WO2016017680A1 - 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 production method thereof

The present invention relates to a graft polymer and a method for producing the same. This application claims the priority of Japanese Patent Application No. 2014-155844 for which it applied to Japan on July 31, 2014, and uses the content here.

In the fields of paints and inks, when dispersing pigments, a dispersant may be used for the purpose of improving dispersibility and storage stability and shortening the dispersion time. As such a dispersant, for example, a dispersant obtained by graft-polymerizing a carboxylic acid group-terminated polycaprolactone to polyethyleneimine is known (Patent Document 1).

Japanese National Patent Publication No. 8-507960

In recent years, dispersants are required to have dispersibility for a wide variety of pigments. However, since the dispersant having polyethyleneimine as the main chain described in Patent Document 1 has a structure in which polyethyleneimine is highly branched and has a three-dimensionally crowded structure, when adsorbing to the pigment, In some cases, the nitrogen atom of the imine cannot sufficiently act on the adsorption site, and a sufficient dispersion effect cannot be obtained depending on the pigment.

Therefore, an object of the present invention is to provide a novel graft polymer that is excellent in dispersibility for a wide variety of pigments.

The present inventors have found that a graft polymer having a specific epoxy-amine adduct as a main chain and a polyester structure as a side chain is excellent in dispersibility to a pigment, and has completed the present invention.

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

［式中、Ｒ²及びＲ³は、同一又は異なって、直鎖、分岐鎖、若しくは環状の二価の脂肪族炭化水素基、又は、直鎖若しくは分岐鎖状の脂肪族炭化水素基の１以上と環状の脂肪族炭化水素基の１以上とが直接又はヘテロ原子を含む連結基を介して連結した二価の基を示す。ｑは、０又は１以上の整数を示す。］
で表されるアミン化合物（Ｂ１）、下記式（ｂ－２）

［式中、Ｒ⁴及びＲ⁵は、同一又は異なって、直鎖、分岐鎖、若しくは環状の二価の脂肪族炭化水素基、又は、直鎖若しくは分岐鎖状の脂肪族炭化水素基の１以上と環状の脂肪族炭化水素基の１以上とが連結して形成される二価の基を示す。ｒは、１以上の整数を示す。］
で表されるアミン化合物（Ｂ２）、及び下記式（ｂ－３）

［式中、Ｒ⁶及びＲ⁸は、同一又は異なって、炭素数１～４のアルキレン基、又は炭素数６～１２のアリーレン基を示す。ｓは、０又は１を示す。Ｒ⁷は、一価の有機基、酸素原子含有基、硫黄原子含有基、窒素原子含有基、又はハロゲン原子を示す。ｔは、０～１０の整数を示す。］
で表されるアミン化合物（Ｂ３）からなる群より選択される少なくとも一種のアミン化合物を含むことが好ましい。 The amine compound (B) is represented by the following formula (b-1)

[Wherein, R ² and R ³ are the same or different and are each a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic hydrocarbon group. A divalent group in which the above and one or more cyclic aliphatic hydrocarbon groups are linked directly or via a linking group containing a hetero atom is shown. q represents 0 or an integer of 1 or more. ]
An amine compound (B1) represented by the following formula (b-2):

[Wherein, R ⁴ and R ⁵ are the same or different and are each a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic hydrocarbon group. A divalent group formed by linking the above and one or more cyclic aliphatic hydrocarbon groups. r represents an integer of 1 or more. ]
And an amine compound (B2) represented by the following formula (b-3):

[Wherein, R ⁶ and R ⁸ are the same or different and each represents an alkylene group having 1 to 4 carbon atoms or an arylene group having 6 to 12 carbon atoms. s represents 0 or 1. R ⁷ represents a monovalent organic group, an oxygen atom-containing group, a sulfur atom-containing group, a nitrogen atom-containing group, or a halogen atom. t represents an integer of 0 to 10. ]
It is preferable that at least 1 type of amine compound selected from the group which consists of amine compound (B3) represented by these is included.

It is preferable that the epoxy compound (A) is a compound represented by the following formula (a).

［式中、Ｘは単結合、又は１以上の原子を有する二価の基を示す。］

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

The polyester structure in the side chain preferably has a carboxyl group-terminated polyester structure obtained by ring-opening polymerization of ε-caprolactone.

The polyester structure in the side chain preferably has a carboxyl group-terminated polyester structure obtained by ring-opening copolymerization of ε-caprolactone and δ-valerolactone.

The present invention also provides a dispersant containing the graft polymer.

An epoxy-amine adduct obtained by reacting an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule with an amine compound (B) having two or more amino groups in the molecule And a carboxyl group-terminated polyester is reacted. A method for producing a graft polymer is provided.

That is, the present invention relates to the following.
[1] Obtained by a reaction between an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule as the main chain. Having the structure of an epoxy-amine adduct,
A graft polymer having a polyester structure as a side chain.

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

［式中、Ｒ¹は、式中に示される窒素原子との結合部位に炭素原子を有するｐ価の有機基（有機残基）を示す。ｐは、２以上の整数を示す。］ [3] The graft polymer according to [1], wherein the amine compound (B) includes a p-valent amine compound represented by the following formula (b).

[Wherein, R ¹ represents a p-valent organic group (organic residue) having a carbon atom at the bonding site with the nitrogen atom shown in the formula. p represents an integer of 2 or more. ]

［式中、Ｒ²及びＲ³は、同一又は異なって、直鎖、分岐鎖、若しくは環状の二価の脂肪族炭化水素基、又は、直鎖若しくは分岐鎖状の脂肪族炭化水素基の１以上と環状の脂肪族炭化水素基の１以上とが直接又はヘテロ原子を含む連結基を介して連結した二価の基を示す。ｑは、０又は１以上の整数を示す。］
で表されるアミン化合物（Ｂ１）、下記式（ｂ－２）

［式中、Ｒ⁴及びＲ⁵は、同一又は異なって、直鎖、分岐鎖、若しくは環状の二価の脂肪族炭化水素基、又は、直鎖若しくは分岐鎖状の脂肪族炭化水素基の１以上と環状の脂肪族炭化水素基の１以上とが連結して形成される二価の基を示す。ｒは、１以上の整数を示す。］
で表されるアミン化合物（Ｂ２）、下記式（ｂ－３）

［式中、Ｒ⁶及びＲ⁸は、同一又は異なって、炭素数１～４のアルキレン基、又は炭素数６～１２のアリーレン基を示す。ｓは、０又は１を示す。Ｒ⁷は、一価の有機基、一価の酸素原子含有基、一価の硫黄原子含有基、一価の窒素原子含有基、又はハロゲン原子を示す。ｔは、０～１０の整数を示す。］
で表されるアミン化合物（Ｂ３）、及び下記式（ｂ－４）

［式中、Ｒ⁹は、式中に示される酸素原子との結合部位に炭素原子を有するｖ価の有機基を示す。Ｒ¹⁰は、直鎖、分岐鎖、若しくは環状の二価の脂肪族炭化水素基、又は、直鎖若しくは分岐鎖状の脂肪族炭化水素基の１以上と環状の脂肪族炭化水素基の１以上とが連結して形成される二価の基を示す。ｕは、１以上の整数を示す。ｖは、３以上の整数を示す。］
で表されるアミン化合物（Ｂ４）からなる群より選択される少なくとも一種のアミン化合物を含む［３］に記載のグラフトポリマー。 [4] The amine compound (B) is represented by the following formula (b-1)

[Wherein, R ² and R ³ are the same or different and are each a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic hydrocarbon group. A divalent group in which the above and one or more cyclic aliphatic hydrocarbon groups are linked directly or via a linking group containing a hetero atom is shown. q represents 0 or an integer of 1 or more. ]
An amine compound (B1) represented by the following formula (b-2):

[Wherein, R ⁴ and R ⁵ are the same or different and are each a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic hydrocarbon group. A divalent group formed by linking the above and one or more cyclic aliphatic hydrocarbon groups. r represents an integer of 1 or more. ]
An amine compound (B2) represented by the following formula (b-3):

[Wherein, R ⁶ and R ⁸ are the same or different and each represents an alkylene group having 1 to 4 carbon atoms or an arylene group having 6 to 12 carbon atoms. s represents 0 or 1. R ⁷ represents a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent sulfur atom-containing group, a monovalent nitrogen atom-containing group, or a halogen atom. t represents an integer of 0 to 10. ]
And an amine compound (B3) represented by formula (b-4):

[Wherein R ⁹ represents a v-valent organic group having a carbon atom at the bonding site with the oxygen atom shown in the formula. R ¹⁰ represents a linear, branched or cyclic divalent aliphatic hydrocarbon group, or one or more of a linear or branched aliphatic hydrocarbon group and one or more of a cyclic aliphatic hydrocarbon group. And a divalent group formed by linking with each other. u represents an integer of 1 or more. v represents an integer of 3 or more. ]
The graft polymer according to [3], comprising at least one amine compound selected from the group consisting of amine compounds (B4) represented by

[5] The amine compound (B) includes at least one amine compound selected from the group consisting of the amine compound (B1), the amine compound (B2), and the amine compound (B3). Graft polymer.

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

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

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

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

[10] The graft polymer according to any one of [1] to [9], wherein the number of alicyclic epoxy groups contained in the molecule of the epoxy compound (A) is selected from 2 to 6.

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

［式中、Ｘは単結合、又は１以上の原子を有する二価の基を示す。］ [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 compound represented by the formula (a) is at least one selected from the group consisting of compounds represented by the following formulas (a-1) to (a-10): Graft polymer.

[Wherein, l and m each represents an integer of 1 to 30; R ′ represents an alkylene group having 1 to 8 carbon atoms; and n1 to n6 each represents an integer of 1 to 30]. ]

[14] The graft polymer according to [12], wherein the compound represented by the formula (a) includes a compound represented by the 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 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] In any one of [1] to [16], the polyester structure in the side chain has a carboxyl group-terminated polyester structure obtained by ring-opening polymerization of a lactone represented by the following formula (1): The graft polymer described.

［式中、Ｒ¹¹は、置換されていてもよい炭素数１～１０のアルキレン基を示す。］

[Wherein R ¹¹ represents an optionally substituted alkylene group having 1 to 10 carbon atoms. ]

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

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

[20] The graft polymer according to any one of [17] to [19], wherein the carboxyl group-terminated polyester is obtained by an addition reaction in which a lactone is added to a monocarboxylic acid.

[21] The graft polymer according to any one of [17] to [19], wherein the carboxyl group-terminated polyester is obtained by an addition reaction in which a lactone is added to a hydroxycarboxylic acid.

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

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

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

[24] A pigment composition comprising the dispersant according to [23] and a pigment.

[25] Epoxy-amine addition obtained by reaction of an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule The method for producing a graft polymer according to any one of [1] to [22], wherein the product is reacted with a carboxyl group-terminated polyester.

The graft polymer of the present invention has excellent dispersibility with respect to a wide variety of pigments by having the above configuration.

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

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

{Epoxy-amine adduct}
The epoxy-amine adduct includes an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule (sometimes simply referred to as “epoxy compound (A)”), and two or more in the molecule. It is an epoxy-amine adduct obtained by a reaction with an amine compound (B) having an amino group (sometimes referred to simply as “amine compound (B)”). The above epoxy-amine adduct has two or more amino groups in the molecule obtained by reacting the alicyclic epoxy group of the epoxy compound (A) with the amino group of the amine compound (B). An epoxy-amine adduct is preferred.
In this specification, the term “amino group” simply means —NH ₂ (unsubstituted amino group), and “—NH— group” refers to the unsubstituted amino group (—NH ₂ ). It shall not be included.

(Epoxy compound (A))
The epoxy compound (A) as a raw material of the epoxy-amine adduct is a polyepoxy compound (alicyclic epoxy compound) having two or more alicyclic epoxy groups in the molecule. An epoxy compound (A) can be used individually or in combination of 2 or more types.

The alicyclic epoxy group possessed by the epoxy compound (A) is an epoxy group composed of two adjacent carbon atoms constituting the alicyclic ring (aliphatic ring) and an oxygen atom. The alicyclic epoxy group is not particularly limited. For example, it forms an aliphatic ring having 4 to 16 carbon atoms (aliphatic hydrocarbon ring) such as a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, or a cycloheptane ring. Examples thereof include an epoxy group composed of two adjacent carbon atoms and an oxygen atom. Especially, the epoxy group (cyclohexene oxide group) comprised by two adjacent carbon atoms which comprise a cyclohexane ring, and an oxygen atom is preferable.

The number of alicyclic epoxy groups in the molecule of the epoxy compound (A) may be two or more, and is not particularly limited, but is preferably 2 to 6, more preferably 2 to 5, and still more preferably 2. Or three. When the number of alicyclic epoxy groups is more than 6, it is not desirable because a crosslinked structure is taken when synthesizing an amine adduct and tends to be highly viscous or hardened.

As the epoxy compound (A), a compound (epoxy compound) represented by the following formula (a) is particularly preferable.

X in the above formula (a) represents a single bond or a linking group (a divalent group having one or more atoms). Examples of the linking group include a divalent hydrocarbon group, an alkenylene group in which part or all of a carbon-carbon double bond is epoxidized, a carbonyl group, an ether bond, an ester bond, a carbonate group, an amide group, and the like. And a group in which two or more of the groups are linked.

Examples of the epoxy compound (A) in which X in the formula (a) is a single bond include 3,4,3 ′, 4′-diepoxybicyclohexane.

Examples of the divalent hydrocarbon group for X in the above formula (a) include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group. Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group. Examples of the divalent alicyclic hydrocarbon group include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And bivalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.

Examples of the alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond in X in the formula (a) is epoxidized (sometimes referred to as “epoxidized alkenylene group”) include: Examples include linear or branched alkenylene groups having 2 to 8 carbon atoms such as vinylene group, propenylene group, 1-butenylene group, 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group, and octenylene group. It is done. In particular, the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.

As the linking group in X in the above formula (a), a linking group containing an oxygen atom is preferable. Specifically, —CO—, —O—CO—O—, —CO—O—, — O—, —CO—NH—, an epoxidized alkenylene group; a group in which a plurality of these groups are linked; a group in which one or more of these groups are linked to one or more of divalent hydrocarbon groups, etc. Is mentioned. Examples of the divalent hydrocarbon group include those 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), 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-epoxycyclohexane-1-yl) ethane), 2,3-bis (3,4-epoxycyclohexyl) oxirane (= 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1- Yl) ethane), bis (3,4-epoxycyclohexylmethyl) ether and the like. In the following formulas (a-5) and (a-7), l and m each represents an integer of 1 to 30. R ′ in the following formula (a-5) represents an alkylene group having 1 to 8 carbon atoms. For example, methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene. A linear or branched alkylene group such as a group, a hexylene group, a heptylene group, and an octylene group. Among these, a linear or branched alkylene group having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group is preferable. In the following formulas (a-9) and (a-10), n1 to n6 each represents an integer of 1 to 30.

As the epoxy compound (A), particularly from the viewpoint of reactivity with an amine compound, the compound represented by the above formula (a-1) [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate Trade name “Celoxide 2021P” (manufactured by Daicel Corporation) and the like] are preferable.

(Amine compound (B))
The amine compound (B) as a raw material of the epoxy-amine adduct is a polyamine compound having two or more amino groups (—NH ₂ ; unsubstituted amino group) in the molecule.

The number of amino groups in the molecule of the amine compound (B) may be 2 or more (for example, 2 to 1000) from the viewpoint of dispersibility and polarity.

The amine compound (B) can be used alone or in combination of two or more. The more the amino group, the higher the polarity, and the less the amino group, the lower the polarity. By using two or more amine compounds (for example, by using two or more amine compounds having different polarities), pigments It is possible to design an optimum structure for the substrate and to improve dispersibility. For this reason, it is preferable to combine two or more amine compounds.

Examples of the amine compound (B) include a p-valent amine compound represented by the following formula (b).

P in the above formula (b) represents an integer of 2 or more. p may be an integer of 2 or more, and is not particularly limited, but is preferably 2 to 6, more preferably 2 to 5, and still more preferably 2 or 3.

R ¹ in the above formula (b) represents a p-valent organic group (organic residue) having a carbon atom at the binding site with the nitrogen atom shown in the formula. Examples of R ¹ include a linear or branched p-valent aliphatic hydrocarbon group; a cyclic p-valent aliphatic hydrocarbon group; a p-valent aromatic hydrocarbon group; and two or more of these groups And a p-valent group linked (bonded) directly or via a linking group (divalent group) containing a hetero atom.

Examples of the linear or branched p-valent aliphatic hydrocarbon group include a linear or branched divalent aliphatic hydrocarbon group, a linear or branched trivalent aliphatic hydrocarbon group, and the like. Examples thereof include a hydrogen group, a linear or branched tetravalent aliphatic hydrocarbon group, and the like. Examples of the linear or branched divalent aliphatic hydrocarbon group include an alkylene group [eg, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, Linear or branched chain having 1 to 30 carbon atoms (C _1-30 ) such as nonylene group, decylene group, undecylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, hexadecylene group, heptadecylene group, octadecylene group, etc. An alkylene group (preferably a C _1-18 alkylene group)], an alkenylene group [an alkenylene group corresponding to the above alkylene group, for example, a linear or branched alkenylene group having 2 to 30 carbon atoms such as a vinylene group or an arylene group. (Preferably a C _2-18 alkenylene group) and the like. Examples of the linear or branched trivalent aliphatic hydrocarbon group include, for example, alkane-triyl group [eg, propane-triyl group, 1,1,1-trimethylpropane-triyl group, etc. 30 linear or branched alkane-triyl groups (preferably a C _3-18 alkane-triyl group) and the like. Examples of the linear or branched tetravalent aliphatic hydrocarbon group include, for example, alkane-tetrayl group [for example, butane-tetrayl group, 2,2-dimethylpropane-tetrayl group and the like having 4 to 30 carbon atoms. A linear or branched alkane-tetrayl group (preferably a C _4-18 alkane-tetrayl group) and the like].

The linear or branched p-valent aliphatic hydrocarbon group may have various substituents (that is, the linear or branched p-valent aliphatic hydrocarbon group is And at least one of the hydrogen atoms it has may be substituted with various substituents). Examples of the substituent include a halogen atom, an oxo group, a hydroxy group, a substituted oxy group (for example, an alkoxy group, an aryloxy group, an aralkyloxy group, and an acyloxy group), a carboxy group, and a substituted oxycarbonyl group (alkoxycarbonyl group). Aryloxycarbonyl group, aralkyloxycarbonyl group, etc.), substituted or unsubstituted carbamoyl group, cyano group, nitro group, substituted or unsubstituted amino group, sulfo group, heterocyclic group and the like. The hydroxy group or carboxy group may be protected with a protective group commonly used in the field of organic synthesis (for example, acyl group, alkoxycarbonyl group, organic silyl group, alkoxyalkyl group, oxacycloalkyl group, etc.).

Examples of the substituted or unsubstituted carbamoyl group include alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group and t-butyl group, or acetyl group and benzoyl group. And a carbamoyl group having an acyl group or an unsubstituted carbamoyl group. Examples of the substituted or unsubstituted amino group include an alkyl group such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, acetyl group, benzoyl group, and the like. And an amino group having an acyl group such as a group, or an unsubstituted amino group.

The heterocyclic ring constituting the heterocyclic group includes an aromatic heterocyclic ring and a non-aromatic heterocyclic ring. Examples of such a heterocyclic ring include, for example, a heterocyclic ring containing an oxygen atom as a hetero atom (for example, a 3-membered ring such as an oxirane ring, a 4-membered ring such as an oxetane ring, a furan ring, a tetrahydrofuran ring, an oxazole ring, and γ-butyrolactone. 5-membered ring such as a ring, 6-membered ring such as 4-oxo-4H-pyran ring, tetrahydropyran ring, morpholine ring, condensed ring such as benzofuran ring, 4-oxo-4H-chromene ring, chroman ring, 3-oxa Bridged ring such as tricyclo [4.3.1.1 ^4,8 ] undecan-2-one ring, 3-oxatricyclo [4.2.1.0 ^4,8 ] nonan-2-one ring ), Hetero rings containing a sulfur atom as a hetero atom (for example, 5-membered rings such as thiophene ring, thiazole ring and thiadiazole ring, 6-membered rings such as 4-oxo-4H-thiopyran ring, benzothiol) A condensed ring such as a thione ring), a heterocyclic ring containing a nitrogen atom as a hetero atom (for example, a 5-membered ring such as a pyrrole ring, a pyrrolidine ring, a pyrazole ring, an imidazole ring, a triazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, 6-membered rings such as pyrazine ring, piperidine ring, piperazine ring, indole ring, indoline ring, quinoline ring, acridine ring, naphthyridine ring, quinazoline ring, purine ring and the like. The heterocyclic group may be a heterocyclic group having a substituent, and the substituent may be, for example, the linear or branched p-valent aliphatic hydrocarbon group. In addition to good substituents, alkyl groups (eg, C _1-4 alkyl groups such as methyl and ethyl groups), alkenyl groups, cycloalkyl groups, cycloalkenyl groups, and aryl groups (eg, phenyl groups, naphthyl groups, etc.) And monovalent hydrocarbon groups. Further, the nitrogen atom constituting the heterocyclic ring in the heterocyclic group is a conventional protective group (for example, an alkoxy group, an alkoxycarbonyl group, an alkenyloxycarbonyl group, an aralkyloxycarbonyl group, an aralkyl group, an acyl group, an arylsulfonyl group). , An alkylsulfonyl group, etc.).

Examples of the cyclic p-valent aliphatic hydrocarbon group include a cyclic divalent aliphatic hydrocarbon group, a cyclic trivalent aliphatic hydrocarbon group, and a cyclic tetravalent aliphatic hydrocarbon group. . Examples of the cyclic divalent aliphatic hydrocarbon group include a cycloalkylene group [for example, a cycloalkylene group having 3 to 20 carbon atoms such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group ( Preferably a C _3-15 cycloalkylene group)], cycloalkenylene group [cycloalkenylene group corresponding to the above cycloalkylene group, for example, a cycloalkenylene group having 3 to 20 carbon atoms such as a cyclohexenylene group (preferably C _{3 -15} cycloalkenylene groups)], cycloalkylidene groups [cycloalkylidene groups corresponding to the above cycloalkylene groups, such as cyclopentylidene groups, cyclohexylidene groups, etc., preferably C 3-20 cycloalkylidene groups (preferably C _3-15 cycloalkylidene group)], a cycloalkadienyl Eni Emissions group [cycloalkadienyl Eni alkylene groups corresponding to the cycloalkylene group, for example, cycloalkadienyl Eni alkylene group (preferably a C _4-15 cycloalkadienyl Eni alkylene group) of 4 to 20 carbon atoms, such as cyclopentadienylide alkylene group such as A divalent polycyclic hydrocarbon group [eg, a divalent spiro hydrocarbon group such as a spiro hydrocarbon (eg, spiro [4.4] nonane, spiro [4.5] decane, etc.)-Diyl group; Ring-assembled hydrocarbons (eg, bicyclopropyl, etc.)-Divalent ring-assembled hydrocarbon groups such as diyl groups; bridged ring hydrocarbons (eg, bicyclo [2.1.0] pentane, bicyclo [3.2.1] And octane, norbornane, norbornene, adamantane, etc.)-Divalent bridged ring hydrocarbon groups such as diyl groups] and the like. Examples of the cyclic trivalent aliphatic hydrocarbon group include a cycloalkane-triyl group and a polycyclic hydrocarbon-triyl group. Examples of the cyclic tetravalent aliphatic hydrocarbon group include a cycloalkane-tetrayl group and a polycyclic hydrocarbon-tetrayl group. The cyclic p-valent aliphatic hydrocarbon group may have a substituent. Examples of the substituent include the linear or branched p-valent aliphatic hydrocarbon group. In addition to the substituents that may be present, monovalents such as alkyl groups (eg, C _1-4 alkyl groups such as methyl and ethyl groups), alkenyl groups, and aryl groups (eg, phenyl and naphthyl groups) And the like.

Examples of the p-valent aromatic hydrocarbon group include groups obtained by removing p hydrogen atoms from an aromatic hydrocarbon in terms of the structural formula. Examples of the aromatic hydrocarbon include benzene, naphthalene, anthracene, 9-phenylanthracene, 9,10-diphenylanthracene, naphthacene, pyrene, perylene, biphenyl, binaphthyl, and bianthryl. The p-valent aromatic hydrocarbon group may have a substituent. Examples of the substituent include the linear or branched p-valent aliphatic hydrocarbon group. In addition to an optional substituent, an alkyl group (eg, a C _1-4 alkyl group such as a methyl group or an ethyl group), a monovalent hydrocarbon group such as an alkenyl group, a cycloalkyl group, or a cycloalkenyl group can be mentioned. It is done.

Examples of the linking group containing a hetero atom (divalent group) include —CO—, —O—, —CO—O—, —O—CO—O—, —CO—NH—, and —CO—NR. ^a — (substituted amide group; R ^a represents an alkyl group), —NH—, —NR ^b — (R ^b represents an alkyl group), —SO—, —SO ₂ — and other heteroatoms (oxygen atom, A divalent group containing a nitrogen atom, a sulfur atom, etc.), a divalent group in which a plurality of these are linked, and the like.

More specifically, as the amine compound (B), an amine compound represented by the following formula (b-1) (amine compound (B1)), a compound represented by the following formula (b-2) (amine compound) (B2)), a compound represented by the following formula (b-3) (amine compound (B3)), a compound represented by the following formula (b-4) (amine compound (B4)), and the like. It is done. Especially, what contains at least 1 type of amine compound selected from the group which consists of an amine compound (B1), an amine compound (B2), and an amine compound (B3) is preferable.

In the above formula (b-1), R ² and R ³ are the same or different and are a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic group. A divalent group in which one or more hydrocarbon groups and one or more cyclic aliphatic hydrocarbon groups are linked (bonded) directly or via a linking group (divalent group) containing a hetero atom. Examples of the linear, branched, or branched divalent aliphatic hydrocarbon group include, for example, the substituted or unsubstituted linear, branched, or branched divalent fat exemplified as R ^1. Group hydrocarbon group. Examples of the divalent group in which one or more of the above-mentioned linear or branched aliphatic hydrocarbon groups and one or more of the cyclic aliphatic hydrocarbon groups are directly bonded include, for example, the following formula (b- Examples include groups exemplified as groups formed by removing two amino groups at both ends from the structural formula represented by 3). Furthermore, as a coupling group containing a hetero atom, the group illustrated as a coupling group containing the hetero atom in R < ¹ > is mentioned, for example.

Among these, R ² is preferably a linear or branched divalent aliphatic hydrocarbon group, more preferably a linear or branched alkylene group having 2 to 6 carbon atoms, and still more preferably 2 carbon atoms. 4 to 4 linear or branched alkylene groups (for example, ethylene group, trimethylene group, propylene group, etc., particularly ethylene group).

Among these, R ³ is preferably a linear or branched divalent aliphatic hydrocarbon group, more preferably a linear or branched alkylene group having 2 to 6 carbon atoms, and still more preferably 2 carbon atoms. 4 to 4 linear or branched alkylene groups (for example, ethylene group, trimethylene group, propylene group, etc., particularly ethylene group). In the case of q is 2 or more integer, R ³ each in brackets (multiple R ³⁾ may be the same or different. Moreover, when it has 2 or more types of R < ³ >, the addition form (polymerization form) of the structure in the parenthesis which attached | subjected q may be a random type, and may be a block type.

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

Note that R ² and R ³ in the above formula (b-1) may be the same or different. Among these, from the viewpoint that the carboxyl group-terminated polyester in the side chain is likely to be uniformly distributed, R ² and R ³ in the above formula (b-1) are preferably the same.

Among them, the compounds represented by the above formula (b-1) include ethylenediamine (EDA) and diethylenetriamine from the viewpoint of reactivity between the epoxy compound (A) and the amine compound (B) and dispersibility of the graft polymer in the pigment. (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA) are preferable, and triethylenetetramine is more preferable. A commercially available product can also be used as the compound represented by the above formula (b-1).

R ⁴ in the above formula (b-2) is a linear, branched or cyclic divalent aliphatic hydrocarbon group, or one or more of a linear or branched aliphatic hydrocarbon group and a cyclic group. A divalent group formed by linking one or more aliphatic hydrocarbon groups. Examples of R ⁴ include the divalent groups exemplified as the above R ² and R ³ .
Among these, R ⁴ is preferably a linear or branched divalent aliphatic hydrocarbon group, more preferably a linear or branched alkylene group having 2 to 6 carbon atoms, and still more preferably 2 carbon atoms. 4 to 4 linear or branched alkylene groups (for example, ethylene group, trimethylene group, propylene group, etc., especially propylene group).

R ⁵ in the above formula (b-2) is a linear, branched or cyclic divalent aliphatic hydrocarbon group or one or more linear or branched aliphatic hydrocarbon groups and a cyclic group. A divalent group formed by linking one or more aliphatic hydrocarbon groups. Examples of R ⁵ include the divalent groups exemplified as the above R ² and R ³ .
Among them, R ⁵ is preferably a linear or branched divalent aliphatic hydrocarbon group, more preferably a linear or branched alkylene group having 2 to 6 carbon atoms, and still more preferably 2 carbon atoms. 4 to 4 linear or branched alkylene groups (for example, ethylene group, trimethylene group, propylene group, etc., especially propylene group). In the case of r is 2 or more integer, R ⁵ each in parentheses (multiple R ⁵⁾ may be the same or different. Moreover, when it has 2 or more types of R < ⁵ >, the addition form (polymerization form) of the structure in the parenthesis to which r is attached may be a random type or a block type.
R ⁴ and R ⁵ in the above formula (b-2) may be the same or different.

In the above formula (b-2), r (the number of repeating structural units in parentheses to which r is attached) represents an integer of 1 or more. For example, r is preferably 1 to 100, more preferably 1 to 70, and still more preferably 1 to 30. By setting r to 100 or less, the dispersibility to the pigment tends to be improved without impairing the heat resistance of the graft polymer of the present invention. On the other hand, by setting r to 1 or more, flexibility can be improved without impairing dispersibility in the pigment.

Among them, the compound represented by the above formula (b-2) includes an amine terminal (both terminal amino acids) from the viewpoint of reactivity between the epoxy compound (A) and the amine compound (B) and dispersibility of the graft polymer in the pigment. Group) polyethylene glycol, amine-terminated polypropylene glycol and amine-terminated polybutylene glycol are preferred, and amine-terminated polypropylene glycol is more preferred. In addition, as the compound represented by the above formula (b-2), commercially available products (for example, “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 each represents an alkylene group having 1 to 4 carbon atoms or an arylene group having 6 to 12 carbon atoms. Specific examples of R ⁶ and R ⁸ include alkylene groups having 1 to 4 carbon atoms (eg, methylene group) and arylene groups having 6 to 12 carbon atoms (aromatic hydrocarbons) exemplified as R ¹ in formula (b). A group in which two hydrogen atoms are removed from).

In the above formula (b-3), s (the number of repeating structural units in parentheses with s) represents 0 or 1.

R ⁷ in the above formula (b-3) represents a substituent on the cyclohexane ring shown in the formula, and is the same or different and is a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent sulfur atom. A containing group, a monovalent nitrogen atom-containing group, or a halogen atom. Specific examples of R ⁷ include, for example, an alkyl group (eg, an alkyl group having 1 to 10 carbon atoms, particularly a methyl group), a halogen atom (a fluorine atom, a chlorine atom, etc.), a hydroxy group, a carboxy group, and an alkoxy group. Alkenyloxy group, aryloxy group, aralkyloxy group, acyloxy group, mercapto group, alkylthio group, alkenylthio group, arylthio group, aralkylthio group, alkoxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group, amino group, Examples thereof include a nitro group, a mono- or dialkylamino group, an acylamino group, an epoxy group, a glycidyl group, an acyl group, a cyano group, an isocyanate group, an isothiocyanate group, a carbamoyl group, and a sulfo group. In the formula (b-3), t represents the number of substituents (R ⁷ ) on the cyclohexane ring shown in the formula, and represents an integer of 0 to 10 (preferably an integer of 1 to 5). When t in the above formula (b-3) is an integer of 2 or more, each R ⁷ may be the same or different.

More specifically, examples of the group formed by removing two amino groups at both ends from the structural formula represented by the above formula (b-3) include 1,2-cyclohexylene-methylene group, 1, 3-cyclohexylene-methylene group, 1,4-cyclohexylene-methylene group, cyclohexylidene-methylene group, 1,2-cyclohexylene-ethylene group, 1,3-cyclohexylene-ethylene group, 1,4-cyclohexylene Silene-ethylene group, cyclohexylidene-ethylene group, methylene-1,5,5-trimethyl-1,3-cyclohexylene group (a divalent group formed by removing two amino groups from isophoronediamine), etc. Cyclohexylene-alkylene group; 1,2-cyclohexylene-phenylene group, 1,3-cyclohexylene-phenylene group, 1,4-cyclohexyl Cyclohexylene-arylene groups such as lenene-phenylene groups; alkylenes such as methylene-1,2-cyclohexylene-methylene groups, methylene-1,3-cyclohexylene-methylene groups, methylene-1,4-cyclohexylene-methylene groups -Cyclohexylene-alkylene group; alkylene-cyclohexylene-phenylene such as methylene-1,2-cyclohexylene-phenylene group, methylene-1,3-cyclohexylene-phenylene group, methylene-1,4-cyclohexylene-phenylene group Groups; arylene-cyclohexylene-arylene groups such as phenylene-1,2-cyclohexylene-phenylene group, phenylene-1,3-cyclohexylene-phenylene group, phenylene-1,4-cyclohexylene-phenylene group, etc.

Among them, the compound represented by the above formula (b-3) is preferably isophoronediamine from the viewpoint of the reactivity between the epoxy compound (A) and the amine compound (B) and the dispersibility of the graft polymer in the pigment. In addition, as the compound represented by the above formula (b-3), a commercially available product (for example, trade name “Vestamine IPD” manufactured by Evonik Degussa Japan Co., Ltd.) can also be used.

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

R ¹⁰ in the above formula (b-4) is a linear, branched or cyclic divalent aliphatic hydrocarbon group or one or more linear or branched aliphatic hydrocarbon groups and a cyclic group. A divalent group formed by linking with one or more aliphatic hydrocarbon groups is exemplified, and examples thereof include the divalent groups exemplified as R ² and R ³ described above. R ⁹ represents a v-valent organic group having a carbon atom at the bonding site with the oxygen atom shown in the formula, and is the same as R ¹ (for example, a linear or branched p-valence). An aliphatic hydrocarbon group, a cyclic p-valent aliphatic hydrocarbon group, etc.).

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

As the amine compound (B), from the viewpoint of the reactivity between the epoxy compound (A) and the amine compound (B) and the dispersibility of the graft polymer with respect to the pigment, the amine compound (B1), the amine compound (B2), and the amine compound ( It is preferably at least one amine compound selected from the group consisting of B3), and more preferably, from the viewpoint of further excellent dispersibility in the pigment, only the amine compound (B1), only the amine compound (B2), and the amine compound It is a combination of (B1) and an amine compound (B3), or a combination of an amine compound (B2) and an amine compound (B3).

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

The epoxy compound (A) and amine compound (B) as raw materials for the epoxy-amine adduct are from the viewpoint of the reactivity between the epoxy compound (A) and the amine compound (B) and the dispersibility of the graft polymer in the pigment. Compound represented by formula (a) and amine compound (B1), compound represented by formula (a), amine compound (B1) and amine compound (B3), compound represented by formula (a) and amine compound (B2), the compound represented by the formula (a), the amine compound (B2), and the amine compound (B3) are preferable. In the above epoxy-amine adduct, an epoxy compound (A) other than the compound represented by the formula (a) and an amine compound other than the amine compounds (B1) (B2) (B3) may be used in combination.

In addition to the dispersibility, further characteristics can be obtained by combining the epoxy compound (A) and the amine compound (B). Specifically, for example, the compound represented by the formula (a) and the amine compound (B1) (more preferably both of the amine compounds (B1) and (B3)) are reacted with the resin. Excellent in heat resistance, heat resistance, and handleability. Moreover, it is excellent in heat resistance by making the compound represented by Formula (a), an amine compound (B2), and an amine compound (B3) react.

In the reaction of the epoxy compound (A) and the amine compound (B), the epoxy equivalent (for example, the equivalent of an alicyclic epoxy group) in the epoxy compound (A) in the reaction raw material and the amine equivalent in the amine compound (B) ( For example, the ratio (equivalent of amino group) (epoxy equivalent in epoxy compound (A) / amine equivalent in amine compound (B)) is not particularly limited, but is preferably 0.3 to 3, more preferably 0.5 to 2, more preferably 0.7 to 1.5, particularly preferably 0.9 to 1.1. By setting the equivalent ratio in 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 resin in which the pigment is dispersed are hardly lowered.

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

When the amine compound (B1) is used in the reaction between the epoxy compound (A) and the amine compound (B), the proportion of the amine compound (B1) in the total amount (100% by weight) of the amine compound (B) is particularly limited. However, it is preferably 10% by weight or more (for example, 10 to 100% by weight), more preferably 20 to 100% by weight, still more preferably 45 to 90% by weight, and particularly preferably 50 to 70% by weight. By setting the ratio of the amine compound (B1) within the above range, the dispersibility can be further improved.

In the reaction between the epoxy compound (A) and the amine compound (B), when the amine compound (B2) is used, the proportion of the amine compound (B2) in the total amount (100% by weight) of the amine compound (B) is particularly limited. However, it is preferably 10% by weight or more (for example, 10 to 100% by weight), more preferably 20 to 100% by weight, still more preferably 30 to 90% by weight, and particularly preferably 40 to 70% by weight. By setting the ratio of the amine compound (B2) within the above range, flexibility can be improved.

When the amine compound (B3) is used in the reaction between the epoxy compound (A) and the amine compound (B), the proportion of the amine compound (B3) in the total amount (100% by weight) of the amine compound (B) is particularly limited. However, it is preferably 10 to 70% by weight, more preferably 20 to 60% by weight, still more preferably 30 to 55% by weight. Heat resistance can be improved by making the ratio of an amine compound (B3) into the said range.

The above reaction (reaction of epoxy compound (A) and amine compound (B)) can be allowed to proceed in the presence of a solvent, or can be allowed to proceed in the absence of a solvent (that is, without solvent). Although it does not specifically limit as said solvent, The thing which can melt | dissolve or disperse | distribute an epoxy compound (A) and an amine compound (B) uniformly is preferable. Specifically, examples of the solvent include aliphatic hydrocarbons such as hexane, heptane, and octane; alicyclic hydrocarbons such as cyclohexane; aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene; chloroform, dichloromethane. Halogenated hydrocarbons such as 1,2-dichloroethane; ethers such as diethyl ether, dimethoxyethane, tetrahydrofuran and dioxane; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate and the like Esters; Amides such as N, N-dimethylformamide and N, N-dimethylacetamide; Nitriles such as acetonitrile, propionitrile and benzonitrile; Methanol, ethanol and isopropyl alcohol Alcohols such as butanol; and dimethyl sulfoxide. In addition, the said solvent can also be used individually by 1 type, and can also be used in combination of 2 or more type.

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

The reaction of the epoxy compound (A) and the amine compound (B) can be caused to proceed by, for example, the following method [1], the following [2], or the following [3]. However, the method for causing the reaction to proceed is not limited to the following methods [1] to [3].
[1] A method in which the epoxy compound (A) and the amine compound (B) are charged all at once in a reaction vessel, and heated to the reaction temperature as necessary to react both.
[2] A method in which the amine compound (B) is sequentially added to a reaction vessel in which the epoxy compound (A) is charged and heated to the reaction temperature as necessary, and both are reacted.
[3] A method in which the epoxy compound (A) is sequentially added to a reaction vessel in which the amine compound (B) is charged and heated to the reaction temperature as necessary, and both are reacted.

The “sequential addition” means continuous addition (a mode of adding over a certain period of time) or intermittent addition (a mode of split addition in multiple times).

Among the above methods [1] to [3], the method according to the above [2] is preferable because the reaction heat can be easily controlled and an epoxy-amine adduct having a high molecular weight and a high glass transition temperature can be easily formed. The method [3] is preferred. On the other hand, the epoxy-amine adduct having a lower molecular weight may be advantageous depending on the application. In such a case, the reaction is preferably carried out by the method [1] above.

The rate at which the amine compound (B) is added in the method [2] is not particularly limited. For example, when the total amount of the amine compound (B) to be added is 100 parts by weight, 0.1 to 20 parts by weight / It can set suitably from the range of minutes. In addition, the rate at which the epoxy compound (A) is added in the method [3] is not particularly limited. For example, when the total amount of the epoxy compound (A) to be added is 100 parts by weight, 0.1 to 20 parts by weight. It can set suitably from the range of a part / minute. The amine compound (B) or epoxy compound (A) to be added can be added as it is, or can be added in the state of a solution or dispersion dissolved or dispersed in a solvent.

In addition, when using 2 or more types of amine compounds (B), in the method of said [2], it may be dripped in the state which mixed each amine compound (B), and it is dripped in the state (each) which is not mixed. May be. In the latter case, each amine compound (B) can be dropped simultaneously or sequentially. The same applies to the dropping in the case of using two or more epoxy compounds (A) in the method [3].

The temperature (reaction temperature) in the above reaction is not particularly limited, but is preferably 30 to 280 ° C, more preferably 80 to 260 ° C, still more preferably 120 to 250 ° C. By setting the reaction temperature to 30 ° C. or higher, the reaction rate tends to increase and the productivity of the epoxy-amine adduct tends to be further improved. On the other hand, when the reaction temperature is 280 ° C. or lower, thermal decomposition of the epoxy compound (A) or the amine compound (B) is suppressed, and the yield of the epoxy-amine adduct tends to be further improved. The reaction temperature may always be constant (substantially constant), or may be changed stepwise or continuously.

The reaction time in the above reaction is not particularly limited, but is preferably 0.2 to 20 hours, more preferably 0.5 to 10 hours, and further preferably 2 to 8 hours. By setting the reaction time to 0.2 hours or longer, the yield of the epoxy-amine adduct tends to be further improved. By setting the reaction time to 20 hours or less, the productivity of the epoxy-amine adduct tends to be improved.

The above reaction can be carried out under normal pressure, under pressure or under reduced pressure. The pressure during the reaction may always be constant (substantially constant), or may be changed stepwise or continuously. In addition, the atmosphere in which the above reaction is performed is not particularly limited, and the reaction can be performed in any atmosphere such as an inert gas (for example, nitrogen, argon, etc.) or air.

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

The above reaction (reaction of epoxy compound (A) and amine compound (B)) gives an epoxy-amine adduct. After the above reaction, the resulting epoxy-amine adduct is obtained by, for example, known or conventional separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these. It is possible to separate and purify by, for example.

The number of amino groups (—NH ₂ ; unsubstituted amino group) possessed by the epoxy-amine adduct is preferably 2 or more, more preferably 2 to 10, further preferably 2 to 4, particularly preferably 2 Or three. The epoxy-amine adduct preferably has substantially no epoxy group (particularly an alicyclic epoxy group derived from the epoxy compound (A)).

The position of the amino group (—NH ₂ ; unsubstituted amino group) in the epoxy-amine adduct is not particularly limited, but the end of the molecular chain of the epoxy-amine adduct (particularly the linear epoxy-amine adduct) In such a case, it is preferable to locate at both ends of the molecular chain of the epoxy-amine adduct.

As described above, the epoxy-amine adduct is generated by the reaction between the alicyclic epoxy group of the epoxy compound (A) and the amino group (—NH ₂ ; unsubstituted amino group) of the amine compound (B). . The epoxy-amine adduct is an —NH— group (substituted amino group) formed by the reaction of the alicyclic epoxy group and an amino group (in addition, when the amine compound (B1) is used, the amine compound (B1 )) -NH- group (when q is 1 or more)) and the cycloaliphatic epoxy group of the epoxy compound (A) are presumed to be poor in reactivity, but usually -NH- The group remains unreacted. The number of —NH— groups in the molecule of the epoxy-amine adduct is not particularly limited, but is preferably 1 to 200, more preferably 1 to 150, and still more preferably 2 to 100. If the epoxy-amine adduct does not have a —NH— group, the reactivity with the carboxyl group-terminated polyester may be reduced. The number of —NH— groups in the epoxy-amine adduct is, for example, the epoxy constituting the epoxy-amine adduct using a molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC). It is possible to calculate by obtaining the number of the compound (A) and the amine compound (B).

The compound obtained by the reaction between the epoxy compound having a glycidyl group and the amine compound (B) includes a reaction between the —NH— group and the glycidyl group generated by the reaction between the glycidyl group and the amino group (unsubstituted amino group). In general, the —NH— group does not substantially remain because of its very high properties.

The number average molecular weight of the epoxy-amine adduct is not particularly limited, but is preferably 200 to 40000, more preferably 300 to 30000, and still more preferably 400 to 20000. By setting the number average molecular weight to 200 or more, the dispersibility of the graft polymer with respect to the pigment tends to be further improved. Moreover, there exists a tendency for the softness | flexibility and toughness of a graft polymer to improve. On the other hand, when the number average molecular weight is 40000 or less, the solubility in the resin and the handling property can be kept good. The number average molecular weight of the epoxy-amine adduct can be calculated using the molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC) method.

The glass transition temperature (Tg) of the epoxy-amine adduct is not particularly limited, but is preferably −50 to 200 ° C., more preferably −40 to 190 ° C., still more preferably −30 to 180 ° C., and particularly preferably 20 ~ 180 ° C. When the glass transition temperature is in the above range, the dispersibility of the graft polymer with respect to the pigment tends to be further improved. The Tg of the epoxy-amine adduct can be measured, for example, by differential scanning calorimetry (DSC) or dynamic viscoelasticity measurement. More specifically, it can be measured by the method disclosed in the examples.

［式（Ｉ）中、Ｘは、上記式（ａ）におけるものと同じ。］

［式（ＩＩ）中、Ｒ²、Ｒ³、及びｑは、上記式（ｂ－１）におけるものと同じ。］

［式（ＩＩＩ）中、Ｒ⁶、Ｒ⁷、Ｒ⁸、ｓ、及びｔは、上記式（ｂ－３）におけるものと同じ。］

［式（ＩＶ）中、Ｒ⁴、Ｒ⁵、及びｒは、上記式（ｂ－２）におけるものと同じ。］ The epoxy-amine adduct has a structural unit (structural unit) derived from the epoxy compound (A) and a structural unit derived from the amine compound (B). Specifically, a structural unit represented by the following formula (I) (structural unit; structural unit derived from the compound represented by formula (a)) and a structural unit represented by the following formula (II) (amine) A structural unit derived from the compound (B1), a structural unit represented by the following formula (III) (a structural unit derived from the amine compound (B3)), and a structural unit represented by the following formula (IV) (an amine compound ( And at least one structural unit selected from the group consisting of structural units derived from B2). Further, it is preferable to have an amino group (—NH ₂ ) at both ends.

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

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

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

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

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

In the above formula (I), when the carbon atom to which X is bonded among the carbon atoms constituting the cyclohexane ring is defined as the “1-position” carbon atom, each cyclohexane ring of the structural unit represented by formula (I) The bonding position of the nitrogen atom (—NH—) of the structural unit derived from the amine compound (B) bonded to is the 3-position carbon atom or 4-position carbon atom of the cyclohexane ring. When the nitrogen atom is bonded to the 3-position carbon atom, the hydroxy group (—OH) bonded to the cyclohexane ring in the formula (I) is bonded to the 4-position carbon atom. When the bonding position of the nitrogen atom is the carbon atom at the 4-position of the cyclohexane ring, the bonding position of the hydroxy group (—OH) bonded to the cyclohexane ring in the formula (I) is the carbon atom at the 3-position. The bonding positions of the nitrogen atoms (or the bonding positions of hydroxy groups) in a plurality of (two or more) cyclohexane rings in the formula (I) may be the same or different. In addition, when the above-mentioned position number is attached | subjected to the carbon atom which comprises the cyclohexane ring in Formula (I), it will become like a following formula.

{Carboxyl-terminated polyester}
As said carboxyl group terminal polyester, the polyester which contains the structural unit produced | generated by ring-opening polymerization of the lactone represented by following formula (1), and has a carboxyl group at the terminal is mentioned, for example. The carboxyl group-terminated polyester preferably has a carboxyl group only at one end of the polyester chain. The said lactone compound can also be used individually by 1 type, and can also be used in combination of 2 or more type. The terminal carboxyl group (at least one of the terminal carboxyl groups) can react with the amino group or hydroxyl group of the epoxy-amine adduct (for example, addition reaction, graft polymerization, etc.).

R ¹¹ in the above formula (1) is an optionally substituted alkylene group having 1 to 10 carbon atoms (straight chain alkylene group, preferably a straight chain alkylene group having 2 to 5 carbon atoms (ethylene group, n-propylene group). N-butylene group, n-hexylene group)).

The substituent in the alkylene group having 1 to 10 carbon atoms in R ¹¹ is not particularly limited. For example, a halogen atom, an oxo group, a hydroxy group, an alkyl group, an alkenyl group, an aryl group (for example, a phenyl group, a naphthyl group) Etc.). Among them, an alkyl group (for example, an alkyl group having 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group) is preferable.

The lactone compound represented by the above formula (1) is not particularly limited. For example, ε-caprolactone, δ-valerolactone, β-methyl-δ-valerolactone, β-propiolactone, γ-butyrolactone, 2 -Methyl caprolactone, 4-methyl caprolactone and the like. Among them, in addition to being industrially easily available, the reactivity for obtaining a ring-opening polymer is excellent, and from the viewpoint of compatibility with a substrate, ε-caprolactone, δ-valerolactone, or a combination thereof Is preferred. That is, the graft polymer of the present invention has, as a side chain polyester structure, a carboxyl group-terminated polyester obtained by ring-opening polymerization of ε-caprolactone or δ-valerolactone, or ε-caprolactone and δ-valerolactone. It preferably has a structure of a carboxyl group-terminated polyester obtained by polymerization.

Although it does not specifically limit as said carboxyl group terminal polyester, For example, the polyester which has a structural unit represented by following formula (2), and has a carboxyl group at the terminal is mentioned.

In the above formula (2), w1 (the number of repeating structural units in parentheses to which w1 is attached) represents an integer of 1 or more, preferably 1 to 100, more preferably 1 to 70, still more preferably 1 to 30 It is. R ¹¹ in the formula (2) is may be the same as those R ¹¹ in the formula (1). Among them, an alkylene group having 1 to 10 carbon atoms (preferably carbon having 1 to 10 carbon atoms (preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group) which may have an alkyl group having 1 to 10 carbon atoms as a substituent. A linear alkylene group of 2 to 5) is preferred. When w1 is an integer of 2 or more, R ¹¹ (plural R ¹¹ ) in each parenthesis may be the same or different. Moreover, when it has 2 or more types of R < ¹¹ >, the addition form (polymerization form) of the structure in the parenthesis attached | subjected to w1 may be a random type, and may be a block type.

The method for synthesizing the carboxyl group-terminated polyester is not particularly limited, but (i) an addition reaction for adding a lactone to a monocarboxylic acid, (ii) an addition reaction for adding a lactone to a hydroxycarboxylic acid, (iii) a monocarboxylic acid, A condensation reaction in which the three components of hydroxycarboxylic acid and lactone are condensed; (iv) a condensation reaction in which the dicarboxylic acid and diol component are condensed with lactone, hydroxycarboxylic acid, monocarboxylic acid, etc .; Examples thereof include a condensation reaction in which a polyvalent carboxylic acid or an acid anhydride thereof, a polyhydric alcohol, a lactone, a hydroxycarboxylic acid or the like is used for condensation. Among these, from the viewpoint that a carboxyl group-terminated polyester having a molecular weight as designed is easily obtained, the synthesis method (i) or (ii) is preferable.

The monocarboxylic acid used for the synthesis of the carboxyl group-terminated polyester is not particularly limited, but is an aliphatic carboxylic acid such as acetic acid, propionic acid, butyric acid, valeric acid, trimethylacetic acid, caproic acid, lauric acid, stearic acid, and methoxyacetic acid. And aromatic carboxylic acids such as abietic acid and phenylacetic acid. Among these, lauric acid is preferable from the viewpoint of industrial availability and dispersibility of the graft polymer with respect to the pigment. The said monocarboxylic acid can also be used individually by 1 type, and can also be used in combination of 2 or more type.

The hydroxycarboxylic acid used for the synthesis of the carboxyl group-terminated polyester is not particularly limited, and examples thereof include saturated or unsaturated aliphatic hydroxycarboxylic acids and aromatic hydroxycarboxylic acids. Specifically, ricinoleic acid, 12-hydroxystearic acid, castor oil fatty acid (castor oil fatty acid condensate), hydrogenated castor oil fatty acid, δ-hydroxyvaleric acid, ε-hydroxycaproic acid, p-hydroxyethyloxycarboxylic acid, 2- Hydroxynaphthalene-3-carboxylic acid, 2-hydroxynaphthalene-6-carboxylic acid, 2,2-dimethylolpropionic acid, 2,2-dimethylolvaleric acid, 2,2-dimethylolpentanoic acid, malic acid, tartaric acid, lactic acid Glycolic acid, gluconic acid, hydroxypivalic acid, 11-oxyhexadecanoic acid, 2-oxidedecanoic acid, salicylic acid or a condensate thereof. Among these, ricinoleic acid, castor oil fatty acid or a condensate thereof is preferable from the viewpoint of industrial availability and dispersibility of the graft polymer with respect to the pigment. The said hydroxy monocarboxylic acid can also be used individually by 1 type, and can also be used in combination of 2 or more type.

Although it does not specifically limit as polyhydric carboxylic acid or its acid anhydride used for the synthesis | combination of the said carboxyl group terminal polyester, Maleic acid, succinic acid, glutaric acid, fumaric acid, adipic acid, sebacic acid, azelaic acid , Dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, hexahydrophthalic acid, methylhexahydrophthalic acid, tetrahydrophthalic acid, trimellitic acid, methyltetrahydrophthalic acid, or anhydrides thereof. The above-mentioned divalent or higher polyvalent carboxylic acid or acid anhydride thereof can be used alone or in combination of two or more.

The polyhydric alcohol used for the synthesis of the carboxyl group-terminated polyester is not particularly limited, and examples thereof include linear or branched polyhydric aliphatic alcohols, alicyclic polyhydric alcohols, and aromatic polyhydric alcohols. . Specifically, ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, neopentyl glycol, 3-methylpentanediol, 1, Examples thereof include 5-pentanediol, 1,6-hexanediol, trimethylolpropane, cyclohexanedimethanol, 1,4-dibenzyl alcohol and the like. The said polyhydric alcohol can also be used individually by 1 type, and can also be used in combination of 2 or more type.

In the synthesis of the carboxyl group-terminated polyester, it is preferable to use a catalyst (esterification catalyst) and / or a reaction solvent from the viewpoint of increasing the reaction rate and improving the heat exchange ability. Moreover, it is preferable to synthesize | combine in inert gas atmosphere, such as nitrogen gas, from a viewpoint of suppressing coloring.

The esterification catalyst used for the synthesis of the carboxyl group-terminated polyester is not particularly limited. Examples thereof include tin compounds such as stannous, tetrabutyl titanate, tetraethyl titanate, and tetrapropyl titanate. Among these, tetrabutyl titanate is preferable from the viewpoint of cost and productivity. The said esterification catalyst can also be used individually by 1 type, and can also be used in combination of 2 or more type.

The amount of the esterification catalyst used (the total amount when two or more esterification catalysts are used) is not particularly limited, but is preferably 0.1 to 3000 ppm based on the total amount of the reaction raw materials. 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 the productivity is improved. Moreover, coloring of carboxyl group-terminated polyester can be suppressed by setting it as 3000 ppm or less.

Examples of the reaction solvent used for the synthesis of the carboxyl group-terminated polyester include dehydrating solvents such as toluene and xylene.

The temperature at the time of synthesizing the carboxyl group-terminated polyester can be appropriately selected depending on the type of raw material, molar ratio, type and amount of catalyst, type and amount of solvent, etc., for example, 120 to 220 ° C (preferably 160 to 210 ° C) Is mentioned. By setting the reaction temperature to 120 ° C. or higher, the reaction rate is increased. When the temperature is 220 ° C. or lower, side reactions (for example, decomposition of a lactone polymer into a lactone monomer, generation of a cyclic lactone dimer, etc.) hardly occur, and a carboxyl-terminated polyester having a target molecular weight is easily obtained. Moreover, coloring of the carboxyl group-terminated polyester can be suppressed.

The carboxyl group-terminated polyester can be synthesized, for example, by charging the above raw materials into a reactor equipped with a dehydrating tube and a condenser and reacting them under an inert gas stream such as nitrogen gas. When a reaction solvent is used, after completion of the reaction, the reaction solvent may be removed by an operation such as distillation or may be used as it is for the reaction with the epoxy-amine adduct.

The acid value of the carboxyl group-terminated polyester is not particularly limited, but is preferably 1 to 200, for example. When the acid value is 1 or more, the viscosity of the carboxyl group-terminated polyester can be adjusted to an appropriate range. When the oxidation is 200 or less, the molecular weight of the carboxyl group-terminated polyester is in an appropriate range, a repellent layer is easily formed around the pigment, and the dispersibility to the pigment is improved. The acid value refers to the acid value measured according to JIS K-1557.

The weight average molecular weight of the carboxyl group-terminated polyester is not particularly limited, but is preferably 100 to 5,000. When the weight average molecular weight is in the above range, a sufficient three-dimensional repellent layer is formed around the pigment to improve dispersibility, and compatibility with pigments such as paints and ink vehicles is improved. In addition, the said weight average molecular weight says the value measured by NMR method.

[Method for producing graft polymer]
The graft polymer of the present invention is, for example, a reaction between the epoxy-amine adduct obtained by the reaction of the epoxy compound (A) and the amine compound (B) with a polyester (for example, the carboxyl group-terminated polyester) (for example, , Graft polymerization). More specifically, for example, derived from the —OH group in the structural unit derived from the epoxy compound (A) (for example, —OH group in the formula (I)) or the amine compound (B) of the epoxy-amine adduct. By reacting a —NH— group (for example, —NH— group in the formulas (II), (III), and (IV)) with a carboxyl group-terminated polyester (eg, a terminal carboxyl group). A graft polymer is produced.

In the reaction of the epoxy-amine adduct and the carboxyl group-terminated polyester, the epoxy in the total amount of raw materials for reaction (total amount of raw materials including the epoxy-amine adduct and the carboxyl group-terminated polyester) (100% by weight) The proportion of the amine adduct is not particularly limited, but is preferably 1 to 50% by weight, more preferably 5 to 40% by weight, and still more preferably 10 to 30% by weight. By setting the ratio of the epoxy-amine adduct within the above range, the reaction efficiency between the epoxy-amine adduct and the carboxyl group-terminated polyester is improved.
When two or more types of epoxy-amine adducts are used, the total amount (total amount) of all epoxy-amine adducts is preferably within the above range.

In the reaction between the epoxy-amine adduct and the carboxyl group-terminated polyester, the carboxyl in the total amount of raw materials for reaction (total amount of raw materials including the epoxy-amine adduct and the carboxyl group-terminated polyester) (100% by weight) The proportion of the base terminal polyester is not particularly limited, but is preferably 50 to 99% by weight, more preferably 60 to 95% by weight, and still more preferably 70 to 90% by weight. By setting the ratio of the carboxyl group-terminated polyester within the above range, the reaction efficiency between the epoxy-amine adduct and the carboxyl group-terminated polyester is improved.
In addition, when using 2 or more types of carboxyl group terminal polyester, it is preferable that the total amount of all the carboxyl group terminal polyesters exists in the said range.

In the reaction between the epoxy-amine adduct and the carboxyl group-terminated polyester, the ratio of the carboxyl group-terminated polyester to the epoxy-amine adduct (weight ratio, carboxyl group-terminated polyester / epoxy-amine adduct) is not particularly limited. Is preferably 1.01 to 10.00, more preferably 1.50 to 8.00, and still more preferably 2.00 to 6.00. By setting the ratio within the above range. The reaction efficiency between the epoxy-amine adduct and the carboxyl group-terminated polyester is improved.

The reaction between the epoxy-amine adduct and the carboxyl group-terminated polyester can be allowed to proceed in the presence of a solvent, or can be allowed to proceed in the absence of a solvent (ie, without solvent). Although it does not specifically limit as said solvent, For example, the solvent illustrated by reaction with the above-mentioned epoxy compound (A) and amine compound (B) is mentioned. The said solvent can also be used individually by 1 type, and can also be used in combination of 2 or more type. The usage-amount of the said solvent is not specifically limited, It can set suitably.

For the reaction between the epoxy-amine adduct and the carboxyl group-terminated polyester, for example, a polymerization initiator, a catalyst, a solvent, an antioxidant or the like may be used.

The reaction between the epoxy-amine adduct and the carboxyl group-terminated polyester can be carried out by a known or conventional method, and is not particularly limited. For example, the reaction between the epoxy-amine adduct and the carboxyl group-terminated polyester is performed. The reaction can be carried out by batch charging into the container, or either one of the epoxy-amine adduct and the carboxyl group-terminated polyester is charged into the reaction container, and the other is added (for example, the above-mentioned sequential addition) to react. You can also. Among them, from the viewpoint of obtaining a graft polymer having a more uniform composition, it is preferable to charge the carboxyl group-terminated polyester into a reaction vessel and charge the epoxy-amine adduct in a batch to react.

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

The above reaction can be carried out under normal pressure, under pressure or under reduced pressure. The atmosphere for carrying out the reaction is not particularly limited, but can be carried out in any atmosphere such as in an inert gas (for example, nitrogen, argon, etc.) or in the air. In addition, the above reaction may be performed with stirring or may not be performed.

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

After the above reaction, the graft polymer of the present invention is separated by known or conventional separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or a combination means combining these. It is possible to purify.

In the graft polymer of the present invention, amino groups in the epoxy-amine adduct (for example, amino groups at both ends of the epoxy-amine adduct) are eliminated by reaction with polyester (for example, carboxyl-terminated polyester). There may be. The graft polymer of the present invention may have an amino group (may be an amino group-containing graft polymer) or may not have an amino group.
The graft polymer of the present invention may have a secondary amino group (for example, —NH— group, etc.) in the main chain (for example, in the structure of an epoxy-amine adduct). The number of secondary amino groups is not particularly limited, and examples thereof include 1 to 1000 (preferably 2 to 800, more preferably 5 to 500, still more preferably 10 to 300).

The graft polymer of the present invention has a polyester structure as a side chain. When it has a plurality of side chains, the structure of each side chain may be the same or different. The polyester structure of the side chain is not particularly limited, but the structure of the carboxyl group-terminated polyester is preferable. Among these, a polyester structure represented by the following formula (3) or (4) is preferable.

R ¹¹ in the formula (3) and (4), and R ¹¹ in the formula (1), the same group. Among them, an alkylene group having 1 to 10 carbon atoms (preferably having a carbon number of 1 to 10 carbon atoms, preferably an alkyl group having 1 to 4 carbon atoms, and more preferably a methyl group) may be used as a substituent. 2-5 linear alkylene groups) are preferred.
R ¹¹ in the above formulas (3) and (4) may be the same or different. R ¹¹ in the formula (3) and (4) may be different or may be the same as R ¹¹ in the formula (1) and / or (2).

Examples of R ¹² in the above formulas (3) and (4) include groups derived from the monocarboxylic acid, the hydroxycarboxylic acid or the polyvalent carboxylic acid used for the synthesis of the carboxyl group-terminated polyester. R ¹² in the above formulas (3) and (4) may be the same or different.

In the above formula (3), w2 (the number of repeating structural units in parentheses to which w2 is attached) and w3 in the above formula (4) (the number of repeating structural units in parentheses to which w3 is attached) are 1 or more. And is preferably 1 to 100, more preferably 1 to 70, and still more preferably 1 to 30. In addition, when w2 and / or w3 are integers of 2 or more, R ¹¹ (plural R ¹¹ ) in each parenthesis may be the same or different. w2 and w3 may be the same or different. Moreover, when it has 2 or more types of R < ¹¹ >, the addition form (polymerization form) of the structure in the parenthesis attached | subjected to w2 or w3 may be a random type, and may be a block type.

Although the use of the graft polymer of the present invention is not particularly limited, it can be used as a pigment dispersant or other inorganic filler dispersant.

The graft polymer of the present invention comprises a reaction between an epoxy compound (A) having a main chain having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule. Because of the structure of the epoxy-amine adduct obtained by the above, the structure of the main chain can be changed variously depending on the type of epoxy compound or amine compound, the degree of freedom of the structure of the main chain is improved, and the graft polymer as a whole The dispersibility of the pigment is improved. Furthermore, the structural unit part derived from the epoxy compound (A) in the main chain and the structural unit part derived from the amine compound (B) have different properties, so that the dispersibility of the graft polymer as a whole can be improved. It is thought that it will be further improved. Moreover, since the graft polymer of this invention can change the structure of the amine adduct part in a principal chain, if an amine compound (B) is changed (for example, if the combination, a ratio, etc. of an amine compound (B) are changed). It is considered that it is easy to adjust wettability and adhesion to various base materials. In the case of having a polyester structure of a carboxyl group-terminated polyester as a side chain, a three-dimensional repellent layer is formed around the pigment to further improve dispersibility. In addition, the graft polymer of the present invention is excellent in storage stability and can form a dispersed state in a short time.

[Dispersant]
The dispersant of the present invention contains the graft polymer of the present invention. The dispersant of the present invention may be only the graft polymer of the present invention, or may contain other dispersible compounds. Especially, it is preferable that it is only the graft polymer of this invention from a viewpoint that it is excellent in the dispersibility with respect to a pigment.

Examples of the other dispersible compounds include, but are not limited to, anionic compounds such as sulfates, sulfonates, and phosphates, cationic compounds such as aliphatic amine salts, nonionic compounds, and polymer compounds. It is done.

The ratio of the graft polymer of the present invention in the dispersant of the present invention is not particularly limited, but is preferably 30 to 100% by weight, more preferably 40 to 95% by weight, based on the total amount of the dispersant (100% by weight). More preferably, it is 50 to 90% by weight.

The dispersant of the present invention may further contain a solvent, a leveling agent, an antifoaming agent, a surfactant, a flame retardant, an antioxidant, an antiseptic, and the like.

[Pigment composition]
By blending (mixing) the dispersant of the present invention and the pigment, a pigment composition (pigment dispersion composition) is obtained. That is, the pigment composition contains at least the graft polymer of the present invention and the pigment. The pigment composition may contain a dispersant other than the dispersant of the present invention.

The above pigments are not particularly limited, but include inorganic pigments such as titanium oxide, zinc oxide, cadmium sulfide, yellow iron oxide, red pepper, yellow lead, carbon black, phthalocyanines, insoluble azo pigments, azo lake pigments, condensed polycyclic systems. Pigments (slen, indigo, perylene, perinone, phthalone, dioxazine, quinacridone, isoindolinone, and diketopyrrolopyrrole pigments).

The pigment composition may contain a coating resin, a solvent, a leveling agent, an antifoaming agent, a surfactant, a flame retardant, an antioxidant, an antiseptic, and the like. Although it does not specifically limit as said resin for coating materials, An alkyd resin, oil free alkyd resin, an acrylic resin, a urethane resin, etc. are mentioned.

The content of the graft polymer of the present invention in the pigment composition is not particularly limited, but is preferably 1 to 50% by weight, more preferably 2 to 40% by weight with respect to the total amount of the pigment composition (100% by weight). More preferably, it is 3 to 30% by weight. By setting the content of the graft polymer in the above range, the dispersibility to the pigment tends to be improved.

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

In the above pigment composition, since the graft polymer of the present invention reacts with the pigment, the graft polymer hardly aggregates or crystallizes in the composition.

As described above, the graft polymer of the present invention exhibits excellent dispersibility (dispersion effect) for a wide variety of pigments. For this reason, the graft polymer of the present invention and the composition containing the same (for example, the above-mentioned dispersant, pigment composition, etc.) are, for example, a filter for fine color separation such as a liquid crystal panel, a thin film transistor side substrate of a liquid crystal panel, etc. A composition for a liquid crystal panel that can be used for: a composition for forming a black matrix in an optical color filter (a composition for forming a black matrix); a coloring composition for forming a color filter; and an oily black pigment writing instrument ink Obtained oily black content dispersion for writing instrument ink; Pigment dispersion containing colored pigment or carbon black (eg, pigment dispersant for paint); Dispersion containing carbon black and black photosensitive composition (eg, photocuring) Black photosensitive composition used for adhesive coatings, photo-curable adhesives, photoresists for printed boards and printed wiring boards, etc.) Active energy ray curable inkjet ink using carbon black; non-aqueous inkjet ink (non-aqueous ink composition); conductive material dispersion (for example, electrode paste in batteries and the like, conductive material dispersion for conductive material-coated active material) Electrophoretic dispersion liquid containing black electrophoretic particles (for example, image display medium, electrophoretic dispersion liquid for image display device); colored composition containing black color material (for example, titanium black) (for example, paint, plastic material) , Inks, coloring compositions for electronic component materials) and the like. By using the graft polymer of the present invention and the composition containing the same in these embodiments and applications, for example, color filters, electrode substrates, liquid crystal display devices (liquid crystal panels), oil-based black pigment writing instrument inks, writing instruments, paints (for example, , Solid paint, metallic paint), photocurable paint, photocurable adhesive, printing board, printed wiring board, inkjet ink (for example, active energy ray curable inkjet ink, non-aqueous inkjet ink), electrode paste, conductive material Coated active material, battery (for example, lithium ion battery) image display medium and image display device (for example, electronic paper) using black electrophoretic particles, plastic material, printing ink, thermal transfer ink, light shielding film, electrocapillary display device, electro Wetting display device, electrochromic display device, optical element ( Eg to optical shutters, optical pickup device, the various articles of a liquid optical lens) or the like is obtained. However, the usage mode and application of the graft polymer of the present invention and the composition containing the same are not limited to these.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.

(Production Example 1)
A 2 L reactor equipped with a condenser, a nitrogen introducing tube, a stirrer, a thermometer, and a dehydrating tube was charged with 171 g of lauric acid (manufactured by acidchem), 829 g of ε-caprolactone and 0.1 g of tetrabutyl titanate, and the nitrogen gas flowed under 200 The reaction was carried out at 0 ° C., and heating was performed until the remaining caprolactone was 1% or less to synthesize a carboxyl group-terminated polyester. The resulting carboxyl group-terminated polyester 1 (side chain 1) had an acid value of 48 KOH mg / g.

(Production Example 2)
A 2 L reactor equipped with a condenser, a nitrogen introducing tube, a stirrer, a thermometer and a dehydrating tube was charged with 723 g of ricinoleic acid, 277 g of ε-caprolactone and 2 g of tetrabutyl titanate, and the acid value of the reaction mixture was 50.5 mgKOH under a nitrogen stream. The mixture was stirred at 170 ° C. for 6 hours under a nitrogen atmosphere until it reached / g to synthesize carboxyl group-terminated polyester 2 (side chain 2, random copolymer).

(Production Example 3)
In a 2 L reactor equipped with a condenser, a nitrogen introduction tube, a stirrer, a thermometer and a dehydration tube, 747 g of condensed ricinoleic acid (trade name “HSC60D”, manufactured by Toyokuni Oil Co., Ltd.), 183 g of ε-caprolactone and tetrabutyl titanate 0 0.1 g was charged, reacted at 150 ° C. under a nitrogen stream, and heated until the remaining caprolactone was 1% or less to synthesize carboxyl group-terminated polyester 3 (side chain 3, block copolymer). The resulting carboxyl group-terminated polyester 3 had an acid value of 48 KOH mg / g.

(Production Example 4)
In a 1 L stainless steel reaction vessel, 372.0 g of an amine compound (triethylenetetramine (trade name “TETA”, manufactured by HUNTSMAN)) was placed, and the epoxy compound (3,4) was added thereto at 160 ° C. in a nitrogen atmosphere. 627.6 g of epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate (trade name “Celoxide 2021P”, manufactured by Daicel Corporation) was added dropwise over 60 minutes. Thereafter, the mixture was reacted by stirring at 200 ° C. for 3 hours and further at 220 ° C. for 2 hours to obtain an epoxy-amine adduct.
After allowing to cool, the content of the content is flowable (130 to 150 ° C.), and then poured out from the reaction vessel onto release paper, further cooled and solidified, and then pulverized to give an epoxy-amine 990 g of adduct 1 (amine adduct 1, main chain 1) was obtained.

(Production Example 5)
In a 1 L stainless steel reaction vessel, amine compound (triethylenetetramine (trade name “TETA”, manufactured by HUNTSMAN) 228.0 g and isophoronediamine (trade name “Vestamine IPD”, manufactured by Evonik Degussa Japan Co., Ltd.) 171.0 g In which the epoxy compound (3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate (trade name “Celoxide 2021P”, Co., Ltd.) was added at 160 ° C. in a nitrogen atmosphere. Manufactured by Daicel)) was added dropwise over a period of 60 minutes. Thereafter, the mixture was reacted by stirring at 200 ° C. for 3 hours and further at 220 ° C. for 2 hours to obtain an epoxy-amine adduct.
After allowing to cool, the content of the content is flowable (130 to 150 ° C.), and then poured out from the reaction vessel onto release paper, further cooled and solidified, and then pulverized to give an epoxy-amine 1000 g of adduct 2 (amine adduct 2, main chain 2) was obtained.

(Production Example 6)
In a 1 L stainless steel reaction vessel, 390.0 g of an amine compound (amine-terminated polypropylene glycol (trade name “JEFFAMINE D-230”, manufactured by HUNTSMAN)) was placed, and an epoxy compound (160 ° C.) was added thereto in a nitrogen atmosphere. 409.8 g of 3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate (trade name “Celoxide 2021P”, manufactured by Daicel Corporation) was added dropwise over 60 minutes. Thereafter, the mixture was reacted by stirring at 200 ° C. for 3 hours and further at 220 ° C. for 2 hours to obtain an epoxy-amine adduct.
After allowing to cool, the content of the content is flowable (130 to 150 ° C.), and then poured out from the reaction vessel onto release paper, further cooled and solidified, and then pulverized to give an epoxy-amine 790 g of adduct 3 (amine adduct 3, main chain 3) was obtained.

(Production Example 7)
In a 1 L stainless steel reaction vessel, amine compound (amine-terminated polypropylene glycol (trade name “JEFFAMINE D-230”, manufactured by HUNTSMAN) 120.0 g and isophoronediamine (trade name “Vestamine IPD”, manufactured by Evonik Degussa Japan Co., Ltd.) ) 120.0 g) and an epoxy compound (3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate (trade name “Celoxide 2021P”, manufactured by Daicel Corporation) 299.5 g, under nitrogen atmosphere An epoxy-amine adduct was obtained by reacting at 160 ° C. for 2 hours with stirring.
After allowing to cool, the content of the content is flowable (130 to 150 ° C.), and then poured out from the reaction vessel onto release paper, further cooled and solidified, and then pulverized to give an epoxy-amine 530 g of adduct 4 (amine adduct 4, main chain 4) was obtained.

(Production Example 8)
A 2 L reactor equipped with a condenser, a nitrogen introducing tube, a stirrer, a thermometer and a dehydrating tube was charged with 171 g of lauric acid (manufactured by acidchem), 441 g of ε-caprolactone, 387 g of δ-valerolactone and 0.1 g of tetrabutyl titanate. The mixture was reacted at 200 ° C. under a nitrogen stream and heated until the remaining caprolactone and valerolactone were 1% or less to synthesize a carboxyl-terminated polyester. The acid value of the resulting carboxyl group-terminated polyester 4 (side chain 4, random copolymer) was 48 KOH mg / g.

(Example 1)
Into a 1000 mL reactor equipped with a condenser, a nitrogen introducing tube, a stirrer and a thermometer, 856 parts of carboxyl group-terminated polyester 1 (side chain 1) were charged, and then 144 parts of epoxy-amine adduct 1 were charged and reacted at 120 ° C. It was. The reaction was stopped 8 hours after the start of the reaction to obtain a graft polymer.

(Examples 2 to 13)
With the composition shown in Table 1, a graft polymer was prepared by the same procedure as in Example 1.

[Evaluation]
The following evaluation was performed about the sample obtained in the Example.

(Acid value)
The acid value was measured according to JIS K-1557.

(Pigment dispersibility)
[Preparation of pigment paste with pigment dispersant]
Into the graft polymer obtained in Example 1 or a commercially available pigment dispersant (Solsperse 24000, manufactured by Lubrizol), a pigment and a solvent are blended in the blending amounts shown in Table 2, and glass beads are further added. After that, the glass beads were removed by filtration to obtain a pigment dispersion paste in which the pigment was dispersed with a pigment dispersant (graft polymer).
About the obtained pigment dispersion paste, the fluidity | liquidity of the pigment dispersion paste was visually evaluated on the following references | standards. The evaluation results are shown in Table 2. In addition, the numerical value in Table 2 shows a weight part.
Observe the filtration state and the viscosity of the filtrate when preparing the pigment dispersion paste. If the glass beads can be filtered and the fluidity is good, the dispersion is good. It was evaluated.

Claims (7)

Epoxy-amine obtained by reaction of an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule and an amine compound (B) having two or more amino groups in the molecule as the main chain Has the structure of an adduct,
A graft polymer having a polyester structure as a side chain. The amine compound (B) is represented by the following formula (b-1)

[Wherein, R ² and R ³ are the same or different and are each a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic hydrocarbon group. A divalent group in which the above and one or more cyclic aliphatic hydrocarbon groups are linked directly or via a linking group containing a hetero atom is shown. q represents 0 or an integer of 1 or more. ]
An amine compound (B1) represented by the following formula (b-2):

[Wherein, R ⁴ and R ⁵ are the same or different and are each a linear, branched or cyclic divalent aliphatic hydrocarbon group, or a linear or branched aliphatic hydrocarbon group. A divalent group formed by linking the above and one or more cyclic aliphatic hydrocarbon groups. r represents an integer of 1 or more. ]
And an amine compound (B2) represented by the following formula (b-3):

[Wherein, R ⁶ and R ⁸ are the same or different and each represents an alkylene group having 1 to 4 carbon atoms or an arylene group having 6 to 12 carbon atoms. s represents 0 or 1. R ⁷ represents a monovalent organic group, a monovalent oxygen atom-containing group, a monovalent sulfur atom-containing group, a monovalent nitrogen atom-containing group, or a halogen atom. t represents an integer of 0 to 10. ]
The graft polymer of Claim 1 containing the at least 1 sort (s) of amine compound selected from the group which consists of amine compound (B3) represented by these. The graft polymer according to 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 structure of a carboxyl group-terminated polyester obtained by ring-opening polymerization of ε-caprolactone as the polyester structure in the side chain. The graft polymer according to any one of claims 1 to 3, which has a carboxyl group-terminated polyester structure obtained by ring-opening copolymerization of ε-caprolactone and δ-valerolactone as the polyester structure in the side chain. A dispersant containing the graft polymer according to any one of claims 1 to 5. An epoxy-amine adduct obtained by reacting an epoxy compound (A) having two or more alicyclic epoxy groups in the molecule with an amine compound (B) having two or more amino groups in the molecule; The method for producing a graft polymer according to any one of claims 1 to 5, wherein a carboxyl group-terminated polyester is reacted.