and R ⁵ are the same or different and represent one or more of a linear, branched chain or cyclic divalent aliphatic hydrocarbon group or a linear or branched chain aliphatic hydrocarbon group and a cyclic group; A divalent group formed by linking one or more kinds of aliphatic hydrocarbon groups. r represents an integer of 1 or more].

The amine compound (B2) represented by the following formula (b-3)

[wherein R ⁶ and R ⁸ are the same or different and represent an alkylene group having 1 to 4 carbon atoms or an exoaryl group having 6 to 12 carbon atoms. s means 0 or 1. R ⁷ represents a monovalent organic group, an oxygen-containing atom group, a sulfur-containing atom group, a nitrogen-containing atom group, or a halogen atom. t represents an integer from 0 to 10].

An amine compound of at least one of the amine compounds (B3) represented.

The epoxy compound (A) is preferably a compound represented by the following formula (a).

[wherein X is a single bond or a divalent group having one or more atoms].

The polyester structure as a side chain is preferably a structure having a carboxyl terminal polyester obtained by ring-opening polymerization of ε-caprolactone.

The polyester structure as a side chain preferably has a structure of a carboxyl terminal polyester obtained by ring-opening copolymerization of ε-caprolactone and δ-valerolactone.

Further, the present invention provides a dispersing agent comprising the above graft polymer.

Further, a method for producing a graft polymer comprising an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine having two or more amine groups in the molecule is provided. The epoxy-amine adduct obtained by the reaction of the compound (B) is reacted with a carboxyl terminal polyester.

That is, the present invention relates to the following.

[1] A graft polymer comprising an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound having two or more amine groups in the molecule (B) The epoxy-amine adduct obtained by the reaction has a structure as a main chain and has a polyester structure as a side chain.

[2] The graft polymer according to [1], wherein the amine compound (B) has 2 to 1000 amine groups in the molecule.

[3] The graft polymer according to [1], wherein the amine compound (B) comprises a p-valent amine compound represented by the following formula (b).

R ¹ (NH ₂ ) _p (b)

[wherein R ¹ represents a p-valent organic group (organic residue) having a carbon atom at a bonding site represented by the formula and a nitrogen atom. p represents an integer of 2 or more].

[4] The graft polymer according to [3], wherein the amine compound (B) comprises a compound selected from the group consisting of the following formula (b-1)

[wherein R ² and R ³ are the same or different and represent a linear, branched chain, or cyclic divalent aliphatic hydrocarbon group, or a linear or branched chain aliphatic hydrocarbon group; One or more kinds of a group of a hydrocarbon group are a divalent group which is bonded directly or via a linking group containing a hetero atom. q represents an integer of 0 or more].

The amine compound (B1) represented by the following formula (b-2)

[wherein R ⁴ and R ⁵ are the same or different and represent one or more of a linear, branched chain or cyclic divalent aliphatic hydrocarbon group or a linear or branched chain aliphatic hydrocarbon group and a cyclic group; A divalent group formed by linking one or more kinds of aliphatic hydrocarbon groups. r represents an integer of 1 or more].

The amine compound (B2) represented by the following formula (b-3)

[wherein R ⁶ and R ⁸ are the same or different and represent an alkylene group having 1 to 4 carbon atoms or an exoaryl group having 6 to 12 carbon atoms. s means 0 or 1. R ⁷ represents a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent sulfur atom group, a monovalent nitrogen atom group, or a halogen atom. t represents an integer from 0 to 10].

The amine compound (B3) represented by the following formula (b-4)

[wherein R ⁹ represents a v-valent organic group having a carbon atom at a bonding site represented by the formula and an oxygen atom. R ¹⁰ represents a straight chain, a branched chain, or a cyclic divalent aliphatic hydrocarbon group, or a combination of one or more of a linear or branched aliphatic hydrocarbon group and a cyclic aliphatic hydrocarbon group. The divalent base. u represents an integer of 1 or more. v represents an integer of 3 or more].

An amine compound of at least one of the group of the amine compounds (B4) represented.

[5] The graft polymer according to [4], wherein the amine compound (B) comprises a compound selected from the group consisting of the aforementioned amine compound (B1) and the aforementioned amine compound (B2), and an amine compound of at least one of the group of the above amine compounds (B3).

[6] The graft polymer according to [4], wherein the amine compound (B) comprises the aforementioned amine compound (B1).

[7] The graft polymer according to [4], wherein the amine compound (B) comprises the aforementioned amine compound (B2).

[8] The graft polymer according to [4], wherein the amine compound (B) comprises the aforementioned amine compound (B1) and the aforementioned amine compound (B3).

[9] The graft polymer according to [4], wherein the amine compound (B) comprises the aforementioned amine compound (B2) and the aforementioned amine compound (B3).

[10] The graft polymer according to any one of [1] to [9] wherein the epoxy compound (A) has an alicyclic epoxy group selected from the group consisting of 2 to 6 in the molecule.

[11] The graft polymer according to any one of [1] to [10] wherein the alicyclic epoxy group of the epoxy compound (A) is an epoxycyclohexane group.

[12] The graft polymer according to [11], wherein the epoxy compound (A) is a compound represented by the following formula (a).

[wherein X represents a single bond or a divalent group having one or more atoms].

[13] The graft polymer according to [12], wherein the compound represented by the formula (a) is at least selected from the group consisting of compounds represented by the following formulas (a-1) to (a-10). 1 species.

[wherein l and m each represent an integer of 1 to 30, R' represents an alkylene group having 1 to 8 carbon atoms, and n1 to n6 each independently represent an integer of 1 to 30].

[14] The graft polymer according to [12], wherein the compound represented by the formula (a) contains the compound represented by the above formula (a-1).

[15] The graft polymer according to any one of [1] to [14] wherein the epoxy-amine adduct has a number average molecular weight of from 200 to 40,000.

[16] The graft polymer according to any one of [1] to [15] wherein the epoxy-amine adduct has a glass transition temperature (Tg) of -50 to 200 °C.

[17] The graft polymer according to any one of [1] to [16], which has a structure of a carboxyl terminal polyester obtained by ring-opening polymerization of a lactone represented by the following formula (1) Side chain polyester structure.

[wherein R ¹¹ represents an alkylene group having 1 to 10 carbon atoms which may be substituted].

[18] The graft polymer according to [17], which has a structure of a carboxyl terminal polyester obtained by ring-opening polymerization of ε-caprolactone as a polyester structure of the aforementioned side chain.

[19] The graft polymer according to [17], which has a structure of a carboxyl terminal polyester obtained by ring-opening copolymerization of ε-caprolactone and δ-valerolactone as a polyester structure of the aforementioned side chain .

[20] The graft polymer according to any one of [17] to [19] wherein the carboxyl terminal polyester can be obtained by an addition reaction of a lactone to a monocarboxylic acid.

[21] The graft polymer according to any one of [17] to [19] wherein the carboxyl terminal polyester can be obtained by an addition reaction of a lactone to a hydroxycarboxylic acid.

[22] The graft polymer according to any one of [17] to [21] wherein the carboxyl terminal polyester has an acid value of from 1 to 200.

[22] The graft polymer according to any one of [17] to [22] wherein the carboxyl terminal polyester has a weight average molecular weight of from 100 to 5,000.

[23] A dispersing agent comprising the graft polymer according to any one of [1] to [22].

[24] A pigment composition comprising the dispersant and pigment described in [23].

[25] The method for producing a graft polymer according to any one of [1] to [22] wherein an epoxy compound having two or more alicyclic epoxy groups in the molecule is used ( A) An epoxy-amine adduct obtained by a reaction with an amine compound (B) having two or more amine groups in the molecule, and reacting with a carboxyl terminal polyester.

The graft polymer of the present invention has good dispersibility for various pigments by having the above-described constitution.

[Graft polymer]

The graft polymer of the present invention has a structure of an epoxy-amine adduct as a main chain and a polyester structure as a side chain. The graft polymer of the present invention is preferably a graft polymer obtained by reacting an epoxy-amine adduct with a polyester having a carboxyl group (for example, a carboxyl terminal polyester described later).

The polyester structure of the graft polymer side chain of the present invention is preferably, for example, a polyester having a carboxyl group at the terminal (for example, a carboxyl terminal polyester described later), although it is not particularly limited. The graft polymer of the present invention may further have other side chains insofar as the effects of the present invention are not impaired.

{epoxy-amine adduct}

The epoxy-amine addition product is an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule (in the case of an epoxy compound (A), for example), and intramolecular An epoxy-amine adduct obtained by a reaction of two or more amine-based amine compounds (B) (in the case of abbreviated as "amine compound (B)"). The above epoxy-amine adduct can be obtained by reacting an alicyclic epoxy group possessed by the epoxy compound (A) with an amine group of the amine compound (B), preferably having 2 in the molecule. More than one amine based epoxy-amine adduct.

In the present specification, the term "amine group" means "NH ₂ (unsubstituted amino group)", and "-NH- group" does not include the unsubstituted amine group (-NH ₂ ).

(epoxy compound (A))

The epoxy compound (A) which is a raw material of the above-mentioned epoxy-amine adduct is a polyepoxy compound (alicyclic epoxy compound) having two or more alicyclic epoxy groups in its molecule. The epoxy compound (A) can be used singly or in combination of two or more.

The alicyclic epoxy group which the epoxy compound (A) has includes an epoxy group which constitutes two adjacent carbon atoms and an oxygen atom of an alicyclic ring (aliphatic ring). The alicyclic epoxy group is not particularly limited, and examples thereof include an aliphatic ring (fat) having a carbon number of 4 to 16 constituting a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring or the like. The adjacent two carbon atoms of the hydrocarbon ring) and the epoxy group of the oxygen atom. Among them, an epoxy group (hexylene oxide group) composed of two adjacent carbon atoms and oxygen atoms constituting the cyclohexane ring is particularly preferable.

The number of the alicyclic epoxy groups in the molecule of the epoxy compound (A) is not particularly limited, and is preferably 2 to 6, more preferably 2 to 5, still more preferably 2 Or three. When the number of alicyclic epoxy groups is more than 6, there is a tendency to cause high viscosity or hardening due to a crosslinked structure when synthesizing an amine adduct, and thus it is not expected.

The epoxy compound (A) is particularly preferably a compound (epoxy compound) represented by the following formula (a).

X of the above formula (a) represents a single bond or a linking group (a divalent group having one or more atoms). As the above-mentioned linking group, bivalent can be exemplified The hydrocarbon group, an alkenyl group which epoxidizes a part or all of the carbon-carbon double bond, a carbonyl group, an ether bond, an ester bond, a carbonate group, a decylamino group, a group in which two or more groups are bonded, and the like.

The epoxy compound (A) wherein X is a single bond in the above formula (a) includes 3,4,3',4'-diepoxybicyclohexane.

The divalent hydrocarbon group of X in the above formula (a) may, for example, be a linear or branched alkyl group having 1 to 18 carbon atoms or a divalent alicyclic hydrocarbon group. As a linear or branched chain alkyl group having a carbon number of 1 to 18, a methylene group, a methylmethylene group, a dimethylmethylene group, an exoethyl group, a propyl group, a trimethylene group, etc. can be exemplified. . The divalent alicyclic hydrocarbon group may, for example, be a 1,2-cyclopentyl group, a 1,3-cyclopentyl group, a cyclopentylene group, a 1,2-cyclohexylene group, a 1,3-cyclohexylene group, or the like. A divalent cycloalkylene group (including a cycloalkylene group) such as a 1,4-cyclohexylene group or a cyclohexylene group.

An alkenyl group which is an alkenyl group which is epoxidized to some or all of the above carbon-carbon double bonds in the above formula (a) (in the case of an "epoxidized alkenyl group"), a propylene group, a 1-butene butyl group, a 2-butenyl butyl group, a butadienyl group, a pentenyl group, a hexenylene group, a heptenyl group, a octenyl group, and the like, and a carbon number of 2 to 8 A chain or a branched chain extending an alkenyl group or the like. Particularly, as the above epoxidized alkenyl group, an alkenyl group in which all carbon-carbon double bonds are epoxidized is preferred, and more preferably an alkenyl group having 2 to 4 carbon atoms which is epoxidized by all carbon-carbon double bonds. .

The above-mentioned linking group of X in the above formula (a) is preferably a linking group containing an oxygen atom, and specific examples thereof include -CO-, -O-CO-O-, -CO-O-, -O-, -CO-NH-, an epoxidized extended alkenyl group; a group linking a plurality of such groups; a group linking one or two or more such groups and one or two divalent hydrocarbon groups. The divalent hydrocarbon group system can be exemplified above.

Representative examples of the alicyclic epoxy compound represented by the above formula (a) include compounds represented by the following formulas (a-1) to (a-10), and 2,2-bis (3,4-). Epoxycyclohexyl)propane (=2,2-bis(3,4-epoxycyclohexane-1-yl)propane), 1,2-bis(3,4-epoxycyclohexyl)ethane (= 1,2-bis(3,4-epoxycyclohex-1-yl)ethane), 2,3-bis(3,4-epoxycyclohexyl)oxirane (=1,2-epoxy) -1,2-bis(3,4-epoxycyclohex-1-yl)ethane), bis(3,4-epoxycyclohexylmethyl)ether, and the like. Further, l and m in the following formulae (a-5) and (a-7) each represent an integer of 1 to 30. R' in the following formula (a-5) represents an alkylene group having 1 to 8 carbon atoms, and examples thereof include a methylene group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. a linear or branched chain alkyl group such as a secondary butyl group, a pentyl group, a hexyl group, a heptyl group, and a octyl group. Among them, a linear or branched chain alkyl group having 1 to 3 carbon atoms such as a methylene group, an ethyl group, a propyl group and an isopropyl group is particularly preferable. N1 to n6 in the following formulas (a-9) and (a-10) each represent an integer of 1 to 30.

The epoxy compound (A) is preferably a compound represented by the above formula (a-1) from the viewpoint of reactivity with an amine compound [3,4-epoxycyclohexylmethyl (3, 4). - Epoxy) cyclohexane carboxylate; trade name "CELLOXIDE 2021P" (manufactured by Daicel Co., Ltd.), etc.].

(amine compound (B))

The amine compound (B) which is a raw material of the above-mentioned epoxy-amine adduct is a polyamine compound having two or more amine groups (-NH ₂ ; an unsubstituted amine group) in the molecule.

The number of amine groups of the amine compound (B) in the molecule may be two or more (for example, 2 to 1,000) from the viewpoint of dispersibility and polarity.

The amine compound (B) can be used singly or in combination of two or more. Since the more polar the amine group is, the less the amine group is, the lower the polarity is. Therefore, it is possible to design the best for pigments and substrates by using two or more kinds of amine compounds (for example, by using two or more kinds of amine compounds having different polarities). Structure and enhance dispersion. Therefore, it is preferred to combine two or more kinds of the amine compounds.

As the amine compound (B), a p-valent amine compound represented by the following formula (b) can be exemplified.

R ¹ (NH ₂ ) _p (b)

p of 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, and is preferably 2 to 6, more preferably 2 to 5, still more preferably 2 or 3.

R ^{1 of the} above formula (b) represents a p-valent organic group (organic residue) having a carbon atom at a bonding site of a nitrogen atom represented by the formula. Examples of the R ¹ system include a linear or branched chain p-valent aliphatic hydrocarbon group; a cyclic p-valent aliphatic hydrocarbon group; and a p-valent aromatic hydrocarbon group; and two or more such groups are directly or via a hetero atom. A p-valent group or the like in which a linking group (divalent group) is bonded (bonded).

The linear or branched chain p-valent aliphatic hydrocarbon group may, for example, be a linear or branched chain divalent aliphatic hydrocarbon group, a linear or branched chain trivalent aliphatic hydrocarbon group, a linear chain or a branched chain. A branched tetravalent aliphatic hydrocarbon group or the like. As the above-mentioned linear or branched chain divalent aliphatic hydrocarbon group, an alkyl group can be exemplified [for example, a methylene group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, Stretching octyl, hydrazine, hydrazine, undecyl, dodecyl, thirteen, tetradecyl, pentadecyl, hexadecyl, ten a linear or branched chain alkyl group (preferably a C _1-18 alkyl group) _{having a} carbon number of 1 to 30 (C _1-30 ) such as a _heptaalkyl group or an octadecyl group; [Alkyl group corresponding to the above alkylene group, for example, a straight-chain or branched chain-extended alkenyl group (preferably a C _2-18 extended alkenyl group) having 2 to 30 carbon atoms such as a vinyl group or a propylene group. ]Wait. As the linear or branched chain trivalent aliphatic hydrocarbon group, an alkane-triyl group such as a propane-triyl group, a 1,1,1-trimethylpropane-triyl group or the like having a carbon number of 3 to 30 can be exemplified. Chain or branched chain alkane- _triyl (preferably C _3-18 alkane- _triyl ), etc.]. As the linear or branched chain tetravalent aliphatic hydrocarbon group, a linear hydrocarbon having a carbon number of 4 to 30 such as a butane-tetrayl group or a 2,2-dimethylpropane-tetrayl group can be exemplified. Or a branched chain alkane-tetrayl group (preferably a C _4-18 alkane-tetrayl group) or the like].

The above-mentioned linear or branched chain p-valent aliphatic hydrocarbon group may also be a compound having various substituents (that is, at least 1 of the hydrogen atoms of the above-mentioned linear or branched chain p-valent aliphatic hydrocarbon group) Replaced by various substituents). Examples of the substituent include a halogen atom, an oxy group, a hydroxyl group, a substituted oxy group (e.g., an alkoxy group, an aryloxy group, an aralkyloxy group, a decyloxy group, etc.), a carboxyl group, a substituted oxycarbonyl group (alkoxycarbonyl group, aryl group). Oxycarbonyl, alkoxycarbonyl, etc.), substituted or unsubstituted aminemethanyl, cyano, nitro, substituted or unsubstituted amine, sulfo, heterocyclic, and the like. The above hydroxyl groups and carboxyl groups may also be protected by a protecting group commonly used in the field of organic synthesis (for example, a mercapto group, an alkoxycarbonyl group, an organic mercapto group, an alkoxyalkyl group, an oxacycloalkyl group, etc.).

As the above-mentioned substituted or unsubstituted aminomethyl fluorenyl group, an alkyl group having a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a secondary butyl group, a tertiary butyl group or the like, or an ethyl fluorenyl group can be exemplified. An amine formazan group such as a fluorenyl group such as a benzamidine group, or an unsubstituted amine methyl group or the like. Further, examples of the substituted or unsubstituted amino group include an alkyl group having a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, a secondary butyl group, a tertiary butyl group, or the like, or a vinyl group or a benzene group. An amine group such as a mercapto group such as a fluorenyl group or an unsubstituted amino group.

The hetero ring constituting the above heterocyclic group includes an aromatic heterocyclic ring and a non-aromatic hybrid ring. As such a ring, a hetero 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 a propylene oxide ring, a furan ring, a tetrahydrofuran ring, or the like) can be exemplified. 5-membered ring of azole ring, γ-butyrolactone ring, 6-membered ring of 4-oxa-4H-pyran ring, tetrahydropyran ring, morpholine ring, benzofuran ring, 4-oxa -4H- a condensed ring of an anthracene ring, a chromane ring, or the like, 3-oxatricyclo[4.3.1.1 ^4,8 ]unden-2-one ring, 3-oxatricyclo[4.2.1.0 ^4,8 ] a bridged ring such as an ind-2-one ring or the like), a heterocyclic ring containing a sulfur atom as a hetero atom (for example, a 5-membered ring such as a thiophene ring, a thiazole ring, or a thiadiazole ring, or 4-oxa-4H-thiopyran) a 6-membered ring such as a ring or a condensed ring such as a benzothiophene ring, or a heterocyclic ring containing a nitrogen atom as a hetero atom (for example, a pyrrole ring, a pyridyl ring, a pyrazole ring, an imidazole ring, or a triazole ring) Ring, pyridine ring, hydrazine Ring, pyrimidine ring, pyridyl Ring, piperidine ring, piperazine a 6-membered ring such as a ring, an anthracene ring, a porphyrin ring, a quinoline ring, an acridine ring, a naphthyridine ring, a quinazoline ring, a condensed ring such as an anthracene ring or the like). The heterocyclic group may be a heterocyclic group having a substituent, and examples of the substituent include, for example, a substituent which the linear or branched chain p-valent aliphatic hydrocarbon group may have. A monovalent hydrocarbon group such as an alkyl group (e.g., a C _1-4 alkyl group such as a methyl group or an ethyl group), an alkenyl group, a cycloalkyl group, a cycloalkenyl group, or an aryl group (e.g., a phenyl group or a naphthyl group). Further, the nitrogen atom of the heterocyclic ring constituting the above heterocyclic group may be a conventional protecting group (for example, alkoxy group, alkoxycarbonyl group, alkoxycarbonyl group, aralkoxycarbonyl group, aralkyl group, fluorenyl group, aromatic group). Protected by sulfonyl, alkylsulfonyl, 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. The cyclic divalent aliphatic hydrocarbon group may, for example, be a cycloalkyl group (for example, a cycloalkyl group such as a cyclopropyl group, a cyclopentene group, a cyclopentyl group or a cyclohexylene group), and a cycloalkyl group having a carbon number of 3 to 20 (more) Preferably, it is a C _3-15 cycloalkylene group, etc., a cycloalkenyl group [corresponding to a cycloalkenyl group of the above cycloalkyl group, for example, a cyclohexenyl group such as a cyclohexenylene group (more) Preferably, it is a C _3-15 cycloalkenyl group, etc.], a cycloalkylene group [a cycloalkylene group corresponding to the above cycloalkyl group, a cycloalkylene group having a carbon number of 3 to 20 such as a cyclopentylene group or a cyclohexylene group; a base (preferably a C _3-15 cycloalkylene group), etc., a cyclodienyl group [corresponding to a cyclodienyl group of the above cycloalkyl group, for example, a cyclopentadienyl group having a carbon number of 4 to 20 a cyclodienyl group (preferably a C _4-15 cyclodienyl group), etc., a divalent polycyclic hydrocarbon group [e.g., a spiro hydrocarbon (e.g., spiro[4.4]decane, spiro[4.5]decane, etc.)- a divalent snail hydrocarbon group of a dibasic group; a divalent ring condensed hydrocarbon group of a ring-collecting hydrocarbon (for example, a bicyclopropyl group)-diyl group; a bridged cyclic hydrocarbon (for example, a bicyclo[2.1.0]pentane, a bicyclo[3.2. 1] a divalent bridged cyclic hydrocarbon group such as octane, ornidyl, ornidyl, adamantane or the like, a dibasic group or the like]. Examples of the cyclic trivalent aliphatic hydrocarbon group include a cycloalkane-triyl group and a polycyclic hydrocarbon group-triyl group. The cyclovalent tetravalent aliphatic hydrocarbon group may, for example, be a cycloalkane-tetrayl group or a polycyclic hydrocarbon group-tetrayl group. The cyclic p-valent aliphatic hydrocarbon group may have a substituent, and examples of the substituent include, for example, a substituent which the linear or branched chain p-valent aliphatic hydrocarbon group may have. (e.g., a C _1-4 alkyl group such as a methyl group or an ethyl group), a monovalent hydrocarbon group such as an alkenyl group or an aryl group (e.g., a phenyl group or a naphthyl group).

Examples of the p-valent aromatic hydrocarbon group include a group in which p hydrogen atoms are removed from an aromatic hydrocarbon in a structural formula. Examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, 9-phenylanthracene, 9,10-diphenylanthracene, fused tetraphenyl, anthracene, anthracene, biphenyl, binaphthyl, and hydrazine. The p-valent aromatic hydrocarbon group may have a substituent, and examples of the substituent include, for example, a substituent which the linear or branched chain p-valent aliphatic hydrocarbon group may have. A monovalent hydrocarbon group such as a C _1-4 alkyl group such as a group or an ethyl group, an alkenyl group, a cycloalkyl group or a cycloalkenyl group.

As the above-mentioned hetero atom-containing linking group (divalent group), -CO-, -O-, -CO-O-, -O-CO-O-, -CO-NH-, -CO-NR ^a - can be exemplified. (Substituted amidino group: R ^a represents an alkyl group), -NH-, -NR ^b - (R ^b represents an alkyl group), -SO-, -SO ₂ - or the like contains a hetero atom (oxygen atom, nitrogen atom, sulfur) A divalent group such as an atom or the like, a divalent group linking a plurality of such groups, or the like.

More specifically, the amine compound (B) includes an amine compound (amine compound (B1)) represented by the following formula (b-1) and 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 particularly preferable to include at least one amine compound selected from the group consisting of an amine compound (B1), an amine compound (B2), and an amine compound (B3).

In the above formula (b-1), R ² and R ³ are the same or different and each represents a linear, branched chain, or cyclic divalent aliphatic hydrocarbon group, or directly or via a linking group containing a hetero atom (divalent A divalent group in which one or more linear or branched aliphatic hydrocarbon groups are bonded (bonded) to one or more cyclic aliphatic hydrocarbon groups. As the above-mentioned linear, branched chain or branched chain divalent aliphatic hydrocarbon group, a divalent aliphatic group which is a substituted or unsubstituted linear, branched chain or branched chain of R ¹ can be exemplified. Hydrocarbyl group. In addition, the divalent group in which one or more linear or branched chain aliphatic hydrocarbon groups and one or more cyclic aliphatic hydrocarbon groups are directly bonded to each other can be exemplified as the following formula (b-3). The structural formula shown is a group which removes the base formed by the two amine groups of the two terminals. In addition, examples of the linking group containing a hetero atom include a group which is a linking group containing a hetero atom of R ¹ .

In particular, the above-mentioned R ^{2 is} preferably a linear or branched chain divalent aliphatic hydrocarbon group, more preferably a linear or branched alkyl group having 2 to 6 carbon atoms, more preferably a carbon number. A linear or branched chain of 2 to 4 alkyl groups (for example, an ethyl group, a trimethylene group, a propyl group, etc., especially an ethyl group).

In particular, the above-mentioned R ^{3 is} preferably a linear or branched chain divalent aliphatic hydrocarbon group, more preferably a linear or branched alkyl group having 2 to 6 carbon atoms, more preferably a carbon number. A linear or branched chain of 2 to 4 alkyl groups (for example, an ethyl group, a trimethylene group, a propyl group, etc., especially an ethyl group). Further, when q is an integer of 2 or more, R ³ (a plurality of R ³ ) in the individual brackets may be the same or different. Further, when two or more kinds of R ³ are present, the addition form (polymerization form) of the structure in parentheses with q may be a random type or a block type.

In the above formula (b-1), q (the number of repetitions of the structural unit in parentheses with q) represents an integer of 0 or more. The q is, for example, preferably 0 to 100, more preferably 0 to 70, still more preferably 1 to 30, still more preferably 1 to 8, and particularly preferably 2 to 5. By setting q to 100 or less, the graft polymer of the present invention tends to further improve the dispersibility of the pigment.

Further, R ² and R ^{3 of the} above formula (b-1) may be the same or different. Among them, R ² and R ^{3 in the} above formula (b-1) are preferably the same, from the viewpoint that the carboxyl terminal polyester of the side chain is easily and uniformly distributed.

In particular, as the compound represented by the above formula (b-1), from the viewpoints of the reactivity of the epoxy compound (A) and the amine compound (B) and the dispersibility of the pigment of the graft polymer, it is preferred. It is ethylenediamine (EDA), diethylenetriamine (DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA), and more preferably triethylenetetramine. Further, as the compound represented by the above formula (b-1), a commercially available product can also be used.

R ^{4 in the} above formula (b-2) represents a linear, branched chain or cyclic divalent aliphatic hydrocarbon group, or one or more kinds of linear or branched chain aliphatic hydrocarbon groups and one or more kinds of cyclic groups. The divalent group formed by the aliphatic hydrocarbon group is bonded. As the above R ⁴ , a divalent group as the above R ² and R ³ can be exemplified.

In particular, as the above R ⁴ , a divalent aliphatic hydrocarbon group which is preferably a linear or branched chain, more preferably a linear or branched alkyl group having 2 to 6 carbon atoms, more preferably carbon. A linear chain of 2 to 4 linear alkyl groups (for example, an ethyl group, a trimethylene group, a propyl group, etc., especially a propyl group).

R ^{5 in the} above formula (b-2) represents a linear, branched chain or cyclic divalent aliphatic hydrocarbon group, or one or more kinds of linear or branched chain aliphatic hydrocarbon groups and one or more kinds of cyclic groups. The divalent group formed by the aliphatic hydrocarbon group is bonded. As the above R ⁵ , a divalent group as the above R ² and R ³ can be exemplified.

In particular, as the above R ⁵ , a linear or branched chain divalent aliphatic hydrocarbon group is preferred, and a linear or branched alkyl group having 2 to 6 carbon atoms is more preferred, and carbon is more preferred. A linear or branched chain alkyl group of 2 to 4 (e.g., an ethyl group, a trimethylene group, a propyl group, etc., especially a propyl group). Further, when r is an integer of 2 or more, R ⁵ (a plurality of R ⁵ ) in the individual brackets may be the same or different. Further, when two or more kinds of R ⁵ are present, the addition form (polymerization form) of the structure in the parentheses with r may be a random type or a block type.

R ⁴ and R ^{5 of the} above formula (b-2) may be the same or different.

r of the above formula (b-2) (number of repeats of the structural unit in parentheses with r) represents an integer of 1 or more. R is, for example, preferably from 1 to 100, more preferably from 1 to 70, still more preferably from 1 to 30. When r is 100 or less, the heat resistance of the graft polymer of the present invention is not impaired, and the dispersibility to the pigment tends to be improved. On the other hand, by setting r to 1 or more, the flexibility can be improved without impairing the dispersibility with respect to the pigment.

In the above, the compound represented by the above formula (b-2) is preferably an amine from the viewpoints of the reactivity of the epoxy compound (A) and the amine compound (B) and the dispersibility of the graft polymer to the pigment. The terminal (di-terminal amino group) polyethylene glycol, the amine terminal polypropylene glycol, the amine terminal polytetramethylene glycol, more preferably the amine terminal polypropylene glycol. In addition, as a compound represented by the above formula (b-2), a commercially available product (for example, a product name "JEFFAMINE" series manufactured by HUNTSMAN Co., Ltd.) can be used.

R ⁶ and R ^{8 in the} above formula (b-3) are the same or different and represent an alkylene group having 1 to 4 carbon atoms or an exoaryl group having 6 to 12 carbon atoms. Specific examples of R ⁶ and R ⁸ include an alkylene group having 1 to 4 carbon atoms (for example, a methylene group) and a carbon number of 6 to 12 as exemplified as R ¹ in the formula (b). (Removal of two hydrogen atoms from an aromatic hydrocarbon) or the like.

The s of the above formula (b-3) (the number of repetitions of the structural unit in parentheses with s) represents 0 or 1.

R ^{7 of the} above formula (b-3) represents a substituent on the cyclohexane ring represented by the formula, which is the same or different and represents a monovalent organic group, a monovalent oxygen atom-containing group, and a monovalent sulfur-containing atom. a monovalent nitrogen-containing atomic group or a halogen atom. Specific examples of R ⁷ include an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms, particularly a methyl group), a halogen atom (such as a fluorine atom or a chlorine atom), a hydroxyl group, a carboxyl group, an alkoxy group, and an alkenyloxy group. Aryloxy, aralkyloxy, decyloxy, decyl, alkylthio, arylthio, arylthio, aralkylthio, alkoxycarbonyl, aryloxycarbonyl, aralkoxycarbonyl, amine, nitro Mono or dialkylamino, decylamino, epoxy, epoxypropyl, decyl, cyano, isocyanate, isothiocyanate, aminomethyl sulfonyl, sulfo and the like. Further, t in the above formula (b-3) represents the number of substituents (R ⁷ ) on the cyclohexane ring represented by the formula, and represents an integer of 0 to 10 (preferably an integer of 1 to 5). When t of the above formula (b-3) is an integer of 2 or more, the individual R ⁷ may be the same or different.

More specifically, as a group formed by removing two amine groups of the two terminal groups from the structural formula represented by the above formula (b-3), 1,2-cyclohexylene-methylene group, 1,3- Stretching cyclohexyl-methylene, 1,4-cyclohexylene-methylene, cyclohexylene-methylene, 1,2-extension ring-extension ethyl, 1,3-extension ring-extension Base, 1,4-extended cyclohexyl-extended ethyl, cyclohexylene-extended ethyl, methylene-1,5,5-trimethyl-1,3-cyclohexylene (removed from isophorone diamine) a divalent group formed by two amine groups, such as a dicyclohexyl-alkylene group; a 1,2-extended cyclohexyl-phenylene group, a 1,3-cyclohexylene-phenylene group, a 1,4-stretch a cyclohexene-extended phenyl group such as a cyclohexyl-phenylene group; a methylene-1,2-alkylene-methylene group, a methylene-1,3-cyclohexylene-methylene group, Methylene-1,4-cyclohexylene-methylene-based alkylene-extended cyclohexyl-alkylene; methylene-1,2-extended cyclohexyl-phenylene, methylene-1,3-extension Cyclohexane-phenylene, methylene-1,4-cyclohexylene-phenylene-like alkylene-cyclo-extension-phenylene; phenylene-1,2-extension ring-phenylene Benzene-1,3-cyclohexylene-phenylene, benzene-1,4-cyclohexylene-phenylene, etc.

Among them, the compound represented by the above formula (b-3) is preferably different from the viewpoint of the reactivity of the epoxy compound (A) and the amine compound (B) and the dispersibility of the graft polymer to the pigment. Carbaryl diamine. In addition, as a compound represented by the above formula (b-3), a commercially available product (for example, Evonik Degussa Japan Co., Ltd., trade name "VESTAMIN IPD") can be used.

The u of the above formula (b-4) (the number of repeating structural units in parentheses in u) represents an integer of 1 or more, preferably 1 to 100, more preferably 1 to 70, still more preferably 1 to 30. Further, v of the above formula (b-4) (the number of structures in parentheses attached to v of R ⁹ ) represents an integer of 3 or more, preferably 3 to 6, more preferably 3 to 5, still more preferably It is 3 or 4.

R ^{10 in the} above formula (b-4) represents a linear, branched or cyclic divalent aliphatic hydrocarbon group, or one or more linear or branched aliphatic hydrocarbon groups and one or more cyclic groups. The divalent group formed by the aliphatic hydrocarbon group linkage can be exemplified as the divalent group of the above R ² and R ³ . Further, R ⁹ represents a v-valent organic group having a carbon atom at a bonding site of an oxygen atom represented by the formula, and for example, the same as R ¹ (for example, a linear or branched chain p-valent aliphatic hydrocarbon group, A cyclic p-valent aliphatic hydrocarbon group or the like).

As the compound represented by the above formula (b-4), a commercially available product (for example, a product name "JEFFAMINE" series manufactured by HUNTSMAN Co., Ltd.) can be used.

The amine compound (B) is preferably selected from the group consisting of an amine compound (B1), from the viewpoint of reactivity of the epoxy compound (A) and the amine compound (B), and dispersibility of the graft polymer to the pigment. The amine compound of at least one of the group of the amine compound (B2) and the amine compound (B3) is more preferably an amine compound (B1) or an amine compound only (B2) from the viewpoint of better dispersibility to the pigment. A combination of the amine compound (B1) and the amine compound (B3), or a combination of the amine compound (B2) and the amine compound (B3).

(Method for producing epoxy-amine adduct)

The above epoxy-amine adduct can be produced by reacting the epoxy compound (A) with the amine compound (B). More specifically, the above epoxy-amine adduct is produced by reacting an alicyclic epoxy group of the epoxy compound (A) with an amine group of the amine compound (B).

The epoxy compound (A) and the amine compound (B) which are raw materials of the above epoxy-amine adduct, the reactivity from the epoxy compound (A) and the amine compound (B), and the dispersion of the graft polymer to the pigment From the viewpoint of the nature, a compound represented by the formula (a) and the amine compound (B1), a compound represented by the formula (a), and an amine compound (B1) and an amine compound (B3) are preferred, and the formula (a) is preferred. The compound and the amine compound (B2), the compound represented by the formula (a), and the amine compound (B2) and the amine compound (B3) are represented. Further, the epoxy-amine addition product may be used in combination with an amine compound other than the epoxy compound (A) or the amine compound (B1) (B2) (B3) other than the compound represented by the formula (a).

Further, characteristics other than dispersibility can be obtained by a combination of the epoxy compound (A) and the amine compound (B). Specifically, for example, by reacting a compound represented by the formula (a) with an amine compound (B1) (more preferably, both of the amine compounds (B1) and (B3)), the resin is wettable, heat resistant, The handleability is good. Moreover, by reacting the compound represented by the formula (a), the amine compound (B2), and the amine compound (B3), heat resistance is improved.

In the reaction of the epoxy compound (A) and the amine compound (B), the epoxy equivalent of the epoxy compound (A) in the reaction raw material (for example, an equivalent of an alicyclic epoxy group) and the amine equivalent of the amine compound (B) (equivalent to the equivalent of the amine group) (the epoxy equivalent of the epoxy compound (A) / the amine equivalent of the amine compound (B)) is not particularly limited, but is preferably 0.3 to 3, more preferably 0.5 to 2, and further It is preferably 0.7 to 1.5, and particularly preferably 0.9 to 1.1. By setting the equivalent ratio to the above range, the residual amount of the epoxy compound (A) and the amine compound (B) can be reduced, and the physical properties of the pigment-dispersed resin are not easily lowered.

When a compound represented by the formula (a) is used in the reaction of the epoxy compound (A) and the amine compound (B), the compound represented by the formula (a) in the total amount (100% by weight) of the epoxy compound (A) The proportion is not particularly limited, but is preferably 80% by weight or more, more preferably 90% by weight or more, still more preferably 98 to 100% by weight. When the ratio of the compound represented by the formula (a) is 80% by weight or more, the reactivity of the epoxy compound (A) and the amine compound (B) tends to be further improved.

When the amine compound (B1) is used in the reaction of the epoxy compound (A) and the amine compound (B), the ratio of the amine compound (B1) in the total amount (100% by weight) of the amine compound (B) is not particularly limited. The limit is preferably 10% by weight or more (for example, 10 to 100% by weight), more preferably 20 to 100% by weight, and then more Preferably, it is 45 to 90% by weight, and particularly preferably 50 to 70% by weight. The dispersibility can be further improved by setting the ratio of the amine compound (B1) to the above range.

When the amine compound (B2) is used in the reaction of the epoxy compound (A) and the amine compound (B), the ratio of the amine compound (B2) in the total amount (100% by weight) of the amine compound (B) is not particularly limited. The limitation is preferably 10% by weight or more (e.g., 10 to 100% by weight), more preferably 20 to 100% by weight, still more preferably 30 to 90% by weight, particularly preferably 40 to 70% by weight. The flexibility can be improved by setting the ratio of the amine compound (B2) to the above range.

When the amine compound (B3) is used in the reaction of the epoxy compound (A) and the amine compound (B), the ratio of the amine compound (B3) in the total amount (100% by weight) of the amine compound (B) is not particularly limited. The limit is preferably from 10 to 70% by weight, more preferably from 20 to 60% by weight, still more preferably from 30 to 55% by weight. The heat resistance can be improved by setting the ratio of the amine compound (B3) to the above range.

The above reaction (reaction of the epoxy compound (A) and the amine compound (B)) can also be carried out in the presence of a solvent, or can also be carried out in the absence of a solvent (i.e., without a solvent). The solvent is not particularly limited, and it is preferred that the epoxy compound (A) and the amine compound (B) are uniformly dissolved or dispersed. Specific examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; and aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; and chloroform; a halogenated hydrocarbon such as dichloromethane or 1,2-dichloroethane; diethyl ether, dimethoxyethane, tetrahydrofuran, An ether such as an alkane; a ketone such as acetone, methyl ethyl ketone or methyl isobutyl ketone; an ester of methyl acetate, ethyl acetate, isopropyl acetate or butyl acetate; N, N- Amidoxime such as dimethylformamide or N,N-dimethylacetamide; a nitrile such as acetonitrile, propionitrile or benzonitrile; an alcohol such as methanol, ethanol, isopropanol or butanol ; dimethyl adenine and the like. Further, the above solvents may be used alone or in combination of two or more.

The amount of the solvent used in the above reaction is not particularly limited and can be appropriately set.

The reaction of the epoxy compound (A) and the amine compound (B) can be carried out, for example, by the method of the following [1], the method of the following [2], or the method of the following [3]. However, the method of carrying out the above reaction is not limited to the following methods [1] to [3].

[1] A method in which an epoxy compound (A) and an amine compound (B) are placed together in a reaction vessel, and if necessary, heated up to the reaction temperature to react the two.

[2] A method in which an amine compound (B) is successively added to a reaction vessel in which the epoxy compound (A) has been charged and heated to a reaction temperature as needed, and the two are reacted.

[3] A method in which an epoxy compound (A) is successively added to a reaction vessel in which the amine compound (B) has been charged and heated to a reaction temperature as needed, and the both are reacted.

In addition, the above-mentioned "sequential addition" means continuous addition (a form that is added at a fixed time) or intermittent addition (a form that is divided into a plurality of pieces to be added in a plurality of stages).

In the above methods [1] to [3], in particular, in the viewpoint of easy control of reaction heat or easy formation of an epoxy-amine adduct having a high molecular weight and a high glass transition temperature, the above [2] is preferred. Method or method of [3]. In addition, depending on the application, it is more appropriate to have a lower molecular weight of the epoxy-amine adduct. In this case, it is preferred to react by the method of the above [1].

The rate of addition of the amine compound (B) in the method of the above [2] is not particularly limited, and, for example, when it is 100 parts by weight based on the total amount of the amine compound (B) to be added, it can be from 0.1 to 20 parts by weight per minute. The range is set appropriately. Moreover, the rate of adding the epoxy compound (A) in the method of the above [3] is not particularly limited, and for example, when the total amount of the epoxy compound (A) to be added is 100 parts by weight, it can be from 0.1 to 20 The range of parts by weight per minute is appropriately set. Further, the amine compound (B) or the epoxy compound (A) to be added may be added in a direct state or may be added in a state of a solution or dispersion which has been dissolved or dispersed in a solvent.

Further, when two or more kinds of the amine compounds (B) are used, the method of the above [2] may be carried out by mixing the state of each of the amine compounds (B), or may be added in an unmixed state (individually). Further, in the latter case, each of the amine compounds (B) can be simultaneously dropped or can be successively dropped. The same applies to the method of the above [3] when the two or more epoxy compounds (A) are used.

The temperature (reaction temperature) of the above reaction is not particularly limited, but is preferably from 30 to 280 ° C, more preferably from 80 to 260 ° C, still more preferably from 120 to 250 ° C. When the reaction temperature is 30° C. or higher, the reaction rate is accelerated to further improve the productivity of the epoxy-amine adduct. On the other hand, when the reaction temperature is 280 ° C or lower, the pyrolysis of the epoxy compound (A) and the amine compound (B) can be suppressed, and the yield of the epoxy-amine adduct is further increased. Further, the above reaction temperature may be fixed at any time (substantially fixed) or may be changed stepwise or continuously.

The reaction time of the above reaction is not particularly limited, but is preferably 0.2 to 20 hours, more preferably 0.5 to 10 hours, still more preferably 2 to 8 hours. By setting the reaction time to 0.2 hours or longer, there is a tendency to further increase the yield of the epoxy-amine adduct. By setting the reaction time to 20 hours or less, there is a tendency to improve the productivity of the epoxy-amine adduct.

The above reaction can be carried out under normal pressure, under pressure, and under reduced pressure. The pressure in the reaction can also be fixed at any time (substantially fixed) or varied in sections or continuously. Further, the environment in which the above reaction is carried out is not particularly limited, and it can be carried out in any environment such as an inert gas (for example, nitrogen gas, argon gas, or the like) or air.

The above reaction is not particularly limited, and can be carried out by any of a batch method (batch type), a half batch method, and a continuous flow method.

An epoxy-amine adduct can be obtained by the above reaction (reaction of epoxy compound (A) and amine compound (B)). After the above reaction, the obtained epoxy-amine adduct is capable of being separated by well-known or conventional means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and the like. The separation means and the like are combined to separate and purify.

The number of the amine group (-NH ₂ ; unsubstituted amino group) of the epoxy-amine adduct is preferably 2 or more, more preferably 2 to 10, still more preferably 2 to 4. It is 2 or 3. Further, the epoxy-amine adduct is preferably substantially free of an epoxy group (particularly an alicyclic epoxy group derived from the epoxy compound (A)).

The position of the amine group (-NH ₂ ; unsubstituted amino group) of the above epoxy-amine adduct is not particularly limited, and is preferably at the molecular chain terminal of the epoxy-amine adduct (especially when it is linear) The epoxy-amine adduct is located at the molecular terminal of the epoxy-amine adduct.

The above epoxy-amine adduct is formed by reacting an alicyclic epoxy group of the epoxy compound (A) with an amine group (-NH ₂ ; an unsubstituted amine group) of the amine compound (B) as described above. . The above epoxy-amine adduct is presumed to be an -NH- group (substituted amine group) formed by the reaction of the above alicyclic epoxy group and an amine group (again, when the amine compound (B1) is used, The reactivity of the -NH- group (when q is 1 or more) which the amine compound (B1) has, and the alicyclic epoxy group of the epoxy compound (A) are insufficient, and generally the intramolecular-NH- group is not The state of the reaction remains. The number of -NH groups of the epoxy-amine adduct in the molecule is not particularly limited, but is preferably 1 to 200, more preferably 1 to 150, still more preferably 2 to 100. When the epoxy-amine adduct does not have a -NH- group, the reactivity with the carboxyl terminal polyester may be lowered. Further, the -NH- group number of the epoxy-amine adduct can be determined by, for example, using a standard polystyrene-equivalent molecular weight measured by a gel permeation chromatography (GPC) method. The number of the epoxy compound (A) and the amine compound (B) of the product is calculated.

Further, a compound which can be obtained by a reaction of an epoxy compound having a glycidyl group and an amine compound (B), and -NH formed by a reaction of a glycidyl group and an amine group (unsubstituted amino group) Since the reactivity of the group and the epoxy propyl group is very high, the -NH- group is not substantially left in general.

The number average molecular weight of the above epoxy-amine adduct is not particularly limited, and is preferably from 200 to 40,000, more preferably from 300 to 30,000, still more preferably from 400 to 20,000. When the number average molecular weight is 200 or more, the graft polymer tends to be more excellent in dispersibility to the pigment. Further, there is a tendency to improve the flexibility and toughness of the graft polymer. On the other hand, it can be good by setting the number average molecular weight to 40,000 or less. The solubility and handleability to the resin are maintained. Further, the number average molecular weight of the epoxy-amine adduct can be calculated using a standard polystyrene-equivalent molecular weight measured by a gel permeation chromatography (GPC) method.

The glass transition temperature (Tg) of the above 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. Good for 20~180°C. When the glass transition temperature is in the above range, the graft polymer tends to be more excellent in dispersibility to the pigment. Further, the Tg of the epoxy-amine adduct can be measured by, for example, differential scanning calorimetry (DSC), dynamic viscoelasticity measurement, or the like. More specifically, it can be determined by the method disclosed in the examples.

The epoxy-amine adduct has a constituent unit (structural unit) derived from the epoxy compound (A) and a constituent unit derived from the amine compound (B). Specifically, it preferably contains a constituent unit selected from the group consisting of a structural unit represented by the following formula (I) (structural unit; a constituent unit derived from the compound represented by the formula (a)), and a constituent unit represented by the following formula (II) ( a constituent unit derived from the amine compound (B1), a constituent unit represented by the following formula (III) (a constituent unit derived from the amine compound (B3)), and a constituent unit represented by the following formula (IV) (from the amine compound (B2) At least one of the group of constituent units). Further, it is preferred that the terminal has an amine group (-NH ₂ ).

[In the formula (I), X is the same as in the above formula (a)].

In the formula (II), R ² , R ³ and q are the same as those of the above formula (b-1).

In the formula (III), R ⁶ , R ⁷ , R ⁸ , s, and t are the same as those of the above formula (b-3).

In the formula (IV), R ⁴ , R ⁵ and r are the same as those of the above formula (b-2).

The addition form (polymerization form) of the epoxy compound (A) and the amine compound (B) may be any of an alternating type, a random type, and a block type.

Further, in the above formula (I), in the carbon atom constituting the cyclohexane ring, if the carbon atom to which X is bonded is a "1-position" carbon atom, the individual bonding in the constituent unit represented by the formula (I) The nitrogen atom (-NH-) bonding site derived from the constituent unit of the amine compound (B) in the cyclohexane ring is a carbon atom at the 3-position or a carbon atom at the 4-position of the cyclohexane ring. When the bonding position of the above nitrogen atom is a 3-position carbon atom, the hydroxyl group (-OH) bonded to the cyclohexane ring of the formula (I) is a 4-position carbon atom. Further, when the bonding position of the above nitrogen atom is the carbon atom at the 4-position of the cyclohexane ring, the hydroxyl group (-OH) bonded to the cyclohexane ring of the formula (I) is a carbon atom at the 3-position. The bonding positions (or the bonding positions of the hydroxyl groups) of the plurality of (two or more) cyclohexane rings in the above formula (I) may be the same or different. Further, when the carbon atom constituting the cyclohexane ring in the formula (I) is added to the above position number, the following formula is used.

{carboxy terminal polyester}

The carboxyl group-terminated polyester can be exemplified by a polyester having a structural unit formed by ring-opening polymerization of a lactone represented by the following formula (1) and having a carboxyl group at the terminal. The above carboxyl terminal polyester preferably has a carboxyl group at only one terminal of the polyester chain. The above lactone compounds may be used alone or in combination of two or more. Further, the terminal carboxyl group (at least one of the terminal carboxyl groups) can be reacted with an amine group, a hydroxyl group or the like of the epoxy-amine adduct (for example, an addition reaction, a graft polymerization, or the like).

R ^{11 in the} above formula (1) represents an alkylene group having a carbon number of 1 to 10 which may be substituted (linear alkyl group, preferably a linear alkyl group having 2 to 5 carbon atoms). Propyl, n-butyl, and hexyl)).

The substituent of the alkyl group having 1 to 10 carbon atoms of R ¹¹ is not particularly limited, and examples thereof include a halogen atom, an oxy group, a hydroxyl group, an alkyl group, an alkenyl group, and an aryl group (e.g., a phenyl group, a naphthyl group, etc.). . Among them, an alkyl group (e.g., 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, and examples thereof include ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, β-propiolactone, and γ. - Butyrolactone, 2-methylcaprolactone, 4-methylcaprolactone, and the like. Among them, ε-caprolactone and δ-valerolactone are preferred from the viewpoints of easy industrial availability, good reactivity for obtaining a ring-opening polymer, and further compatibility with a substrate. Or a combination thereof. That is, the graft polymer of the present invention, as the side chain polyester structure, preferably has a carboxyl terminal polyester obtained by ring-opening polymerization of ε-caprolactone or δ-valerolactone, or ε-hexene The structure of the carboxyl terminal polyester obtained by ring-opening copolymerization of lactone and δ-valerolactone.

The carboxyl group-terminated polyester is not particularly limited, and a polyester having a constituent unit represented by the following formula (2) and having a carboxyl group at the terminal can be exemplified.

W1 of the above formula (2) (the number of repeating structural units in parentheses in w1) represents an integer of 1 or more, preferably 1 to 100, more preferably 1 to 70, still more preferably 1 to 30. R ¹¹ is the above formula (2) and can be exemplified by the formula R (1) The same as in ^11. Particularly preferably, it is preferably an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group) as a substituent having 1 to 10 carbon atoms. (preferably a linear alkyl group having 2 to 5 carbon atoms). Further, when w1 is an integer of 2 or more, R ¹¹ (a plurality of R ¹¹ ) in the individual brackets may be the same or different. Further, when two or more kinds of R ¹¹ are present, the addition form (polymerization form) of the structure in parentheses attached to w1 may be a random type or a block type.

The method for synthesizing the above carboxyl terminal polyester is not particularly limited, and examples thereof include (i) an addition reaction of adding a lactone to a monocarboxylic acid; and (ii) an addition reaction of adding a lactone to a hydroxycarboxylic acid. (iii) a condensation reaction in which three components of a monocarboxylic acid, a hydroxycarboxylic acid, and a lactone are condensed; (iv) a condensation reaction using a lactone, a hydroxycarboxylic acid, a monocarboxylic acid, or the like in a dicarboxylic acid or a diol component; The condensation reaction; (v) a condensation reaction in which a polyvalent carboxylic acid having a divalent or higher value or an acid anhydride thereof, a polyhydric alcohol, a lactone, a hydroxycarboxylic acid or the like is condensed is used. Among them, the synthesis method of the above (i) or (ii) is preferred from the viewpoint of easily obtaining a carboxyl terminal polyester having a molecular weight as designed.

The monocarboxylic acid used for the synthesis of the carboxyl terminal polyester is not particularly limited, and examples thereof include acetic acid, propionic acid, butyric acid, oxalic acid, trimethylacetic acid, caproic acid, lauric acid, stearic acid, and A. An aliphatic carboxylic acid such as oxyacetic acid, an aromatic carboxylic acid such as abietic acid or phenylacetic acid, or the like. Among them, lauric acid is preferred from the viewpoint of easiness in industrial production and the dispersibility of the graft polymer to the pigment. The above-mentioned monocarboxylic acid type may be used alone or in combination of two or more.

The hydroxycarboxylic acid to be used for the synthesis of the carboxyl terminal polyester is not particularly limited, and examples thereof include a saturated or unsaturated aliphatic hydroxycarboxylic acid and an aromatic hydroxycarboxylic acid. Specific examples thereof include ricinoleic acid, 12-hydroxystearic acid, castor oil fatty acid (castor oil fatty acid condensate), hydrogenated castor oil fatty acid, δ-hydroxy gibberellic acid, ε-hydroxycaproic acid, and p-hydroxy ethoxylate. Carboxylic acid, 2-hydroxynaphthalene-3-carboxylic acid, 2-hydroxynaphthalene-6-carboxylic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylol oxalic acid, 2,2-di Hydroxymethyl valeric acid Fruit acid, tartaric acid, lactic acid, glycolic acid, gluconic acid, hydroxytrimethylacetic acid, 11-oxyhexadecanoic acid, 2-oxydodecanoic acid, salicylic acid or the like. Among them, ricinoleic acid, castor oil fatty acid or these condensates are preferred from the viewpoint of easiness of industrial production and the dispersibility of the graft polymer to the pigment. The above-mentioned hydroxymonocarboxylic acid can also be used singly or in combination of two or more.

The divalent or higher polyvalent carboxylic acid or an anhydride thereof used for the synthesis of the carboxyl terminal polyester is not particularly limited, and examples thereof include maleic acid, succinic acid, glutaric acid, fumaric acid, and Diacid, azelaic acid, sebacic acid, dodecanedioic acid, citric acid, meta-antimonic acid, p-nonanoic acid, hexahydrononanoic acid, methyl hexahydrophthalic acid, tetrahydrofurfuric acid, trimellitic acid, Methyltetrahydrofurfuric acid, or such anhydrides, and the like. The above-mentioned divalent or higher polyvalent carboxylic acid or an acid anhydride thereof may be used alone or in combination of two or more.

The polyol to be used for the synthesis of the carboxyl terminal polyester is not particularly limited, and examples thereof include a linear or branched chain polybasic aliphatic alcohol, an alicyclic polyol, and an aromatic polyol. Specific examples thereof include ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,3-butylene glycol, 1,4-butanediol, neopentyl glycol, and 3- Methyl pentanediol, 1,5-pentanediol, 1,6-hexanediol, trimethylolpropane, cyclohexanedimethanol, 1,4-dibenzyl alcohol, and the like. The above polyols may be used alone or in combination of two or more.

The synthesis of the carboxyl terminal polyester is preferably a catalyst (esterification catalyst) and/or a reaction solvent from the viewpoint of accelerating the reaction rate and improving the heat exchange ability. Further, from the viewpoint of suppressing coloration, it is preferably synthesized under an inert gas atmosphere such as nitrogen.

The esterification catalyst used for the synthesis of the carboxyl terminal polyester is not particularly limited, and examples thereof include organotin compounds such as tin octylate, dibutyltin oxide, dibutyltin laurate, and monobutyltin hydroxybutyl oxide. A tin compound such as tin or stannous chloride, tetrabutyl titanate, tetraethyl titanate or tetrapropyl titanate. Among them, tetrabutyl titanate is preferred from the viewpoint of cost and productivity. These esterification catalysts can also be used singly or in combination of two or more.

The amount of the esterification catalyst used (the total amount when two or more kinds of esterification catalysts are used) is not particularly limited, and is preferably from 0.1 to 3,000 ppm based on the total amount of the reaction raw materials. When the amount of the esterification catalyst used is 0.1 ppm or more, the ring-opening polymerization rate of the lactone is increased, and productivity is improved. Moreover, the coloring of the carboxyl terminal polyester can be suppressed by being 3000 ppm or less.

The reaction solvent used for the synthesis of the carboxyl terminal polyester can be exemplified by a dehydrating solvent such as toluene or xylene.

The temperature at which the carboxyl terminal polyester is synthesized can be appropriately selected by the kind of the raw material, the molar ratio, the type and amount of the catalyst, the type and amount of the solvent, and the like, and can be, for example, 120 to 220 ° C (preferably 160). ~210°C). The reaction rate is accelerated by setting the reaction temperature to 120 ° C or higher. In addition, it is possible to easily obtain a desired molecular weight of a carboxyl terminal polymerization by causing a side reaction (for example, decomposition of a lactone polymer, formation of a cyclic lactone dimer, etc.) by 220 ° C or less. ester. Further, the coloration of the carboxyl terminal polyester can be suppressed.

The above carboxyl terminal polyester can be, for example, placed in a reactor equipped with a dehydration tube and a condenser by inertia such as nitrogen. It is synthesized by reaction under a gas stream. When the reaction solvent is used, the reaction solvent may be removed by distillation or the like after completion of the reaction or may be directly used for the reaction with the epoxy-amine adduct.

The acid value of the above carboxyl terminal polyester is not particularly limited, and is, for example, preferably from 1 to 200. The viscosity of the carboxyl terminal polyester can be made into an appropriate range by setting the acid value to 1 or more. By setting the acid value to 200 or less, the molecular weight of the carboxyl terminal polyester is in an appropriate range, and a reciprocating layer is easily formed around the pigment to improve the dispersibility to the pigment. Further, the above acid value means an acid value measured in accordance with JIS K-1557.

The weight average molecular weight of the above carboxyl terminal polyester is not particularly limited, and is preferably from 100 to 5,000. By setting the weight average molecular weight to the above range, a sufficient three-dimensional back-repellent layer is formed around the pigment to improve the dispersibility, and the compatibility of the paint, the ink for vehicle, and the like with respect to the pigment is improved. Further, the above weight average molecular weight means a value measured by an NMR method.

[Method for Producing Grafted Polymer]

The graft polymer of the present invention can be obtained by, for example, the above epoxy-amine adduct and polyester obtained by the reaction of the epoxy compound (A) and the amine compound (B) (for example, the above carboxyl terminal polyester) Obtained by a reaction such as graft polymerization. More specifically, for example, an -OH group derived from a constituent unit of the epoxy compound (A) (for example, an -OH group of the formula (I), etc.), and an amine compound derived from an epoxy-amine adduct can be used ( The -NH- group of the structural unit of B) (for example, the -NH- group of the formula (II), (III), (IV), etc.), and the carboxyl terminal polyester (for example, terminal carboxyl group, etc.) are reacted to form a graft polymer. .

In the reaction of the above epoxy-amine adduct and the above-mentioned carboxyl terminal polyester, the total amount of the reaction raw materials (the total amount of the raw materials including the epoxy-amine adduct and the carboxyl terminal polyester) (100% by weight) is the above ring The proportion of the oxy-amine adduct is not particularly limited, but is preferably from 1 to 50% by weight, more preferably from 5 to 40% by weight, still more preferably from 10 to 30% by weight. By setting the ratio of the epoxy-amine adduct to the above range, the reaction efficiency of the epoxy-amine adduct and the carboxyl terminal polyester is improved.

Further, when two or more kinds of epoxy-amine adducts are used, it is preferred that the total amount (total amount) of all the epoxy-amine adducts is within the above range.

In the reaction of the above epoxy-amine adduct and the above-mentioned carboxyl terminal polyester, the total amount of the reaction raw materials (the total amount of the raw materials including the epoxy-amine adduct and the carboxyl terminal polyester) (100% by weight) The proportion of the carboxyl terminal polyester is not particularly limited, and is preferably from 50 to 99% by weight, more preferably from 60 to 95% by weight, still more preferably from 70 to 90% by weight. By setting the ratio of the carboxyl terminal polyester to the above range, the reaction efficiency of the epoxy-amine adduct and the carboxyl terminal polyester is improved.

Further, when two or more kinds of carboxyl terminal polyesters are used, it is preferred that the total amount of all carboxyl terminal polyesters is within the above range.

The ratio of the carboxyl-terminated polyester of the epoxy-amine adduct to the carboxyl-terminated polyester (weight ratio, carboxyl terminal polyester/epoxy-amine adduct) There is no particular limitation, and it is preferably 1.01 to 10.00, more preferably 1.50 to 8.00, still more preferably 2.00 to 6.00. By setting the ratio to the above range, the reaction efficiency of the epoxy-amine adduct and the carboxyl terminal polyester is improved.

The reaction of the above epoxy-amine adduct with the above carboxyl terminal polyester can also be carried out in the presence of a solvent or in the absence of a solvent (i.e., without a solvent). The solvent is not particularly limited, and examples thereof include the solvents exemplified for the reaction of the epoxy compound (A) and the amine compound (B). These solvents can also be used singly or in combination of two or more. The amount of the solvent to be used is not particularly limited and can be appropriately set.

In the reaction between the epoxy-amine adduct and the carboxyl terminal polyester, for example, a polymerization initiator, a catalyst, a solvent, an antioxidant, or the like can be used.

The reaction of the above epoxy-amine adduct and the above-mentioned carboxyl terminal polyester can be carried out by a known or customary method, and is not particularly limited, and for example, an epoxy-amine adduct and a carboxyl terminal polyester can also be used together. The reaction vessel is placed in the reaction or it is also possible to first react the epoxy-amine adduct and the carboxyl terminal polyester into a reaction vessel and then add the other (for example, the above-mentioned sequential addition). Among them, in particular, in order to obtain a graft polymer having a uniform composition, it is preferred to first put a carboxyl terminal polyester into a reaction vessel, and to put an epoxy-amine adduct together to carry out a reaction.

The temperature (reaction temperature) of the above reaction is not particularly limited, and can be suitably selected, for example, from 0 to 200 ° C (for example, from 15 to 150 ° C). Further, the time (reaction time) for carrying out the above reaction is not particularly limited, and for example, it can be appropriately selected from the range of 0.2 to 20 hours (for example, 1 to 10 hours).

The above reaction can be carried out arbitrarily under normal pressure, under pressure, and under reduced pressure. Moreover, the environment in which the above reaction is carried out is not particularly limited. It can also be carried out in any environment such as an inert gas (for example, nitrogen, argon, etc.) or air. Further, the above reaction may or may not be carried out while stirring.

The above reaction can be carried out by any one of a batch method (batch type), a half batch method, and a continuous circulation method without any particular limitation.

After the above reaction, the graft polymer of the present invention can be separated or separated by a well-known or conventional separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, and the like. Means, etc. to separate and refine.

In the graft polymer of the present invention, an amine group in an epoxy-amine adduct (for example, an epoxy-amine adduct second terminal) is removed by a reaction with a polyester (for example, a carboxyl terminal polyester or the like). The case of the amine group, etc.). The graft polymer of the present invention may also have an amine group (which may also be an amine group-containing graft polymer) or may have no amine group.

Further, the graft polymer of the present invention may have a 2-stage amine group (for example, an -NH- group or the like) in a main chain (for example, a structure of an epoxy-amine adduct). The number of the second-stage amine groups is not particularly limited, and can be 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. When having a plurality of side chains, the structures of the individual side chains may be the same or different. The polyester structure of the side chain is not particularly limited, and is preferably a structure of the above carboxyl terminal polyester. Among them, a polyester structure represented by the following formula (3) or (4) is particularly preferable.

R in the above formula (3) and (4) the lines ¹¹ of the same group can be exemplified by the formula (1) R ^11. Particularly preferably, it is preferably an alkyl group having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group) as a substituent having 1 to 10 carbon atoms. (preferably a linear alkyl group having 2 to 5 carbon atoms).

R ^{11 of the} above formulas (3) and (4) may be the same or different. R ^{11 of the} above formulas (3) and (4) may be the same as or different from R ^{11 of the} above formula (1) and/or (2).

The R ¹² of the above formulae (3) and (4) may be a group derived from the above monocarboxylic acid, the above-mentioned hydroxycarboxylic acid or the above polyvalent carboxylic acid used for the synthesis of the carboxyl terminal polyester. R ^{12 of the} above formulas (3) and (4) may be the same or different.

W2 of the above formula (3) (the number of repeating structural units in parentheses with w2) and w3 of the above formula (4) (number of repeating structural units in parentheses with w3) represent an integer of 1 or more, preferably 1 ~100, more preferably 1~70, and even more preferably 1~30. Further, when w2 and/or w3 is an integer of 2 or more, R ¹¹ (a plurality of R ¹¹ ) in the individual brackets may be the same or different. W2 and w3 may also be the same or different. Further, when two or more kinds of R ¹¹ are present, the addition form (polymerization form) of the structure in parentheses with w2 or w3 may be a random type or a block type.

The use of the graft polymer of the present invention is not particularly limited, and a dispersant as a pigment, a dispersant of another inorganic filler, or the like can be used.

The graft polymer of the present invention has an epoxy compound (A) having two or more alicyclic epoxy groups in the main chain of the molecule, and an amine compound (B) having two or more amine groups in the molecule. By reacting the obtained epoxy-amine adduct structure, it is possible to change the main chain structure into various types by the kind of the epoxy compound and the amine compound, thereby increasing the degree of freedom of the main chain structure, and as a graft polymerization. The whole thing enhances the dispersibility of the pigment. In addition, it is considered that since the constituent unit portion derived from the epoxy compound (A) in the main chain and the constituent unit portion derived from the amine compound (B) have different properties, the graft polymer as a whole is further improved. Dispersibility. In addition, since the graft polymer of the present invention can change the structure of the amine adduct moiety in the main chain as long as the amine compound (B) is changed (for example, if the combination and ratio of the amine compound (B) are changed), it is considered to be easy. Adjust the wettability and adhesion to various substrates. When a polyester structure having a carboxyl terminal polyester is used as a side chain, a stereoscopic back-draw layer is formed around the pigment to further enhance the dispersibility. Further, the graft polymer of the present invention is also excellent in storage stability and can be dispersed in a short period of time.

[Dispersant]

The dispersant of the present invention comprises the graft polymer of the present invention. The dispersing agent of the present invention may also be only the graft polymer of the present invention or may also contain other dispersing compounds. Among them, from the viewpoint of good dispersibility to the pigment, it is preferably only the graft polymer of the present invention.

The other dispersible compound is not particularly limited, and examples thereof include an anionic compound such as a sulfate, a sulfonate or a phosphate, a cationic compound such as an aliphatic amine salt, a nonionic compound, and a polymer compound.

The proportion of the graft polymer of the present invention in the dispersant of the present invention is not particularly limited, and is preferably from 30 to 100% by weight, more preferably from 40 to 95% by weight, based on the total amount of the dispersing agent (100% by weight). It is preferably 50 to 90% by weight.

The dispersing agent of the present invention may further comprise a solvent, a leveling agent, an antifoaming agent, a surfactant, a flame retardant, an antioxidant, a preservative, and the like.

[Pigment composition]

A pigment composition (pigment dispersion composition) can be obtained by blending (mixing) the dispersant and pigment of the present invention. That is, the above pigment composition contains at least the graft polymer and pigment of the present invention. The above pigment composition may also contain a dispersing agent other than the dispersing agent of the present invention.

The pigment is not particularly limited, and examples thereof include inorganic pigments such as titanium oxide, zinc oxide, cadmium sulfide, yellow iron oxide, red iron oxide, chrome yellow, and carbon black, indigo, insoluble azo pigment, and azo. Lake pigment, condensed polycyclic pigment (threne, indigo, lanthanum, ketone, ketone, two , quinacridone, isoindolinone, diketopyrrolopyrrole pigments, and the like.

The pigment composition may also include a coating resin, a solvent, a leveling agent, an antifoaming agent, a surfactant, a flame retardant, an antioxidant, a preservative, and the like. The coating resin is not particularly limited and can Examples include alkyd resins, oil-free alkyd resins, acrylic resins, urethane resins, and the like.

The content of the graft polymer of the present invention in the above pigment composition is not particularly limited, and is preferably from 1 to 50% by weight, more preferably from 2 to 40% by weight, based on the total amount of the pigment composition (100% by weight). It is preferably from 3 to 30% by weight. When the content of the graft polymer is in the above range, the dispersibility to the pigment tends to be improved.

The method for producing the pigment composition is not particularly limited, and it can be produced by stirring and mixing the respective components such as the graft polymer and the pigment of the present invention at a predetermined ratio.

In the above pigment composition, since the graft polymer of the present invention reacts with the pigment, the graft polymer in the composition is coagulated and is not easily crystallized.

As described above, the graft polymer of the present invention exerts good dispersibility (dispersion effect) for various pigments. Therefore, the graft polymer of the present invention and the composition containing the same (for example, the above-mentioned dispersant, pigment composition, etc.) can be preferably used for a fine color separation filter such as a liquid crystal panel, and can be used for a composition for a liquid crystal panel such as a thin film transistor side substrate of a liquid crystal panel; a composition for forming a black matrix of an optical color filter (a composition for forming a black matrix); and a colored composition for forming a color filter; An oily black content dispersion for writing ink for oily black pigment writing ink; a pigment dispersion containing coloring pigment or carbon black (for example, a pigment dispersant for coating); a dispersion containing carbon black and black photosensitivity Composition (eg photocurable coating, photohardening) An adhesive agent, a printing plate, a black photosensitive composition used for a photoresist for printed wiring boards, etc.; an active energy ray-curable inkjet ink using carbon black; and a non-aqueous inkjet ink (non-aqueous inkjet) a composition: a conductive material dispersion (for example, an electrode paste for a battery or the like, a conductive material dispersion for a conductive material coated with an active material); and an electrophoretic dispersion containing black electrophoretic particles (for example, an electrophoretic dispersion for an image display medium or an image display device) Liquid); a coloring composition containing a black color material (for example, titanium black) (for example, a paint, a plastic material, an ink, or a colored composition for an electronic part material). It is possible to obtain, for example, a color filter, an electrode substrate, a liquid crystal display device (liquid crystal panel), and an oily black pigment writing ink by using the graft polymer of the present invention and a composition containing the same in such a mode. , writing materials, coatings (such as solid coatings, metallic coatings), photocurable coatings, photocurable adhesives, printing plates, printed wiring boards, inkjet inks (eg, active energy ray-curable inkjet inks, non-aqueous systems) Inkjet ink, electrode paste, conductive material coated active material, battery (for example, lithium ion battery) image display medium and image display device (such as electronic paper) using black electrophoretic particles, plastic material, printing ink, thermal transfer Various items such as ink, light-shielding film, electric capillary display device, electrowetting display device, electrochromic display device, optical element (for example, optical shutter, optical head device, liquid optical lens). However, the use of the graft polymer of the present invention and the composition comprising the same is not limited thereto.

[Examples]

The invention is further illustrated by the following examples, but the invention is not limited thereto.

[Manufacturing Example 1]

In a 2 L reactor equipped with a condenser, a nitrogen gas introduction tube, a stirrer, a thermometer, and a dehydration tube, 171 g of lauric acid (manufactured by Acidchem Co., Ltd.), 829 g of ε-caprolactone, and 0.1 g of tetrabutyl titanate were placed under a nitrogen stream. The reaction was carried out at 200 ° C, and heating was carried out until the residual caprolactone became 1% or less to synthesize a carboxyl terminal polyester. The acid value of the obtained carboxyl terminal polyester 1 (side chain 1) was 48 KOH mg/g.

[Manufacturing Example 2]

In a 2L reactor equipped with a condenser, a nitrogen inlet tube, a stirrer, a thermometer and a dehydration tube, 723 g of ricinoleic acid, 277 g of ε-caprolactone and 2 g of tetrabutyl titanate were placed under a nitrogen stream until the acid value of the reaction mixture The carboxyl terminal polyester 2 (side chain 2, random copolymer) was synthesized by reaching 50.5 mgKOH/g and stirring at 170 ° C for 6 hours under a nitrogen atmosphere.

[Manufacturing Example 3]

747g condensed ricinoleic acid (trade name "HSC60D", manufactured by Fengguo Oil Co., Ltd.), 183g ε-caprolactone and 0.1g in a 2L reactor equipped with a condenser, a nitrogen gas introduction tube, a stirrer, a thermometer and a dehydration tube Tetrabutyl titanate was placed, reacted at 150 ° C under a nitrogen stream, and heated until the residual caprolactone became 1% or less to synthesize carboxyl terminal polyester 3 (side chain 3, block copolymer). The acid value of the obtained carboxyl terminal polyester 3 was 48 KOHmg/g.

[Manufacturing Example 4]

372.0 g of an amine compound (triethylethylenetetramine (trade name "TETA", manufactured by HUNTSMAN)) was placed in a 1 L stainless steel reaction vessel, and 627.6 g of epoxidized gas was subjected to a nitrogen atmosphere at 160 ° C for 60 minutes. The compound (3,4-epoxycyclohexylmethyl (3,4-epoxy)cyclohexanecarboxylate (trade name "CELLOXIDE 2021P", manufactured by Daicel Co., Ltd.) was dropped thereinto. Then, the reaction was carried out by stirring at 200 ° C for 3 hours and then at 220 ° C for 2 hours to obtain an epoxy-amine adduct.

After standing to cool, it was poured from a reaction container onto a release paper at a stage where the content had fluidity (130 to 150 ° C), and after further cooling and solidifying, 990 g of an epoxy-amine adduct 1 was obtained by pulverization ( Amine adduct 1, main chain 1).

[Manufacturing Example 5]

In a 1 L stainless steel reaction vessel, 228.0 g of an amine compound (mixed triethylamine (trade name "TETA", manufactured by HUNTSMAN) and 171.0 g of isophorone diamine (trade name "VESTAMIN IPD", Evonik) were added. Degussa Japan Co., Ltd.)), put 632.5g of epoxy compound (3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane at 160 ° C under nitrogen for 60 minutes. A carboxylic acid ester (trade name "CELLOXIDE 2021P", manufactured by Daicel Co., Ltd.) was dropped therein. Then, the reaction was carried out by stirring at 200 ° C for 3 hours and then at 220 ° C for 2 hours to obtain an epoxy-amine adduct.

After standing to cool, it was poured from a reaction container onto a release paper at a stage where the content had fluidity (130 to 150 ° C), and after further cooling and solidifying, 1000 g of an epoxy-amine adduct 2 was obtained by pulverization ( Amine adduct 2, main chain 2).

[Manufacturing Example 6]

In a 1 L stainless steel reaction vessel, 390.0 g of an amine compound (amine terminal polypropylene glycol (trade name "JFFFAMINE D-230", HUNTSMAN) Made by the company)), 409.8g of epoxy compound (3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexane carboxylate (trade name) at 160 ° C under nitrogen for 60 minutes "CELLOXIDE 2021P", manufactured by Daicel Co., Ltd.)) was dropped into it. Then, the reaction was carried out by stirring at 200 ° C for 3 hours and then at 220 ° C for 2 hours to obtain an epoxy-amine adduct.

After standing to cool, it was poured from a reaction container onto a release paper at a stage where the content had fluidity (130 to 150 ° C), and after further cooling and solidifying, 790 g of an epoxy-amine adduct 3 was obtained by pulverization ( Amine adduct 3, main chain 3).

[Manufacturing Example 7]

In a 1 L stainless steel reaction vessel, an amine compound (120.0 g of amine-terminated polypropylene glycol (trade name "JEFFAMINE D-230", manufactured by HUNTSMAN) and 120.0 g of isophorone diamine (trade name "VESTAMIN IPD", Evonik) were used. Degussa Japan Co., Ltd.)) and 299.5g of epoxy compound (3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate (trade name "CELLOXIDE 2021P", limited by Daicel) The product was placed in a nitrogen atmosphere and stirred at 160 ° C for 2 hours to obtain an epoxy-amine adduct.

After standing to cool, it was poured from a reaction container onto a release paper at a stage where the content had fluidity (130 to 150 ° C), and after further cooling and solidifying, 530 g of an epoxy-amine adduct 4 was obtained by pulverization ( Amine adduct 4, main chain 4).

[Manufacturing Example 8]

In a 2 L reactor equipped with a condenser, a nitrogen gas introduction tube, a stirrer, a thermometer, and a dehydration tube, 171 g of lauric acid (manufactured by Acidchem Co., Ltd.) was placed. 441 g of ε-caprolactone, 387 g of δ-valerolactone, and 0.1 g of tetrabutyl titanate were reacted at 200 ° C under a nitrogen stream, and heated until the residual caprolactone and valerolactone became 1% or less to synthesize a carboxyl terminal polyester. The acid value of the obtained carboxyl terminal polyester 4 (side chain 4, random copolymer) was 48 KOHmg/g.

[Example 1]

In a 1000 mL reactor equipped with a condenser, a nitrogen inlet tube, a stirrer, and a thermometer, 856 parts of carboxyl terminated polyester 1 (side chain 1) were placed, followed by 144 parts of epoxy-amine adduct 1 at 120 ° C. reaction. The reaction was terminated 8 hours after the start of the reaction to obtain a graft polymer.

[Examples 2 to 13]

The graft polymer was prepared by the same procedure as in Example 1 in the composition shown in Table 1.

[assessment]

For the samples obtained in the examples, the following evaluations were carried out.

(acid price)

The acid value was measured in accordance with JIS K-1557.

(pigment dispersion)

[Preparation of pigment paste by pigment dispersant]

The graft polymer obtained in Example 1 or a commercially available pigment dispersant (Solsperse 24000, manufactured by Lubrizol Co., Ltd.) was blended as shown in Table 2. The pigment and the solvent are blended in a mixed amount, further added to the glass beads, dispersed in a dispersing machine (manufactured by Red Devil Co., Ltd.), and then the glass beads are removed by filtration to obtain a pigment which disperses the pigment by the pigment dispersing agent (graft polymer). Disperse paste.

The fluidity of the pigment dispersion paste was evaluated by visual observation from the obtained pigment dispersion paste by the following criteria. The evaluation results are shown in Table 2. Further, the numerical values in Table 2 represent parts by weight.

The filtration state and the viscosity of the filtrate when the pigment dispersion paste was prepared were observed, and the glass beads were filtered, and those having good fluidity were evaluated as "dispersed well", and those who could not filter the glass beads were evaluated as "undispersible".

Claims (7)

A graft polymer characterized by having an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amine groups in the molecule The obtained epoxy-amine adduct structure has a structure as a main chain and a polyester structure as a side chain. The graft polymer of claim 1, wherein the amine compound (B) comprises an amine compound (B2) selected from the group consisting of the amine compound (B1) represented by the following formula (b-1) and represented by the following formula (b-2) And at least one amine compound in the group of the amine compound (B3) represented by the following formula (b-3); [wherein R ² and R ³ may be the same or different and represent a linear, branched chain, or cyclic divalent aliphatic hydrocarbon group, or one or more linear or branched chain aliphatic hydrocarbon groups and 1 The above-mentioned cyclic aliphatic hydrocarbon group is a divalent group directly or via a linking group containing a hetero atom; q represents an integer of 0 or more]; [wherein R ⁴ and R ⁵ may be the same or different and each represents a linear, branched chain, or cyclic divalent aliphatic hydrocarbon group, or one or more linear or branched chain aliphatic hydrocarbon groups and one type a divalent group formed by linking the above cyclic aliphatic hydrocarbon group; r represents an integer of 1 or more]; Wherein R ⁶ and R ⁸ may be the same or different and represent an alkylene group having 1 to 4 carbon atoms or an extended aryl group having 6 to 12 carbon atoms; s represents 0 or 1; and R ⁷ represents a monovalent organic group; The valence includes an oxygen atom group, a monovalent sulfur atom group, a monovalent nitrogen atom group, or a halogen atom; t represents an integer of 0 to 10]. The graft polymer of claim 1 or 2, wherein the epoxy compound (A) is a compound represented by the following formula (a); [wherein, X represents a single bond or a divalent group having one or more atoms]. The graft polymer according to any one of claims 1 to 3, which has a carboxyl terminal polyester structure obtained by ring-opening polymerization of ε-caprolactone as a polyester structure of the side chain. The graft polymer according to any one of claims 1 to 3, which has a carboxyl terminal polyester structure obtained by ring-opening copolymerization of ε-caprolactone and δ-valerolactone as a polyester structure of the side chain . A dispersing agent comprising the graft polymer of any one of claims 1 to 5. A method for producing a graft polymer according to any one of claims 1 to 5, which comprises an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule, and an intramolecular molecule The epoxy-amine adduct obtained by the reaction of the amine compound (B) having two or more amine groups is reacted with a carboxyl terminal polyester.