JP2008222843A - Polymer compound and its manufacturing method, aqueous pigment dispersant, aqueous pigment dispersion composition, and aqueous ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer compound exhibiting excellent pigment-dispersing properties and dispersing stability. <P>SOLUTION: The polymer compound is represented by general formula (1) [wherein R<SP>1</SP>is an (m+n)-valent organic linking group; R<SP>2</SP>is a single bond or a bivalent organic linking group; A<SP>1</SP>is a monovalent organic group containing at least one portion selected from among an organic pigment structure, heterocyclic structure, acidic group, group having a basic nitrogen atom, urea group, urethane group, group having a coordinative oxygen atom, 4C or higher hydrocarbon group, alkoxysilyl group, epoxy group, isocyanate group, hydroxy group and ionic functional group (wherein n pieces of A<SP>1</SP>s and R<SP>2</SP>s may be each independently the same or different); m is 1-8; n is 2-9; (m+n) is 3-10; P<SP>1</SP>is a polymer skeleton (when A<SP>1</SP>is a monovalent organic group containing no ionic functional group, P<SP>1</SP>is an ionic polymer skeleton and m pieces of P<SP>1</SP>s may be the same or different)]. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel polymer compound and a production method thereof, an aqueous pigment dispersant, an aqueous pigment dispersion composition, and an aqueous ink.

  In recent years, paints and inks (hereinafter also referred to as “inks”) are becoming water-based due to increasing needs such as resource protection, environmental protection, and improvement of work stability. The quality required for water-based paints and water-based inks is fluidity, storage stability, gloss of film, vividness, coloring power and the like, similar to oil-based paints and oil-based inks. However, since most pigments are remarkably inferior in suitability for pigment dispersibility and the like as compared with an oily vehicle with respect to an aqueous vehicle, satisfactory quality cannot be obtained by a normal dispersion method. Therefore, the use of various additives such as aqueous pigment dispersion resins and surfactants has been studied so far, but they satisfy all the above-mentioned suitability and are comparable to existing high-quality oil-based paints or oil-based inks. No water-based paint or water-based ink has been obtained.

  In order to solve such a problem, for example, a polymer-type dispersant in which an organic dye such as anthraquinone is introduced at the end of a polymer portion has been proposed (for example, see Patent Documents 1 and 2). In Patent Documents 1 and 2, an organic dye or a heterocyclic ring is efficiently adsorbed on the pigment surface, and a sufficient adsorbent layer for dispersion stabilization is secured by giving sufficient affinity between the polymer portion and the dispersion medium. By using a chain transfer agent having an organic dye, it is said that it is industrially advantageous in terms of productivity.

In addition, graft copolymers composed of a hydrophobic macromonomer and a hydrophilic monomer composed of aromatic monomers such as styrene and vinyltoluene and (meth) acrylic acid esters, and (meth) acrylic acid, maleic A graft copolymer composed of a hydrophilic macromonomer containing monomers such as acid and (meth) acrylhydroxyalkylesters and a hydrophobic monomer is known (for example, Patent Document 3).
Similarly, a pigment dispersant (for example, a patent dispersant consisting of an acrylic acid graft copolymer having a main chain composed of a hydrophobic (meth) acrylic acid monomer and an anionic and nonionic hydrophilic side chain bonded to the main chain. Document 4) and water-based inks composed of a graft copolymer having a side chain of a (meth) acrylic macromer having a polymer composed of a cation or anion monomer as a skeleton are disclosed (for example, Patent Document 5). .
JP-A-9-77985 JP-A-9-77993 JP-A-6-100810 JP 2002-179978 A JP 2001-247796 A

However, in the polymer type dispersants described in Patent Documents 1 and 2, a plurality of organic dyes are not introduced at the ends of the polymer, and the introduction is difficult, and the adsorption to the pigment surface is sufficiently strong. Is hard to say. Therefore, there may be a case where a sufficient adsorption layer for dispersion stabilization cannot be secured.
Further, in the case of the aqueous ink using the graft copolymer of Patent Document 3, it cannot be said that the dispersion stability of the colorant is sufficient, and it is particularly difficult to stably disperse carbon black in the aqueous medium. In addition, in the case of the dispersants described in Patent Document 4 and Patent Document 5, it is necessary to introduce a lot of hydrophilic side chains in order to make the graft copolymer water-soluble. However, there is a problem that it cannot be manufactured at low cost.

  The present invention has been made in view of the above, and provides a polymer compound excellent in dispersibility and dispersion stability of a pigment, and a production method capable of industrially producing the polymer compound, and a high pigment. An object is to provide a water-based pigment dispersant, a water-based pigment dispersion composition, and a water-based ink having dispersibility and dispersion stability, and an object is to achieve the object.

  In the present invention, introduction of a plurality of structures or functional groups capable of adsorbing pigments at the ends of the polymer is effective in improving dispersibility when used as an aqueous pigment dispersant and dispersion stability after dispersion. In addition, the introduction of a plurality of the above-mentioned structures or functional groups at the end of the polymer is because the use of a polyfunctional mercaptan compound increases the degree of structural freedom in consideration of ease of synthesis and steric repulsion. The knowledge that it was useful was obtained, and it was achieved based on this knowledge. Specific means for achieving the above object are as follows.

<1> A polymer compound represented by the following general formula (1).

In the formula, R ¹ represents an (m + n) -valent organic linking group, and R ² represents a single bond or a divalent organic linking group. A ¹ is an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, A monovalent organic group containing at least one site selected from an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group. n A ¹ and R ² may be the same or different independently. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer skeleton. However, when A ¹ is a monovalent organic group containing at least one ionic functional group, P ¹ may be a nonionic polymer skeleton or an ionic polymer skeleton. ^{When 1} is a monovalent organic group not containing an ionic functional group, P ¹ represents an ionic polymer skeleton. The m P ¹ may be the same or different.

<2> The polymer compound according to <1>, which is represented by the following general formula (2).

In the formula, R ³ represents an (m + n) -valent organic linking group, and R ⁴ and R ⁵ each independently represents a single bond or a divalent organic linking group. A ² represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, A monovalent organic group containing at least one site selected from an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group. n A ² and R ⁴ may be the same or different independently. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ² represents a polymer skeleton. However, when A ² is a monovalent organic group containing at least one ionic functional group, P ² may be a nonionic polymer skeleton or an ionic polymer skeleton. ^{When 2} is a monovalent organic group not containing an ionic functional group, P ² represents an ionic polymer skeleton. m P ² and R ⁵ may be the same or different independently.

<3> The A ¹ is a monovalent organic group including at least one portion selected from an organic dye structure, a heterocyclic structure, a hydrocarbon group having 4 or more carbon atoms, and an ionic functional group. <1> The polymer compound according to <1>.
<4> The A ² is a monovalent organic group including at least one portion selected from an organic dye structure, a heterocyclic structure, a hydrocarbon group having 4 or more carbon atoms, and an ionic functional group. The polymer compound according to <2>.

<5> The polymer compound according to <1> or <3>, wherein the polymer skeleton represented by P ¹ is a polymer or copolymer of a vinyl monomer.
<6> polymer backbone represented by P ² is a polymer compound according to, which is a polymer or copolymer of a vinyl monomer <2> or <4>.
<7> The polymer compound according to any one of <1> to <6>, wherein the weight average molecular weight is 3000 to 100,000.

<8> The polymer according to any one of <1> to <7>, which is obtained by performing a radical polymerization reaction in the presence of a compound represented by the following general formula (3): A compound.

In the formula, R ⁶ represents an (m + n) -valent organic linking group, and R ⁷ represents a single bond or a divalent organic linking group. A ³ is an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group Represents a monovalent organic group containing at least one site selected from an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group. n A ³ and R ⁷ may be the same or different independently. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10.

<9> A method for producing a polymer compound according to any one of <1> to <8>, wherein a radical polymerization reaction is performed in the presence of a compound represented by the following general formula (3). This is a method for producing a characteristic polymer compound.

In the formula, R ⁶ represents an (m + n) -valent organic linking group, and R ⁷ represents a single bond or a divalent organic linking group. A ³ is an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group Represents a monovalent organic group containing at least one site selected from an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group. n A ³ and R ⁷ may be the same or different independently. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10.

<10> The compound represented by the general formula (3) is:
(A) a compound having 3 to 10 mercapto groups in one molecule;
(B) an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, A compound having at least one site selected from an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group, and a functional group capable of reacting with a mercapto group;
<9> The method for producing a polymer compound according to <9>, which is an addition reaction product of

<11> An aqueous pigment dispersant containing the polymer compound according to any one of <1> to <8>.
<12> An aqueous pigment dispersion composition containing the pigment and the aqueous pigment dispersant described in <11> in an aqueous medium.
<13> An aqueous ink comprising the aqueous pigment dispersion composition according to <12>.
<14> The water-based ink according to <13>, which is for inkjet recording.

  According to the present invention, it is possible to provide a polymer compound excellent in pigment dispersibility and dispersion stability, and a production method capable of industrially producing the polymer compound, and achieve high pigment dispersibility and dispersion stability. An aqueous pigment dispersant, an aqueous pigment dispersion composition, and a water-based ink having a low viscosity and excellent storage stability can be provided.

Hereinafter, the present invention will be described in detail.
<Polymer compound>
The polymer compound of the present invention is a polymer compound represented by the following general formula (1). The polymer compound represented by the following general formula (1) has an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, and a coordinating oxygen atom at the end of the polymer. A plurality of monovalent organic groups containing at least one site selected from a group having a carbon number, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group. It has various characteristics such as excellent adsorbability on the surface, excellent micelle formation ability, surface activity, and the like. For example, it can be suitably used as an aqueous pigment dispersant.

In the general formula (1), A ¹ represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms. Represents a monovalent organic group containing at least one portion selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group. The n A ¹ may be the same or different.

That is, the A ¹ has a structure capable of adsorbing to a pigment such as an organic dye structure or a heterocyclic structure, an acid group, a group having a basic nitrogen atom, a urea group, a urethane group, or a coordinating oxygen atom. A monovalent organic group containing at least one functional group capable of adsorbing to a pigment, such as a group, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group. To express.
Hereinafter, the site having the ability to adsorb to the pigment (the above structure and functional group) will be collectively referred to as “adsorption site” as appropriate.

The adsorption sites are in one A ^1, it may be contained at least one, may contain two or more kinds.
Further, in the present invention, the “monovalent organic group containing at least one kind of adsorption site” means the above-mentioned adsorption site, 1 to 200 carbon atoms, 0 to 20 nitrogen atoms, 0 to It is a monovalent organic group formed by bonding up to 100 oxygen atoms, 1 to 400 hydrogen atoms, and an organic linking group consisting of 0 to 40 sulfur atoms. In the case where adsorption sites themselves may constitute a monovalent organic group, adsorption sites itself may be a monovalent organic group represented by A ^1.
First, the adsorption site constituting A ¹ will be described below.

  Examples of the “organic dye structure” include phthalocyanine, insoluble azo, azo lake, anthraquinone, quinacridone, dioxazine, diketopyrrolopyrrole, anthrapyridine, anthanthrone, indanthrone, flavan. Examples of preferable dye structures of throne, perinone, perylene, and thioindigo are phthalocyanine, azo lake, anthraquinone, dioxazine, and diketopyrrolopyrrole, and phthalocyanine and anthraquinone. A diketopyrrolopyrrole dye structure is particularly preferred.

  Examples of the “heterocyclic structure” include thiophene, furan, xanthene, pyrrole, pyrroline, pyrrolidine, dioxolane, pyrazole, pyrazoline, pyrazolidine, imidazole, oxazole, thiazole, oxadiazole, triazole, thiadiazole, pyran, pyridine. , Piperidine, dioxane, morpholine, pyridazine, pyrimidine, piperazine, triazine, trithiane, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, indole, quinoline, carbazole, acridine, acridone, Anthraquinone is mentioned as a preferred example, pyrroline, pyrrolidine, pyrazole, pyrazoline, pyrazolidine, imidazole, Riazor, pyridine, piperidine, morpholine, pyridazine, pyrimidine, piperazine, triazine, isoindoline, isoindolinone, benzimidazolone, benzothiazole, succinimide, phthalimide, naphthalimide, hydantoin, carbazole, acridine, acridone, anthraquinone are more preferable.

  The “organic dye structure” or “heterocyclic structure” may further have a substituent. Examples of the substituent include alkyl groups having 1 to 20 carbon atoms such as a methyl group and an ethyl group. An acyloxy group having 1 to 6 carbon atoms, such as an aryl group having 6 to 16 carbon atoms such as a hydroxyl group, a phenyl group or a naphthyl group, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group or an acetoxy group. Alkoxy groups having 1 to 20 carbon atoms such as methoxy group and ethoxy group, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group , A cyano group, a carbonate group such as t-butyl carbonate, and the like. Here, these substituents may be bonded to the organic dye structure or the heterocyclic ring through the following structural unit or a linking group formed by combining the structural units.

  Preferred examples of the “acidic group” include a carboxylic acid group, a sulfonic acid group, a monosulfate group, a phosphoric acid group, a monophosphate group, and a boric acid group. Sulfuric acid ester groups, phosphoric acid groups, and monophosphoric acid ester groups are more preferable, and carboxylic acid groups, sulfonic acid groups, and phosphoric acid groups are particularly preferable.

Examples of the “group having a basic nitrogen atom” include an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), a guanidyl group represented by the following formula (a1), Preferred examples include the amidinyl group represented by a2).

In formula (a1), R ¹¹ and R ¹² each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.
In formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.

Among these, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ each independently has 1 to 10 carbon atoms. An alkyl group, a phenyl group, and a benzyl group.), A guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 10 carbon atoms. Represents a phenyl group or a benzyl group. ] An amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 10 carbon atoms, a phenyl group, or a benzyl group. ] Is more preferable.
In particular, an amino group (—NH ₂ ), a substituted imino group (—NHR ⁸ , —NR ⁹ R ¹⁰ , wherein R ⁸ , R ⁹ , and R ¹⁰ are each independently an alkyl group having 1 to 5 carbon atoms. , A phenyl group and a benzyl group.), A guanidyl group represented by the formula (a1) [in the formula (a1), R ¹¹ and R ¹² are each independently an alkyl group having 1 to 5 carbon atoms, phenyl Represents a benzyl group. ] An amidinyl group represented by the formula (a2) [in the formula (a2), R ¹³ and R ¹⁴ each independently represents an alkyl group having 1 to 5 carbon atoms, a phenyl group, or a benzyl group. Etc. are preferably used.

Examples of the “urea group” include —NR ¹⁵ CONR ¹⁶ R ¹⁷ (wherein R ¹⁵ , R ¹⁶ , and R ¹⁷ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a carbon number, Preferred examples include aryl groups having 6 or more and aralkyl groups having 7 or more carbon atoms, and —NR ¹⁵ CONHR ¹⁷ (wherein R ¹⁵ and R ¹⁷ are each independently a hydrogen atom or 1 carbon atom). More preferably an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms.) —NHCONHR ¹⁷ (wherein R ¹⁷ represents a hydrogen atom or 1 to 10 carbon atoms) An alkyl group, an aryl group having 6 or more carbon atoms, and an aralkyl group having 7 or more carbon atoms are particularly preferable.

Examples of the “urethane group” include —NHCOOR ¹⁸ , —NR ¹⁹ COOR ²⁰ , —OCONHR ²¹ , —OCONR ²² R ²³ (where R ¹⁸ , R ¹⁹ , R ²⁰ , R ²¹ , R ²² and R ²³ are Each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like. -NHCOOR ¹⁸ , -OCONHR ²¹ (here And R ¹⁸ and R ²¹ each independently represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 or more carbon atoms, or an aralkyl group having 7 or more carbon atoms), and the like, more preferably —NHCOOR ¹⁸ , -OCONHR ^{21 (wherein,} R ^{18, R 21} each independently represents an alkyl group having from 1 to 10 carbon atoms, having 6 or more ant carbon Group, represents a number of 7 or more aralkyl group having a carbon.), Etc. are particularly preferred.

  Examples of the “group having a coordinating oxygen atom” include an acetylacetonato group and a crown ether.

  Preferred examples of the “hydrocarbon group having 4 or more carbon atoms” include an alkyl group having 4 or more carbon atoms, an aryl group having 6 or more carbon atoms, an aralkyl group having 7 or more carbon atoms, and the like. More preferred are an alkyl group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an alkyl group having 4 to 15 carbon atoms (for example, an octyl group, a dodecyl group, etc.), and an aryl having 6 to 15 carbon atoms. A group (for example, phenyl group, naphthyl group, etc.), an aralkyl group having 7 to 15 carbon atoms (for example, benzyl group, etc.) and the like are particularly preferable.

  Examples of the “alkoxysilyl group” include a trimethoxysilyl group and a triethoxysilyl group.

Examples of the “ionic functional group” include an anionic functional group such as an alkali metal salt of the “acidic group” and a salt of the “acidic group” and an organic amine.
The alkali metal salt of an acidic group, Na salts, such as K salts can be ^{mentioned, -COO - Na +, -COO -} K +, -SO 3 - Na +, a salt with an acidic group and an organic amine include an equal ^{the, -COO - HN + R 32 R} 33 R 34, -SO 3 - in ^{HN + R 35 R 36 R 37} (R 32, R 33, R 34, R 35, R 36, R 37 are each independently, A hydrogen atom or a substituent (for example, a hydroxyl group, a sulfonamide group, an N-sulfonylamide group, an acyloxy group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 7 carbon atoms) Group, a cyano group, a carbonate group, etc.) Moreover, the salt represented by the following general formula is also mentioned suitably as a cationic functional group.

R ⁴⁸ , R ⁴⁹ , R ⁵⁰ and R ⁵¹ may each independently have a hydrogen atom or a substituent, and may be linked to form a saturated or unsaturated cyclic structure. To 18 alkyl groups, aryl groups, and aralkyl groups.
X ⁻ represents an organic acid anion such as a halogen anion (eg, Cl ⁻ , Br ⁻ , I ⁻ ), R ⁵² COO ⁻ , R ⁵³ SO ₃ ^— (R ⁵² and R ⁵³ each independently has a substituent). Or an anion such as an alkyl group having 1 to 18 carbon atoms, an aryl group, or an aralkyl group, which may be linked to form a saturated or unsaturated cyclic structure.
Z represents an atomic group that forms a heterocyclic group with nitrogen.

The organic linking group bonded to the adsorption site may be a single bond or 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200. An organic linking group consisting of up to 20 hydrogen atoms and 0 to 20 sulfur atoms is preferred, and this organic linking group may be unsubstituted or may further have a substituent.
Specific examples of the organic linking group include the following structural units or groups formed by combining the structural units.

  When the organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, and a carbon group having 6 to 16 carbon atoms such as a phenyl group and a naphthyl group. C1-C6 alkoxy such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide group, acetoxy group, etc., C1-C6 acyloxy group, methoxy group, ethoxy group, etc. Group, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group and cyclohexyloxycarbonyl group, carbonate groups such as cyano group and t-butyl carbonate, etc. Can be mentioned.

In the above, A ¹ is a monovalent organic group including at least one site selected from an organic dye structure, a heterocyclic structure, a hydrocarbon group having 4 or more carbon atoms, and an ionic functional group. preferable.

The A ¹ is more preferably a monovalent organic group represented by the following general formula (4).

In the general formula (4), B ¹ represents the adsorption site (that is, an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, or a group having a coordinating oxygen atom). And a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group, and an ionic functional group), and R ²⁴ is a single bond or an (a + 1) -valent organic linking group. Represents. a represents an integer of 1 to 10, and a number of B ¹ may be the same or different.

Examples of the adsorption site represented by B ¹ include the same examples as the adsorption site constituting A ¹ in the general formula (1) described above, and preferred examples are also the same.
Among these, a site selected from an organic dye structure, a heterocyclic structure, a hydrocarbon group having 4 or more carbon atoms, and an ionic functional group is preferable.

R ²⁴ represents a single bond or an (a + 1) -valent organic linking group, and a represents 1 to 10. Preferably, a is 1-7, more preferably, a is 1-5, and particularly preferably, a is 1-3.
(A + 1) valent organic linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, And groups consisting of 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.

  Specific examples of the (a + 1) -valent organic linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure).

R ²⁴ may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and An (a + 1) valent organic linking group consisting of 0 to 10 sulfur atoms is preferred, a single bond or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 More preferred are (a + 1) valent organic linking groups consisting of up to 1 oxygen atom, 1 to 50 hydrogen atoms, and 0 to 7 sulfur atoms, a single bond, or 1 to 10 (A + 1) valence consisting of 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms The organic linking group is particularly preferred.

  Among the above, when the (a + 1) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, a naphthyl group, and the like. Such as an aryloxy group having 6 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups, and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl carbonate And the like, and the like.

In the general formula (1), R ² represents a single bond or a divalent organic linking group. n R ² may be the same or different.
The divalent organic linking group includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to 200 hydrogen atoms, and 0 Groups comprising from 20 to 20 sulfur atoms are included and may be unsubstituted or further substituted.

  Specific examples of the divalent organic linking group include the following structural units or groups formed by combining the structural units.

R ² may be a single bond or 1 to 50 carbon atoms, 0 to 8 nitrogen atoms, 0 to 25 oxygen atoms, 1 to 100 hydrogen atoms, and Divalent organic linking groups consisting of 0 to 10 sulfur atoms are preferred, single bond or 1 to 30 carbon atoms, 0 to 6 nitrogen atoms, 0 to 15 And more preferably a divalent organic linking group consisting of 1 to 50 hydrogen atoms and 0 to 7 sulfur atoms, a single bond or 1 to 10 carbon atoms, A divalent organic linking group consisting of 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms, in particular preferable.

  Among the above, when the divalent organic linking group has a substituent, examples of the substituent include carbon having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a carbon such as a phenyl group and a naphthyl group. Carbon number such as acyloxy group having 1 to 6 carbon atoms such as aryl group, hydroxyl group, amino group, carboxyl group, sulfonamido group, N-sulfonylamido group, acetoxy group, etc., methoxy group, ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl group, ethoxycarbonyl group, cyclohexyloxycarbonyl group, cyano group, t-butyl carbonate, etc. And carbonate ester groups.

In the general formula (1), R ¹ represents an (m + n) -valent organic linking group. m + n satisfies 3-10.
The (m + n) -valent organic linking group represented by R ¹ includes 1 to 100 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups consisting of up to 200 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.

  Specific examples of the (m + n) -valent organic linking group include the following structural units or groups formed by combining the structural units (which may form a ring structure).

  The (m + n) -valent organic linking group includes 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 40 oxygen atoms, and 1 to 120 hydrogen atoms. And groups consisting of 0 to 10 sulfur atoms are preferred, 1 to 50 carbon atoms, 0 to 10 nitrogen atoms, 0 to 30 oxygen atoms, 1 to 100 More preferred are groups consisting of up to 0 hydrogen atoms and 0 to 7 sulfur atoms, 1 to 40 carbon atoms, 0 to 8 nitrogen atoms, 0 to 20 oxygen atoms. Particularly preferred are groups consisting of atoms, 1 to 80 hydrogen atoms, and 0 to 5 sulfur atoms.

  Among the above, when the (m + n) -valent organic linking group has a substituent, examples of the substituent include an alkyl group having 1 to 20 carbon atoms such as a methyl group and an ethyl group, a phenyl group, and a naphthyl group. Such as an aryloxy group having 6 to 16 carbon atoms, a hydroxyl group, an amino group, a carboxyl group, a sulfonamide group, an N-sulfonylamide group, an acetoxy group and the like, an acyloxy group having 1 to 6 carbon atoms, a methoxy group, an ethoxy group, etc. Alkoxy groups having 1 to 6 carbon atoms, halogen atoms such as chlorine and bromine, alkoxycarbonyl groups having 2 to 7 carbon atoms such as methoxycarbonyl groups, ethoxycarbonyl groups, and cyclohexyloxycarbonyl groups, cyano groups, and t-butyl carbonate And the like, and the like.

Specific examples (specific examples (1) to (17)) of the (m + n) -valent organic linking group represented by R ¹ are shown below. However, the present invention is not limited to these.

  Among the above specific examples, the most preferable (m + n) -valent organic linking group is the following group from the viewpoint of availability of raw materials, ease of synthesis, and solubility in various solvents.

In said general formula (1), m represents 1-8. As m, 1-5 are preferable, 1-4 are more preferable, and 1-3 are especially preferable.
Moreover, in said general formula (1), n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

In the general formula (1), P ¹ represents a polymer skeleton and can be selected from known polymers according to the purpose and the like. However, when A ¹ is a monovalent organic group containing at least one ionic functional group, P ¹ may be a nonionic polymer skeleton or an ionic polymer skeleton. ^{When 1} is a monovalent organic group not containing an ionic functional group, P ¹ represents an ionic polymer skeleton. The m P ¹ may be the same or different.

Among the polymers, in constituting the polymer skeleton represented by P ^1, the polymer or copolymer of vinyl monomers, ester polymers, ether-based polymer, urethane polymer, an amide polymer, an epoxy polymer, Silicone-based polymers, and modified products or copolymers thereof [eg, polyether / polyurethane copolymers, copolymers of polyether / vinyl monomers, etc. (random copolymers, block copolymers, grafts, etc. Any of copolymers may be included). At least one selected from the group consisting of: a vinyl monomer polymer or copolymer, an ester polymer, an ether polymer, a urethane polymer, and a modified product or copolymer thereof. At least one kind is more preferred, and a polymer or copolymer of vinyl monomers is particularly preferred.

  Furthermore, the polymer is preferably dispersible in an aqueous medium (hereinafter also referred to as “aqueous solvent”) or soluble in an aqueous solvent. When the polymer is dispersible in an aqueous solvent or soluble in an aqueous solvent, for example, when used as an aqueous pigment dispersant, it can more effectively improve the affinity with a dispersion medium, Adsorption layer sufficient for dispersion stabilization can be ensured.

  As the aqueous solvent, water, a water-soluble organic solvent or a mixed solvent thereof is suitable. The water is preferably ion exchange water (deionized water) or distilled water. Examples of the water-soluble organic solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol and other alkyl alcohols having 1 to 4 carbon atoms, dimethylformamide, Amides such as dimethylacetamide, ketones or ketoalcohols such as acetone and diacetone alcohol, ethers such as tetrahydrofuran and dioxane, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, ethylene glycol, propylene glycol, butylene glycol, Ethylene glycol, 1,2-hexanediol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethyleneglycol Polyhydric alcohols (preferably alkylene glycols in which the alkylene group contains 2 to 6 carbon atoms), glycerin, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl And lower alkyl ethers of polyhydric alcohols such as (or ethyl) ether, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. Among these water-soluble organic solvents, water, polyhydric alcohols such as diethylene glycol (preferably alkylene glycols in which the alkylene group contains 2 to 6 carbon atoms), triethylene glycol monomethyl (or butyl) ether, etc. Preferred are lower alkyl ethers of monohydric alcohols and mixed solvents thereof.

The polymer or copolymer of the vinyl monomer will be described.
Although it does not restrict | limit especially as said vinyl monomer, For example, the vinyl monomer which has an acidic group, a nitrogen-containing vinyl monomer, an ionic vinyl monomer (anionic vinyl monomer, cationic vinyl monomer), (meth) acrylic acid esters, croton Acid esters, vinyl esters, maleic acid diesters, fumaric acid diesters, itaconic acid diesters, (meth) acrylamides, styrenes, vinyl ethers, vinyl ketones, olefins, maleimides, (meth) acrylonitrile, etc. Is preferred.

Hereinafter, preferable examples of these vinyl monomers will be described.
Examples of the vinyl monomer having an acidic group include (meth) acrylic acid, vinyl benzoic acid, maleic acid, maleic acid monoalkyl ester, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid. And acrylic acid dimer. Further, addition reaction product of a monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate and a cyclic anhydride such as maleic anhydride, phthalic anhydride, or cyclohexanedicarboxylic anhydride, ω-carboxy-polycaprolactone Mono (meth) acrylates can also be used. Moreover, you may use anhydride containing monomers, such as maleic anhydride, itaconic anhydride, and citraconic anhydride, as a precursor of a carboxyl group.

  Moreover, as a vinyl monomer which has a sulfonic acid group, 2-acrylamido-2-methylpropane sulfonic acid, styrene sulfonic acid, 3-sulfopropyl (meth) acrylic acid ester, sulfuric acid monoester of 2-hydroxyethyl (meth) acrylic acid Examples of the vinyl monomer having a phosphate group include phosphoric acid mono (2-acryloyloxyethyl ester), phosphoric acid mono (1-methyl-2-acryloyloxyethyl ester), and the like.

As an example of nitrogen-containing vinyl monomer,
Examples of the monomer having a heterocyclic ring include vinyl pyridine, vinyl imidazole, vinyl triazole, and the like as (meth) acrylic acid ester, (meth) acrylic acid N, N-dimethylaminoethyl, (meth) acrylic acid N, N- Dimethylaminopropyl, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylate, N, N-dimethylaminohexyl (meth) acrylate, N, N-diethylamino (meth) acrylate Ethyl, (meth) acrylic acid N, N-diisopropylaminoethyl, (meth) acrylic acid N, N-di-n-butylaminoethyl, (meth) acrylic acid N, N-di-i-butylaminoethyl, ( Morpholinoethyl (meth) acrylate, piperidinoethyl (meth) acrylate, 1-pyrrole (meth) acrylate Noethyl, N, N-methyl-2-pyrrolidylaminoethyl (meth) acrylate, N, N-methylphenylaminoethyl (meth) acrylate, and the like. As (meth) acrylamides, N- (N ′ , N′-dimethylaminoethyl) acrylamide, N- (N ′, N′-dimethylaminoethyl) methacrylamide, N- (N ′, N′-diethylaminoethyl) acrylamide, N- (N ′, N′-diethylamino) Ethyl) methacrylamide, N- (N ′, N′-dimethylaminopropyl) acrylamide, N- (N ′, N′-dimethylaminopropyl) methacrylamide, N- (N ′, N′-diethylaminopropyl) acrylamide, N- (N ′, N′-diethylaminopropyl) methacrylamide, 2- (N, N-dimethylamino) ethyl (meth) acrylate Luamide, 2- (N, N-diethylamino) ethyl (meth) acrylamide, 3- (N, N-diethylamino) propyl (meth) acrylamide, 3- (N, N-dimethylamino) propyl (meth) acrylamide, 1- (N, N-dimethylamino) -1,1-dimethylmethyl (meth) acrylamide and 6- (N, N-diethylamino) hexyl (meth) acrylamide, morpholino (meth) acrylamide, piperidino (meth) acrylamide, N-methyl -2-pyrrolidyl (meth) acrylamide and the like, and examples of styrenes include N, N-dimethylaminostyrene, N, N-dimethylaminomethylstyrene and the like.

  Examples of ionic vinyl monomers (anionic vinyl monomers, cationic vinyl monomers) include, as anionic vinyl monomers, alkali metal salts of vinyl monomers having the acidic group, organic amines (for example, triethylamine, dimethylaminoethanol, etc.) And a tertiary amine), and the like.

  As the cationic vinyl monomer, the nitrogen-containing vinyl monomer is an alkyl halide (alkyl group: C1-18, halogen atom: chlorine atom, bromine atom or iodine atom); benzyl halide such as benzyl chloride, benzyl bromide; Alkylsulfonic acid esters such as methanesulfonic acid (alkyl group: C1-18); arylsulfonic acid alkyl esters such as benzenesulfonic acid and toluenesulfonic acid (alkyl group: C1-18); dialkyl sulfate (alkyl group: C1-4) ) And the like, and dialkyl diallylammonium salts.

  Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, and n-butyl (meth) acrylate. , Isobutyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, t-butylcyclohexyl (meth) acrylate, (Meth) acrylic acid 2-ethylhexyl, (meth) acrylic acid t-octyl, (meth) acrylic acid dodecyl, (meth) acrylic acid octadecyl, (meth) acrylic acid acetoxyethyl, (meth) acrylic acid phenyl, (meth) 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, (meth 3-hydroxypropyl acrylate, 4-hydroxybutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 2- (2-methoxyethoxy) (meth) acrylate Ethyl, 3-methoxy-2-hydroxypropyl (meth) acrylate, 2-chloroethyl (meth) acrylate, glycidyl (meth) acrylate, 3,4-epoxycyclohexylmethyl (meth) acrylate, (meth) acrylic acid Vinyl, 2-phenylvinyl (meth) acrylate, 1-propenyl (meth) acrylate, allyl (meth) acrylate, 2-allyloxyethyl (meth) acrylate, propargyl (meth) acrylate, (meth) acrylic Benzyl acid, (meth) acrylic acid diethylene glycol monomethyl ether (Meth) acrylic acid diethylene glycol monoethyl ether, (meth) acrylic acid triethylene glycol monomethyl ether, (meth) acrylic acid triethylene glycol monoethyl ether, (meth) acrylic acid polyethylene glycol monomethyl ether, (meth) acrylic acid polyethylene glycol Monoethyl ether, β-phenoxyethoxyethyl (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, (meth) acrylic acid Trifluoroethyl, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, dicyclopentanyl (meth) acrylate, (meth) acrylic Tribromophenyl, (meth) tribromophenyl oxyethyl acrylate, and (meth) acrylic acid γ- butyrolactone.

Examples of crotonic acid esters include butyl crotonate and hexyl crotonate.
Examples of vinyl esters include vinyl acetate, vinyl chloroacetate, vinyl propionate, vinyl butyrate, vinyl methoxyacetate, vinyl benzoate, and the like.
Examples of maleic acid diesters include dimethyl maleate, diethyl maleate, and dibutyl maleate.
Examples of the fumaric acid diesters include dimethyl fumarate, diethyl fumarate, and dibutyl fumarate.
Examples of itaconic acid diesters include dimethyl itaconate, diethyl itaconate, and dibutyl itaconate.

  (Meth) acrylamides include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and Nn-butyl. Acrylic (meth) amide, Nt-butyl (meth) acrylamide, N-cyclohexyl (meth) acrylamide, N- (2-methoxyethyl) (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N -Diethyl (meth) acrylamide, N-phenyl (meth) acrylamide, N-nitrophenyl acrylamide, N-ethyl-N-phenyl acrylamide, N-benzyl (meth) acrylamide, (meth) acryloylmorpholine, diacetone acrylamide, N- Methylo Acrylamide, N- hydroxyethyl acrylamide, vinyl (meth) acrylamide, N, N- diallyl (meth) acrylamide, such as N- allyl (meth) acrylamide.

  Examples of styrenes include styrene, methyl styrene, dimethyl styrene, trimethyl styrene, ethyl styrene, isopropyl styrene, butyl styrene, hydroxy styrene, methoxy styrene, butoxy styrene, acetoxy styrene, chlorostyrene, dichlorostyrene, bromostyrene, chloromethyl Examples thereof include styrene, hydroxystyrene protected with a group that can be deprotected by an acidic substance (for example, t-Boc and the like), methyl vinylbenzoate, and α-methylstyrene.

Examples of vinyl ethers include methyl vinyl ether, ethyl vinyl ether, 2-chloroethyl vinyl ether, hydroxyethyl vinyl ether, propyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, octyl vinyl ether, methoxyethyl vinyl ether, and phenyl vinyl ether.
Examples of vinyl ketones include methyl vinyl ketone, ethyl vinyl ketone, propyl vinyl ketone, and phenyl vinyl ketone.
Examples of olefins include ethylene, propylene, isobutylene, butadiene, isoprene and the like.
Examples of maleimides include maleimide, butyl maleimide, cyclohexyl maleimide, and phenyl maleimide.

  (Meth) acrylonitrile, heterocyclic groups substituted with vinyl groups (for example, vinylpyridine, N-vinylpyrrolidone, vinylcarbazole, etc.), N-vinylformamide, N-vinylacetamide, N-vinylimidazole, vinylcaprolactone, etc. are also used. it can.

In addition to the above compounds, for example, vinyl monomers having a functional group such as a urethane group, a urea group, a sulfonamide group, a phenol group, and an imide group can also be used.
The vinyl monomer having a urethane group or a urea group can be appropriately synthesized using, for example, an addition reaction between an isocyanate group and a hydroxyl group or an amino group. Specifically, an addition reaction between an isocyanate group-containing monomer and a compound containing one hydroxyl group or a compound containing one primary or secondary amino group, or a hydroxyl group-containing monomer or primary or secondary amino group It can be appropriately synthesized by an addition reaction between a group-containing monomer and monoisocyanate.

When P ¹ is a nonionic polymer skeleton, the vinyl monomer polymer or copolymer may be a vinyl monomer other than the ionic vinyl monomer, and when P ¹ is an ionic polymer skeleton, At least one or more ionic vinyl monomers may be homopolymerized, or at least one or more ionic vinyl monomers and a vinyl monomer other than the ionic vinyl monomer may be copolymerized.
The ionic polymer skeleton is prepared by the above-described method, a method of neutralizing an acidic group in the polymer skeleton with an organic base or an inorganic base, or a nitrogen-containing basic group in the polymer skeleton with an organic acid or an inorganic acid. You may obtain by the method of summing.

  Among the polymer compounds represented by the general formula (1), the polymer compound represented by the following general formula (2) is preferable.

In the general formula (2), A ² represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, or 4 or more carbon atoms. Represents a monovalent organic group containing at least one portion selected from a hydrocarbon group, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group. However, when A ² is a monovalent organic group containing at least one ionic functional group, P ² may be a nonionic polymer skeleton or an ionic polymer skeleton. ^{When 2} is a monovalent organic group not containing an ionic functional group, P ² represents an ionic polymer skeleton. The n A ² may be the same or different.
Incidentally, A ² has the same meaning as the A ¹ in the general formula (1), a preferable embodiment thereof is also the same.

In the general formula (2), R ⁴ and R ⁵ each independently represents a single bond or a divalent organic linking group. n R ⁴ and m R ⁵ may be the same or different independently.
R ⁴ and R ⁵ have the same meaning as R ² in the general formula (1), and the preferred embodiments are also the same.

In the general formula (2), R ³ represents an (m + n) -valent organic linking group. m + n satisfies 3-10.
Examples of the (m + n) -valent organic linking group represented by R ³ include 1 to 60 carbon atoms, 0 to 10 nitrogen atoms, 0 to 50 oxygen atoms, 1 to Groups consisting of up to 100 hydrogen atoms and 0 to 20 sulfur atoms are included, which may be unsubstituted or further substituted.
The (m + n) -valent organic linking group represented by R ³ has the same meaning as the (m + n) -valent organic linking group represented by R ¹ , and the preferred embodiments thereof are also the same.

In said general formula (2), m represents 1-8. As m, 1-5 are preferable, 1-4 are more preferable, and 1-3 are especially preferable.
Moreover, in said general formula (2), n represents 2-9. As n, 2-8 are preferable, 2-7 are more preferable, and 3-6 are especially preferable.

Further, P ² in the general formula (2) represents a polymer skeleton and can be selected from known polymers according to the purpose and the like. the m P ² can be the same or different. The preferred embodiment of the polymer, has the same meaning as P ¹ in Formula (1), the same applies to its preferred embodiment.

A preferable form of the polymer compound represented by the general formula (2) includes a form satisfying all of R ³ , R ⁴ , R ⁵ , P ² , m, and n shown below.
R ³ : Specific examples (1), (2), (10), (11), (16), or (17) of the (m + n) -valent organic linking group represented by R ¹
R ⁴ : a single bond or the following structural unit or a combination of the structural units: “1 to 10 carbon atoms, 0 to 5 nitrogen atoms, 0 to 10 oxygen atoms” A divalent organic linking group comprising an atom, 1 to 30 hydrogen atoms, and 0 to 5 sulfur atoms (which may have a substituent, for example, C1-C20 alkyl group such as methyl group and ethyl group, aryl group having 6 to 16 carbon atoms such as phenyl group and naphthyl group, hydroxyl group, amino group, carboxyl group, sulfonamide group, N-sulfonylamide Group, acyloxy group having 1 to 6 carbon atoms such as acetoxy group, alkoxy group having 1 to 6 carbon atoms such as methoxy group and ethoxy group, halogen atom such as chlorine and bromine, methoxycarbonyl group An ethoxycarbonyl group, an alkoxycarbonyl group having from 2 to 7 carbon atoms such as cyclohexyl oxycarbonyl group, a cyano group, carbonate group, such as t- butyl carbonate, and the like.)

R ⁵ : single bond, ethylene group, propylene group, the following group (a), or the following group (b)
In the following groups, R ²⁵ represents a hydrogen atom or a methyl group, and l represents 1 or 2.

P ² : Polymer or copolymer of vinyl monomer m: 1 to 3
n: 3-6

Among the preferred forms of the polymer compound represented by the general formula (2) (forms satisfying all of the aforementioned R ³ , R ⁴ , R ⁵ , P ² , m, and n), A ² is an organic dye structure. , A monovalent organic group containing at least one moiety selected from a heterocyclic structure and a hydrocarbon group having 4 or more carbon atoms, wherein P ² is a vinyl monomer polymer containing at least one ionic vinyl monomer Or the form which is a copolymer is more preferable.

Alternatively, among the preferable forms of the polymer compound represented by the general formula (2) (the form satisfying all of R ³ , R ⁴ , R ⁵ , P ² , m, and n described above), A ² is an ion More preferred is a monovalent organic group containing at least one ionic functional group, and P ² is a polymer or copolymer of vinyl monomers other than ionic vinyl monomers.

  The molecular weight of the polymer compound of the present invention is preferably 3000 to 100,000, more preferably 3000 to 80000, and particularly preferably 3000 to 60000 in terms of weight average molecular weight. When the weight average molecular weight is within the above range, the effects of the plurality of adsorption sites introduced at the ends of the polymer are sufficiently exerted, and the performance with excellent adsorptivity to the solid surface, micelle formation ability, and surface activity is achieved. Demonstrate. In particular, when the polymer compound according to the present invention is used as an aqueous pigment dispersant, good dispersibility and dispersion stability can be achieved.

(Synthesis method)
The polymer compound represented by the general formula (1) (including those represented by the general formula (2)) is not particularly limited, but can be synthesized by the following method.
1. A polymer in which a functional group selected from a carboxyl group, a hydroxyl group, an amino group or the like is introduced at the terminal, an acid halide having a plurality of the adsorption sites, an alkyl halide having a plurality of the adsorption sites, or a plurality of the adsorption sites. A method of polymerizing the isocyanate and the like.
2. A method in which a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having a plurality of the adsorption sites are subjected to a Michael addition reaction.
3. A method of reacting a polymer having a carbon-carbon double bond introduced at a terminal thereof and a mercaptan having the adsorption site in the presence of a radical generator.
4). A method in which a polymer having a plurality of mercaptans introduced at its terminal is reacted with a compound having a carbon-carbon double bond and the adsorption site in the presence of a radical generator.
5. A method of radical polymerizing a vinyl monomer in the presence of a mercaptan compound having a plurality of the adsorption sites.

  Among the above, the polymer compound of the present invention is preferably a synthesis method of 2, 3, 4, 5 and more preferably a synthesis method of 3, 4, 5 because of ease of synthesis. In particular, when the polymer compound of the present invention has a structure represented by the general formula (2), it is most preferable to synthesize by the synthesis method 5 because of ease of synthesis.

  More specifically, the synthesis method 5 is preferably a method in which a vinyl monomer is radically polymerized in the presence of a compound represented by the following general formula (3) (hereinafter, a compound represented by the general formula (3)). Is also referred to as “mercaptan compound represented by formula (3)” or “mercaptan compound according to the present invention”).

In the general formula (3), R ⁶ , R ⁷ , A ³ , m, and n have the same meanings as R ³ , R ⁴ , A ² , m, and n in the general formula (2), respectively. The preferred embodiment is also the same.

The compound represented by the general formula (3) can be synthesized by the following method or the like, but the following method 7 is more preferable because of ease of synthesis.
6). A method for converting a halide compound having a plurality of adsorption sites into a mercaptan compound (a method in which the halide compound is reacted with thiourea to hydrolyze, a method in which the halide compound is directly reacted with NaSH, and the halide compound is converted to CH ₃ COSNa. And the method of hydrolyzing it and the like)
7). Method of addition reaction of a compound having 3 to 10 mercapto groups in one molecule and a compound having the adsorption site and having a functional group capable of reacting with a mercapto group

Preferable examples of the “functional group capable of reacting with a mercapto group” in the synthesis method 7 include acid halides, alkyl halides, isocyanates, and carbon-carbon double bonds.
It is particularly preferable that the “functional group capable of reacting with a mercapto group” is a carbon-carbon double bond, and the addition reaction is a radical addition reaction. The carbon-carbon double bond is more preferably a mono- or di-substituted vinyl group in terms of reactivity with the mercapto group.

  Specific examples of the compound having 3 to 10 mercapto groups in one molecule [specific examples (18) to (34)] include the following compounds.

  Among the above, the following compounds are particularly preferable from the viewpoints of availability of raw materials, ease of synthesis, and solubility in various solvents.

  A compound having the adsorption site and having a carbon-carbon double bond (specifically, an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a coordination group) A group having a coordinated oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group, and a carbon-carbon Although it does not restrict | limit especially as a compound which has a double bond, The following are mentioned.

  The radical addition reaction product of the “compound having 3 to 10 mercapto groups in one molecule” and the “compound having the adsorption site and having a carbon-carbon double bond” is, for example, The above “compound having 3 to 10 mercapto groups in one molecule” and “compound having the adsorption site and having a carbon-carbon double bond” are dissolved in an appropriate solvent, It is obtained using a method (thiol-ene reaction method) in which a radical generator is added and added at about 50 ° C. to 100 ° C.

Examples of suitable solvents used in the thiol-ene reaction method include “compound having 3 to 10 mercapto groups in one molecule”, “having the adsorption site, and carbon-carbon double. It can be arbitrarily selected according to the solubility of the “compound having a bond” and the “radical addition reaction product to be produced”.
For example, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran, dimethyl Examples include formamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  In addition, as radical generators, 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate An azo compound such as benzoyl peroxide, a peroxide such as benzoyl peroxide, and a persulfate such as potassium persulfate and ammonium persulfate can be used.

The vinyl monomer used in the synthesis method of 5 is not particularly limited, for example, those similar to the vinyl monomers used in obtaining the polymer skeleton represented by P ¹ of the general formula (1) is used It is done.

  The above vinyl monomers may be polymerized alone or in combination of two or more.

The polymer compound of the present invention is a conventional method using these vinyl monomers and a compound represented by the general formula (3) (hereinafter sometimes simply referred to as “chain transfer agent”) by a known method. Obtained by polymerization according to
For example, a method in which these vinyl monomers and the chain transfer agent are dissolved in a suitable solvent, a radical polymerization initiator is added thereto and polymerized in a solution at about 50 ° C. to 220 ° C. (solution polymerization method) ) To obtain.

  Examples of suitable solvents used in the solution polymerization method can be arbitrarily selected depending on the monomers used and the solubility of the resulting copolymer. For example, water, methanol, ethanol, propanol, isopropanol, 1-methoxy-2-propanol, 1-methoxy-2-propyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, methoxypropyl acetate, ethyl lactate, ethyl acetate, acetonitrile, tetrahydrofuran , Dimethylformamide, chloroform, and toluene. These solvents may be used as a mixture of two or more.

  Examples of radical polymerization initiators include 2,2′-azobis (isobutyronitrile) (AIBN), 2,2′-azobis- (2,4′-dimethylvaleronitrile), and 2,2′-azobisisobutyric acid. Azo compounds such as dimethyl and azobis (2-amidinopropane) hydrochloride, peroxides such as benzoyl peroxide, and persulfates such as potassium persulfate and ammonium persulfate can be used.

<Aqueous pigment dispersant>
The aqueous pigment dispersant of the present invention contains the above-described polymer compound of the present invention as an aqueous pigment dispersant for dispersing a pigment. In addition to the polymer compound of the present invention, For the purpose of further improving dispersibility, conventionally known dispersants such as pigment dispersants and surfactants, and other components may be added.

Known dispersants (pigment dispersants) include polymer dispersants such as polyamidoamines and salts thereof, polycarboxylic acids and salts thereof, high molecular weight unsaturated acid esters, modified polyurethanes, modified polyesters, and modified poly (meth). Acrylate, (meth) acrylic copolymer, naphthalenesulfonic acid formalin condensate], polyoxyethylene alkyl phosphate ester, polyoxyethylene alkylamine, alkanolamine, pigment derivative, and the like.
The polymer dispersant can be further classified into a linear polymer, a terminal-modified polymer, a graft polymer, and a block polymer according to the structure.

  The polymer dispersant is adsorbed on the surface of the pigment and acts to prevent reaggregation. Therefore, a terminal-modified polymer, a graft polymer and a block polymer having an anchor site to the pigment surface can be mentioned as preferred structures. On the other hand, the pigment derivative has an effect of promoting the adsorption of the polymer dispersant by modifying the pigment surface.

  As specific examples of known dispersants (pigment dispersants) that can be used in the present invention, those having a small amount and a large dispersion effect are preferable. For example, various polymers in which the dispersion function in an aqueous medium and the adsorption function to fine particles are separated Can be mentioned. Specifically, ethylene oxide-propylene oxide block copolymer, ethylene oxide-tetrahydrofuran block copolymer, styrene- (meth) acrylic acid block copolymer, (meth) acrylic acid ester- (meth) acrylic acid block copolymer. Polymer, styrene- (meth) acrylic acid polyethylene glycol ester block copolymer, styrene-maleic acid copolymer polyethylene glycol ester, styrene-maleic acid copolymer ethylene glycol propylene glycol ester, (meth) acrylic acid ester- ( (Meth) acrylic acid polyethylene glycol ester block copolymer, styrene or comb polymer composed of (meth) acrylic acid ester and polyethylene glycol macromer, styrene or (meth) acrylic It includes comb polymers consisting of a macromer and polyethylene glycol esters. In addition, a polymer having an affinity for an organic pigment and having a functional group such as a primary to tertiary amino group bonded to a terminal or a side chain can also be used. Of these, styrene-maleic acid copolymer alkylene oxide adducts such as styrene-maleic acid copolymer polyethylene glycol ester and styrene-maleic acid copolymer polyethylene glycol polypropylene glycol ester are preferable.

  Examples of the known dispersant include commercially available products such as BYK Chemie, EFKA, Ajinomoto Fan Techno, Kyoeisha Chemical, Enomoto Kasei, Kao, Lubrizol, and Nikko Chemical. An aqueous dispersant can be suitably used.

  As the aqueous pigment dispersant of the present invention, the polymer compound of the present invention may be used alone or in combination with one or more of the known dispersants.

<Aqueous pigment dispersion composition>
The aqueous pigment dispersion composition of the present invention comprises at least one pigment in the aqueous medium and the aqueous pigment dispersant of the present invention described above, and other components such as a resin component as necessary. Can be used. This water-based pigment dispersion composition contains at least one of the polymer compounds of the present invention described above as a water-based pigment dispersant, so that the dispersion state of the pigment in the water-based medium becomes good and good color characteristics are obtained. In addition, for example, when used as a water-based ink, it has a low viscosity and excellent storage stability.

(Pigment)
The water-based pigment dispersion composition of the present invention can be used by appropriately selecting various conventionally known inorganic pigments or organic pigments.
In consideration of the fact that it is preferable that the pigment has a high color density, whether it is an inorganic pigment or an organic pigment, it is preferable to use a pigment having a particle size as small as possible. In consideration of handling properties, the average particle size of the pigment is 0. 0.005 to 15 μm is preferable, 0.005 to 5 μm is more preferable, and 0.01 to 1 μm is most preferable.

  Examples of the inorganic pigment include carbon black (furnace black, thermal lamp black, acetylene black, channel black, etc.), metal compounds represented by metal oxides, metal complex salts, and the like. Specifically, iron, Examples thereof include metal oxides such as cobalt, aluminum, cadmium, lead, copper, titanium, magnesium, chromium, zinc, and antimony, and composite oxides of the above metals.

Examples of the organic pigment include:
C. I. Pigment Yellow 1, 2, 3, 11, 13, 16, 24, 31, 53, 83, 93, 99, 108, 109, 110, 138, 139, 147, 150, 151, 154, 155, 167, 180, 185, 199;
C. I. Pigment orange 36, 38, 43, 71;
C. I. Pigment Red 5, 7, 12, 48 (Ca), 48 (Mn), 57 (Ca), 81, 105, 112, 122, 149, 150, 155, 171, 175, 176, 177, 209, 220, 224 , 242, 254, 255, 264, 270;
C. I. Pigment violet 19, 23, 32, 37, 39;
C. I. Pigment blue 1, 2, 3, 15, 15: 1, 15: 3, 15: 6, 16, 22, 60, 66;
C. I. Pigment green 7, 36, 37;
C. I. Pigment brown 25, 28;
C. I. Pigment black 1, 7;
Etc.

  As content in the aqueous pigment dispersion composition of a pigment, 40-95 mass% is preferable with respect to the total solid (mass) of this composition, and 50-90 mass% is more preferable. When the pigment content is within the above range, the color density is sufficient and it is effective to ensure excellent color characteristics.

(Aqueous pigment dispersant)
The details of the aqueous pigment dispersant are as described above, and the same applies to the preferred embodiments of the components constituting the aqueous pigment dispersant.
Further, the content of the aqueous pigment dispersant in the aqueous pigment dispersion composition is preferably 0.5 to 100% by mass, more preferably 3 to 100% by mass, and more preferably 5 to 80% with respect to the mass of the pigment. Mass% is particularly preferred. When the amount of the aqueous pigment dispersant is within the above range, a sufficient pigment dispersion effect can be obtained.
In order to sufficiently obtain the pigment dispersibility effect of the polymer compound of the present invention, the content of the polymer compound of the present invention with respect to the total aqueous pigment dispersant in the water-based pigment dispersion composition of the present invention is 10 It is preferably at least mass%, preferably at least 30 mass%, and preferably at least 50 mass%.

(Aqueous medium)
As the aqueous medium, water, a water-soluble organic solvent, or a mixed solvent thereof is suitable. The water is preferably ion exchange water (deionized water) or distilled water. Examples of the water-soluble organic solvent include methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol and other alkyl alcohols having 1 to 4 carbon atoms, dimethylformamide, Amides such as dimethylacetamide, ketones or ketoalcohols such as acetone and diacetone alcohol, ethers such as tetrahydrofuran and dioxane, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, ethylene glycol, propylene glycol, butylene glycol, Ethylene glycol, 1,2-hexanediol, 1,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethyleneglycol Polyhydric alcohols (preferably alkylene glycols in which the alkylene group contains 2 to 6 carbon atoms), glycerin, ethylene glycol monomethyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl And lower alkyl ethers of polyhydric alcohols such as (or ethyl) ether, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone and the like. Among these water-soluble organic solvents, water, polyhydric alcohols such as diethylene glycol (preferably alkylene glycols in which the alkylene group contains 2 to 6 carbon atoms), triethylene glycol monomethyl (or butyl) ether, etc. Preferred are lower alkyl ethers of monohydric alcohols and mixed solvents thereof.

(Other ingredients)
The aqueous pigment dispersion composition of the present invention may contain an aqueous resin in addition to the pigment, the aqueous pigment dispersant, and the aqueous medium. Aqueous resins include acrylic-based copolymers, styrene-acrylic acid-based copolymers, styrene-maleic acid-based copolymers, alkyd-based, epoxy-based, polyester-based, urethane-based water-dispersed resins or water-soluble resins. However, an acrylic copolymer water-dispersed resin or water-soluble resin is particularly preferable.
The water-soluble resin or water-soluble resin of the acrylic copolymer may be produced by emulsion polymerization, soap-free polymerization, suspension polymerization or the like, or free carboxylic acid polymerized in a hydrophilic organic solvent. An aqueous dispersible resin obtained by neutralizing an acrylic copolymer resin having ammonia or an organic amine and adding water may be used.
Moreover, you may add the well-known and usual various additives normally added to a coating material and water-based ink to the water-system pigment dispersion composition of this invention. Such additives include curing agent resins (such as melamine resins), curing catalysts, surfactants, antifoaming agents, preservatives, antisettling agents, chelating agents, thickeners, anticorrosives, antioxidants, etc. Can be mentioned. Surfactants include anionic surfactants such as fatty acid salts, higher alcohol sulfates, liquid fatty oil sulfates, alkylallyl sulfonates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl esters, poly Nonionic surfactants such as oxyethylene sorbitan alkyl esters, acetylene alcohol, acetylene glycol and the like can be mentioned.

  The preparation of the aqueous pigment dispersion composition of the present invention is not particularly limited. For example, a vertical or horizontal sand grinder, a pin mill, a slit mill, an ultrasonic disperser, etc., with a pigment, an aqueous pigment dispersant and an aqueous medium. Can be obtained by performing fine dispersion treatment with beads made of glass, zirconia or the like having a particle diameter of 0.01 to 1 mm.

<Water-based ink>
The aqueous ink of the present invention comprises the above-mentioned aqueous pigment dispersion composition.
The amount of the dispersant contained in the aqueous ink of the present invention is preferably in the range of 0.1 to 30% by mass and more preferably in the range of 1 to 15% by mass with respect to the total mass of the ink.

  The amount of the pigment (colorant) contained in the aqueous ink is preferably in the range of 1 to 30% by mass, and more preferably in the range of 2 to 15% by mass. The content ratio of the dispersant and the pigment (colorant) contained in the water-based ink is preferably in the range of 1: 1 to 1: 200 (mass ratio), and is preferably 1: 1 to 1:33. More preferred.

  The amount of the water-soluble organic solvent contained in the aqueous ink is preferably in the range of 3 to 50% by mass, more preferably in the range of 3 to 40% by mass with respect to the total mass of the aqueous ink. The amount of water contained in the aqueous ink of the present invention is preferably in the range of 10 to 90% by mass, and more preferably in the range of 30 to 80% by mass.

The pH of the water-based ink is preferably in the range of 7-10. By setting the pH within this range, storage stability can be improved, and corrosion of members of an apparatus (for example, an ink jet recording apparatus) to which aqueous ink is applied can be suppressed.
For adjusting the pH of the water-based ink, inorganic alkali agents such as alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, organic amines such as diethanolamine and triethanolamine, and organic acids such as citric acid and tartaric acid, Mineral acids such as hydrochloric acid and phosphoric acid can be used as a pH adjuster.

  The water-based ink of the present invention contains an aqueous pigment dispersion obtained by mixing and dispersing the above components. The water-based pigment dispersion can be diluted with an aqueous medium as it is or, if necessary, with an anti-drying agent or other additives to obtain an aqueous ink. The obtained water-based ink can be used, for example, as a water-based ink for a writing instrument such as an ink-jet water-based ink, a water-based ballpoint pen, or a marker pen. In this case, in order to prevent the inkjet nozzle and the nib from being clogged by drying, it is preferable to add a low-volatile or non-volatile solvent among the water-soluble organic solvents. In order to increase the permeability to the recording medium, a volatile solvent may be added. In particular, when used for water-based ink for ink jet recording, it is also preferable to add a surfactant in order to give the ink an appropriate surface tension.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further more concretely, it is not limited to a following example. Unless otherwise specified, “%” and “part” are based on mass.

(Examples 1-8)
As Examples 1 to 8, polymer compounds C-1 to C-8 of the present invention were synthesized by the method shown below.
<Synthesis of Mercaptan Compound Represented by General Formula (3)>
As shown below, chain transfer agents B-1 to B-5 (mercaptan compounds represented by the general formula (3) described above) were synthesized.
[Synthesis Example B-1]
Dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd., the following compound (33)] 7.83 parts, and an adsorption site, and a carbon-carbon double bond 6.51 parts of a compound having the following (compound (A-1) below) was dissolved in 33.45 parts of 1-methoxy-2-propanol and heated to 70 ° C. under a nitrogen stream. To this, 0.06 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Furthermore, 0.06 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, the following 30% solution of the mercaptan compound (chain transfer agent B-1) according to the present invention was obtained.

[Synthesis Example B-2]
4.89 parts of pentaerythritol tetrakis (3-mercaptopropionate) [PEMP; manufactured by Sakai Chemical Industry Co., Ltd., the following compound (27)], and has an adsorption site and a carbon-carbon double bond 6.88 parts of the compound (compound (A-2) below) was dissolved in 47.08 parts of n-propanol and heated to 70 ° C. under a nitrogen stream. To this, 0.04 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Further, 0.04 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, the following 20% solution of the mercaptan compound (chain transfer agent B-2) according to the present invention was obtained.

[Synthesis Example B-3]
Dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd., the following compound (33)] 7.83 parts, and an adsorption site, and a carbon-carbon double bond 10.39 parts of compound (N- [2- (methacryloyloxy) ethyl] -N, N, N-trimethylammonium chloride, the following compound (A-3)) having 72.88 parts of 1-methoxy-2-propanol And heated to 70 ° C. under a nitrogen stream. To this, 0.06 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Furthermore, 0.06 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, a 20% solution of the mercaptan compound (chain transfer agent B-3) according to the present invention shown below was obtained.

[Synthesis Example B-4]
Dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd., the following compound (33)] 7.83 parts, and the following adsorption site, and carbon-carbon double 15.57 parts of a compound having a bond (the following compound (A-4)) was dissolved in 93.60 parts of dimethylformamide and heated to 70 ° C. under a nitrogen stream. To this, 0.06 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Furthermore, 0.06 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, a 20% solution of a mercaptan compound (chain transfer agent B-4) according to the present invention shown below was obtained.

[Synthesis Example B-5]
Dipentaerythritol hexakis (3-mercaptopropionate) [DPMP; manufactured by Sakai Chemical Industry Co., Ltd., the following compound (33)] 7.83 parts, and an adsorption site, and a carbon-carbon double bond 7.71 parts of a compound having the following (compound (A-5) below) was dissolved in 62.16 parts of methyl ethyl ketone and heated to 70 ° C. under a nitrogen stream. To this, 0.06 part of 2,2′-azobis (2,4-dimethylvaleronitrile) [V-65, manufactured by Wako Pure Chemical Industries, Ltd.] was added and heated for 3 hours. Furthermore, 0.06 part of V-65 was added and reacted at 70 ° C. for 3 hours under a nitrogen stream. By cooling to room temperature, a 20% solution of a mercaptan compound (chain transfer agent B-5) according to the present invention shown below was obtained.

<Synthesis of polymer compounds>
Subsequently, as shown below, polymer compounds C-1 to C-8 of the present invention were synthesized.
[Synthesis Example C-1]
A mixed solution of 20.16 parts of a 20% solution of chain transfer agent B-1 obtained in Synthesis Example B-1 and 20 parts of n-butyl methacrylate (BMA; monomer) was heated to 80 ° C. in a nitrogen stream. did. To this was added 0.013 part of 2,2′-azobis (isobutyronitrile) [AIBN, manufactured by Wako Pure Chemical Industries, Ltd.] and heated for 3 hours, and then 0.013 part of AIBN was added again under a nitrogen stream. And reacted at 80 ° C. for 3 hours. Then, it cooled to room temperature and diluted with acetone. After reprecipitation using a large amount of ion-exchanged water / methanol, it was dried under reduced pressure to obtain 19 parts of a polymer solid. The weight average molecular weight in terms of polystyrene of the obtained polymer was 14,000.
Subsequently, a methyl ethyl ketone solution (solid content: 10 wt%) of the above polymer was prepared, and neutralized by adding diethyl ethanolamine equivalent to the carboxyl group of the polymer and ion-exchanged water. Then, the solvent was removed under reduced pressure to remove methyl ethyl ketone to obtain an aqueous dispersion of the polymer compound (C-1) of the present invention shown below (solid content: 30%).

[Synthesis Example C-2]
In Synthesis Example C-1, 20.26 parts of a 20% solution of chain transfer agent B-1 was changed to 16.27 parts, and n-butyl methacrylate was changed to benzyl methacrylate. Synthesis Example C- In the same manner as in Example 1, an aqueous dispersion of the polymer compound (C-2) of the present invention shown below was obtained (solid content: 30 wt%). In addition, 17 parts of the polymer before neutralization was obtained, and the weight average molecular weight in terms of polystyrene was 16000.

[Synthesis Example C-3]
In Synthesis Example C-1, except that 20.20 parts of a 20% solution of chain transfer agent B-1 was changed to 27.53 parts and n-butyl methacrylate was changed to styrene, Synthesis Example C-1 and Similarly, an aqueous dispersion of the polymer compound (C-3) of the present invention shown below was obtained (solid content: 30 wt%). In addition, 12 parts of polymer before neutralization was obtained, and the weight average molecular weight of polystyrene conversion was 16000.

[Synthesis Example C-4]
A mixed solution of 23.50 parts of a 20% solution of chain transfer agent B-2 obtained in Synthesis Example B-2 and 20 parts of methyl methacrylate was heated to 80 ° C. under a nitrogen stream. To this was added 0.013 part of 2,2′-azobis (isobutyronitrile) [AIBN, manufactured by Wako Pure Chemical Industries, Ltd.] and heated for 3 hours, and then 0.013 part of AIBN was added again under a nitrogen stream. And reacted at 80 ° C. for 3 hours. Then, it cooled to room temperature and diluted with acetone. After reprecipitation using a large amount of hexane, the precipitate was dried under reduced pressure to obtain 16 parts of a polymer solid.
Subsequently, ion-exchanged water was mixed into the polymer and stirred to obtain an aqueous dispersion of the polymer compound (C-4) of the present invention shown below (solid content: 30%).

[Synthesis Example C-5]
In Synthesis Example C-4, 23.50 parts of 20% solution of chain transfer agent B-2 was changed to 25.62 parts of 20% solution of chain transfer agent B-3, and methyl methacrylate was changed to n-butyl methacrylate. Except that, an aqueous dispersion of the polymer compound (C-5) of the present invention shown below was obtained in the same manner as in Synthesis Example C-4 (solid content: 30 wt%). In addition, 12 parts of the polymer before neutralization was obtained.

[Synthesis Example C-6]
A mixed solution of 49.13 parts of a 20% solution of chain transfer agent B-4 obtained in Synthesis Example B-4 and 18 parts of methyl methacrylate and 2 parts of methacrylic acid was heated to 80 ° C. in a nitrogen stream. To this was added 0.013 part of 2,2′-azobis (isobutyronitrile) [AIBN, manufactured by Wako Pure Chemical Industries, Ltd.] and heated for 3 hours, and then 0.013 part of AIBN was added again under a nitrogen stream. And reacted at 80 ° C. for 3 hours. Then, it cooled to room temperature and diluted with acetone. After reprecipitation using a large amount of ion-exchanged water / methanol, it was dried under reduced pressure to obtain 16 parts of a polymer solid. The weight average molecular weight in terms of polystyrene of the obtained polymer was 12,000.
Subsequently, a methyl ethyl ketone solution (solid content: 10 wt%) of the above polymer was prepared, and neutralized by adding diethyl ethanolamine equivalent to the carboxyl group of the polymer and ion-exchanged water. Then, the solvent was removed under reduced pressure to remove methyl ethyl ketone to obtain an aqueous dispersion of the polymer compound (C-6) of the present invention shown below (solid content: 30%).

[Synthesis Example C-7]
45.84 parts of a 20% solution of chain transfer agent B-4 obtained in Synthesis Example B-4 and 18 parts of methyl methacrylate, N- [2- (methacryloyloxy) ethyl] -N, N, N-trimethyl A mixed solution of 2 parts of ammonium chloride was heated to 80 ° C. under a nitrogen stream. To this was added 0.013 part of 2,2′-azobis (isobutyronitrile) [AIBN, manufactured by Wako Pure Chemical Industries, Ltd.] and heated for 3 hours, and then 0.013 part of AIBN was added again under a nitrogen stream. And reacted at 80 ° C. for 3 hours. Then, it cooled to room temperature and diluted with acetone. After reprecipitation using a large amount of hexane, it was dried under reduced pressure to obtain 15 parts of a polymer solid. The weight average molecular weight in terms of polystyrene of the obtained polymer was 13,000.
Subsequently, ion-exchanged water was mixed into the polymer and stirred to obtain an aqueous dispersion of the polymer compound (C-7) of the present invention shown below (solid content: 30%).

[Synthesis Example C-8]
In the synthesis example C-6, except that 49.13 parts of the 20% solution of the chain transfer agent B-4 was changed to 31.55 parts of the 20% solution of the chain transfer agent B-5, the synthesis example C-6 and Similarly, an aqueous dispersion of the polymer compound (C-8) of the present invention shown below was obtained (solid content: 30 wt%). In addition, 17 parts of the polymer before neutralization was obtained.

Below, the synthesis example (C-9, C-10) for a comparative example is shown.
[Synthesis Example C-9]
A mixed solution of 70 parts of methyl methacrylate macromonomer (product name AA-6, manufactured by Toagosei Co., Ltd.), 20 parts of methacrylic acid, 10 parts of 2-hydroxylethyl methacrylate, and 100 parts of 1-methoxy-2-propyl acetate, Under a nitrogen stream, 0.78 parts of 2,2′-azobis (isobutyronitrile) [AIBN, manufactured by Wako Pure Chemical Industries, Ltd.] was added at 80 ° C. and heated for 3 hours, and then 0.78 parts of AIBN was again added. In addition, the reaction was carried out at 80 ° C. for 3 hours under a nitrogen stream. Thereafter, 90 parts of polymer solid was obtained by reprecipitation purification and drying under reduced pressure. The weight average molecular weight in terms of polystyrene of the obtained polymer was 25000.
Subsequently, a methyl ethyl ketone solution (solid content: 10 wt%) of the above polymer was prepared, and neutralized by adding diethyl ethanolamine equivalent to the carboxyl group of the polymer and ion-exchanged water. Then, the solvent was removed under reduced pressure to remove methyl ethyl ketone, and an aqueous dispersion of the polymer compound (C-9) was obtained (solid content: 30%).

  In the polymer compound (C-9), X represents a linking group.

[Synthesis Example C-10]
A copolymer of methyl methacrylate / methacrylic acid was synthesized using the following mercaptan compound (weight average molecular weight 15000).

  Subsequently, a methyl ethyl ketone solution (solid content 10 wt%) of the polymer was prepared, and neutralized by adding diethyl ethanolamine and ion-exchanged water equivalent to the carboxyl group of the polymer. Then, the solvent was removed under reduced pressure to remove methyl ethyl ketone to obtain an aqueous dispersion of the polymer compound (C-10) (solid content: 30%).

Example 9
Ingredients having the following composition were mixed, and the rotational speed was 3,000 r.m. using a homogenizer. p. m. And mixed for 10 minutes to prepare a mixed solution.
〔composition〕
Carbon black: 15.0 parts Aqueous dispersion of polymer compound obtained in Synthesis Example C-1 (30 wt%) 7.0 parts Ion-exchanged water 78 parts

Subsequently, the mixed solution obtained above was further subjected to a dispersion treatment for 3 hours using a bead disperser disperse mat (manufactured by GETZMANN) using 1.0 mmφ zirconia beads (filling rate 50%).
After the above dispersion treatment, centrifugal separation treatment (12,000 RPM, 20 minutes) is performed to remove coarse particles, 40 parts of a dispersion liquid is added to 5 parts of glycerin, 15 parts of diethylene glycol, 2 parts of 2-pyrrolidone and ion exchange. 38 parts of water was mixed, and the pH was adjusted to 8 to 10 with diethylethanolamine, followed by filtration using a membrane filter having a pore size of 5.0 μm to obtain a desired aqueous ink.

≪Evaluation of water-based ink≫
The obtained water-based ink was evaluated for the following items (a) to (d).
(A) Particle size of water-based ink After water was added to the obtained aqueous dispersion and diluted 100 times, the volume average particle size of the water-based ink was measured.
(B) Dispersion stability of aqueous dispersion After the obtained aqueous ink was allowed to stand at 60 ° C. for 6 months in a sealed state, the pigment particles were agglomerated and thickened, and “x” was defective. Were evaluated as good “◯”.
(C) Printing density Solid printing was performed on recycled paper for PPC (manufactured by Nippon Processing Paper Co., Ltd.) using a micro bubble jet printer (manufactured by Canon, model number BJ-10VL). Then, the optical density of the print after naturally drying at room temperature for 24 hours was measured with a Macbeth densitometer RD918 (manufactured by Macbeth). A print density of 1.4 or higher was evaluated as “◯”, and a print density of less than 1.4 was evaluated as “X”. Microbubble jet printer is a registered trademark of Canon Inc.
(D) Image quality characteristics When black solid images are printed, the occurrence of image density unevenness and white streaks is indicated as “◯” when there is no occurrence, “△” when slightly recognized, and “×” when clearly recognized. did.

(Examples 10 to 16)
In Example 9, the aqueous dispersion (30 wt%) of the polymer compound obtained in Synthesis Example C-1 was changed to the aqueous dispersion (30 wt%) of the polymer compound obtained in Synthesis Examples C-2 to C-8. %), A water-based ink was prepared in the same manner as in Example 9, and the same evaluation was performed.

(Comparative Examples 1-2)
In Example 9, the aqueous dispersion (30 wt%) of the polymer compound obtained in Synthesis Example C-1 was used as the aqueous dispersion (30 wt%) of the polymer compound obtained in Synthesis Examples C-9 to C-10. In the following, water-based ink was prepared in the same manner as in Example 9, and the same evaluation was performed.

  As shown in Table 1, the water-based ink of the example gave better results than the water-based ink of the comparative example. This is probably because the dispersion stability of the dispersant used in each example is superior to that of the comparative example.

Claims (14)

A polymer compound represented by the following general formula (1).

[Wherein, R ¹ represents an (m + n) -valent organic linking group, and R ² represents a single bond or a divalent organic linking group. A ¹ is an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, A monovalent organic group containing at least one site selected from an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group. n A ¹ and R ² may be the same or different independently. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ¹ represents a polymer skeleton. However, when A ¹ is a monovalent organic group containing at least one ionic functional group, P ¹ may be a nonionic polymer skeleton or an ionic polymer skeleton. ^{When 1} is a monovalent organic group not containing an ionic functional group, P ¹ represents an ionic polymer skeleton. The m P ¹ may be the same or different. ] It is represented by the following general formula (2), The polymer compound according to claim 1.

[Wherein R ³ represents an (m + n) -valent organic linking group, and R ⁴ and R ⁵ each independently represents a single bond or a divalent organic linking group. A ² represents an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, A monovalent organic group containing at least one site selected from an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group. n A ² and R ⁴ may be the same or different independently. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. P ² represents a polymer skeleton. However, when A ² is a monovalent organic group containing at least one ionic functional group, P ² may be a nonionic polymer skeleton or an ionic polymer skeleton. ^{When 2} is a monovalent organic group not containing an ionic functional group, P ² represents an ionic polymer skeleton. m P ² and R ⁵ may be the same or different independently. ] The A ¹ is a monovalent organic group containing at least one site selected from an organic dye structure, a heterocyclic structure, a hydrocarbon group having 4 or more carbon atoms, and an ionic functional group. Item 5. The polymer compound according to Item 1. The A ² is a monovalent organic group containing at least one site selected from an organic dye structure, a heterocyclic structure, a hydrocarbon group having 4 or more carbon atoms, and an ionic functional group. Item 5. The polymer compound according to Item 2. 4. The polymer compound according to claim ¹ , wherein the polymer skeleton represented by P ¹ is a polymer or copolymer of a vinyl monomer. 5. The polymer compound according to claim ² , wherein the polymer skeleton represented by P ² is a polymer or copolymer of a vinyl monomer.   The polymer compound according to any one of claims 1 to 6, wherein the weight average molecular weight is 3000 to 100,000. The polymer compound according to any one of claims 1 to 7, which is obtained by performing a radical polymerization reaction in the presence of a compound represented by the following general formula (3).

[Wherein R ⁶ represents an (m + n) -valent organic linking group, and R ⁷ represents a single bond or a divalent organic linking group. A ³ is an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group Represents a monovalent organic group containing at least one site selected from an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group. n A ³ and R ⁷ may be the same or different independently. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. ] A method for producing a polymer compound according to any one of claims 1 to 8, wherein the polymer is subjected to a radical polymerization reaction in the presence of a compound represented by the following general formula (3): A method for producing a compound.

[Wherein R ⁶ represents an (m + n) -valent organic linking group, and R ⁷ represents a single bond or a divalent organic linking group. A ³ is an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group Represents a monovalent organic group containing at least one site selected from an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group. n A ³ and R ⁷ may be the same or different independently. m represents 1 to 8, n represents 2 to 9, and m + n satisfies 3 to 10. ] The compound represented by the general formula (3) is:
(A) a compound having 3 to 10 mercapto groups in one molecule;
(B) an organic dye structure, a heterocyclic structure, an acidic group, a group having a basic nitrogen atom, a urea group, a urethane group, a group having a coordinating oxygen atom, a hydrocarbon group having 4 or more carbon atoms, an alkoxysilyl group, A compound having at least one site selected from an epoxy group, an isocyanate group, a hydroxyl group and an ionic functional group, and a functional group capable of reacting with a mercapto group;
The method for producing a polymer compound according to claim 9, which is an addition reaction product of   An aqueous pigment dispersant containing the polymer compound according to any one of claims 1 to 8.   An aqueous pigment dispersion composition comprising a pigment and the aqueous pigment dispersant according to claim 11 in an aqueous medium.   A water-based ink comprising the aqueous pigment dispersion composition according to claim 12.   The water-based ink according to claim 13, which is for inkjet recording.