JP2007131832A - Pigment composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a pigment composition excellent in dispersibility, fluidity and storage stability. <P>SOLUTION: The pigment composition comprises a pigment, at least one basic group-bearing synergist(Y) selected from the group consisting of basic group-bearing pigment derivative, basic group-bearing anthraquinone derivative, basic group-bearing acridone derivative and basic group-bearing triazine derivative, and a dispersant(S). In this pigment composition, the dispersant(S) is such as to be obtained by reaction between a polymer(POH) bearing a hydroxy group on one end thereof or a polymer(PNH<SB>2</SB>) bearing a primary amino group on one end thereof and a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a pigment composition excellent in dispersibility, fluidity and storage stability.

  In general, when producing a pigment composition, it is known that it is difficult to stably disperse the pigment at a high concentration, which causes various problems to the production process and the product itself.

  For example, pigment compositions containing pigments composed of fine particles often exhibit high viscosity, making it difficult to remove and transport the product from a disperser, and in the worst case, cause gelation during storage, It may even be difficult to use. Furthermore, regarding the surface of the color-developed product of the pigment composition, a poor state such as a decrease in gloss and poor leveling occurs. In addition, when different types of pigments are used in combination, color unevenness due to aggregation or phenomena such as sedimentation may cause color unevenness or a significant reduction in coloring power.

  Therefore, in general, a dispersant is used in order to maintain a good dispersion state. The dispersant has a structure of a site that adsorbs to the pigment and a site that has a high affinity for the solvent that is the dispersion medium, and the performance of the dispersant is determined by the balance of these two functional sites. Various dispersants are used in accordance with the surface state of the pigment to be dispersed, but an acidic dispersant is generally used for pigments having a surface that is biased toward basicity. In this case, the acidic functional group becomes the adsorption site of the pigment. Dispersants having a carboxylic acid as an acidic functional group are described in, for example, Patent Document 1, Patent Document 2, Patent Document 3, and Patent Document 4.

  However, these have some dispersibility, but in order to make a low viscosity and stable dispersion, it is necessary to increase the amount of the dispersant contained in the pigment composition. However, increasing the amount used is not preferable in view of development in inks, paints, etc., because the resistance of the coating film may be reduced.

  On the other hand, Patent Literature 5, Patent Literature 6, Patent Literature 7 and the like propose a method in which a pigment is used as a base skeleton and a synergist having an acidic group or a basic group as a substituent in the side chain is mixed with the pigment composition. . However, this alone does not necessarily provide a satisfactory effect, and it has been proposed to use a dispersant having a counter ion for synergists having an acidic group or basic group as a substituent as described above. (Patent Documents 8 and 9). Here, the synergist has a structure similar to the chemical structure of the pigment that forms the pigment, and is strongly adsorbed to the pigment by π-π interaction, and the surface of the pigment is covered by the ionic functional group contained in the synergist. The effect of the dispersant or pigment carrier having a counter ion is increased by making it acidic or basic.

Patent Document 8 exemplifies a pigment composition containing a synergist having a basic group as a substituent and a dispersant having a phosphate group. A dispersant having a phosphoric acid group has a certain degree of pigment dispersion ability in combination with a synergist having a basic group as a substituent, but has poor storage stability or a defect derived from phosphoric acid, such as low heat resistance. In some cases, problems may arise due to poor chemical resistance and poor compatibility. The same applies to the dispersant having sulfonic acid. Pigment compositions using such dispersants having phosphoric acid groups or sulfonic acid groups are poor in expandability to applied inks and paints, etc., while conventional dispersants using carboxylic acids are basic. In the pigment composition combined with a synergist having a group as a substituent, there is no problem in terms of heat resistance, chemical resistance, compatibility, but high viscosity, poor stability, poor pigment fine dispersion, There was a problem.
JP-A-61-61623 JP-A-1-141968 Japanese Patent Laid-Open No. 2-219866 JP 11-439842 A JP-A-63-305137 JP-A-1-247468 JP-A-3-26767 JP-A 63-248864 JP-A-9-176511

  An object of this invention is to provide the pigment composition excellent in a dispersibility, fluidity | liquidity, and storage stability.

Pigments,
A synergist (Y) having at least one basic group selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group;
A pigment composition comprising a dispersant (S),
The dispersant (S) comprises a polymer having a hydroxyl group at one end (POH) or a polymer having a primary amino group at one end (PNH ₂ ), a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride. The present invention relates to a pigment composition obtained by reacting.

  In the present invention, the basic group of the synergist (Y) having a basic group is represented by the following general formula (1), the following general formula (2), the following general formula (3), and the following general formula (4). It is at least one selected from the group described above.

[In General formula (1)-General formula (4),
Each J independently represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ —, or a direct bond;
f represents an integer of 1 to 10,
R ¹ and R ² are each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ¹ and R ² in the formula Together with a nitrogen atom, a nitrogen atom, an oxygen atom, or a sulfur atom, which represents an optionally substituted heterocyclic residue,
R ³ represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group;
R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. ,
K represents —NR ⁸ —Z—NR ⁹ — or a direct bond,
R ⁸ and R ⁹ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group;
Z represents an alkylene group which may be substituted, an alkenylene group which may be substituted, or a phenylene group which may be substituted;
W represents a substituent represented by the general formula (1) or a substituent represented by the general formula (3), and Q represents a hydroxyl group, an alkoxyl group, or a substituent represented by the general formula (1). Or a substituent represented by the general formula (3). ]
In the present invention, the polymer having a hydroxyl group at one end (POH) or the polymer having a primary amino group at one end (PNH ₂ ) is represented by the following general formula (5): The present invention relates to a pigment composition.

General formula (5):

[In general formula (5),
Y ¹ is a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms,
X ² is —O—, —S—, or —N (R ^b ) — (where R ^b is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms),
Z ¹ is —OH or —NH ₂ ;
G ¹ is a repeating unit represented by —R ¹¹ O—,
G ² is a repeating unit represented by —C (═O) R ¹² O—,
G ³ is a repeating unit represented by —C (═O) R ¹³ C (═O) —OR ¹⁴ O—,
R ¹¹ is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms,
R ¹² is a linear or branched alkylene group having 1 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms,
R ¹³ is a linear or branched alkylene group having 2 to 6 carbon atoms, a linear or branched alkenylene group having 2 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or carbon An arylene group having 6 to 20 atoms,
R ¹⁴ is represented by —CH (R ¹⁵ ) —CH (R ¹⁶ ) —,
One of R ¹⁵ and R ¹⁶ is a hydrogen atom, and the other is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyl group The alkyloxymethylene group having 1 to 20 carbon atoms in the moiety, the alkenyloxymethylene group having 2 to 20 carbon atoms in the alkenyl moiety, the aryl moiety having 6 to 20 carbon atoms in the aryl moiety, and optionally substituted with a halogen atom An aryloxymethylene group, an N-methylene-phthalimide group,
R ¹⁷ is R ¹¹ , —C (═O) R ¹² —, or —C (═O) R ¹³ C (═O) —OR ¹⁴ —,
m1 is an integer of 0 to 100, m2 is an integer of 0 to 60, m3 is an integer of 0 to 30, provided that m1 + m2 + m3 is 1 or more and 100 or less,
The arrangement of the repeating units G ^{1 to} G ^{3 in} the general formula (5) does not limit the order thereof, and in the polymer represented by the general formula (5), between the group X ² and the group R ^17. Indicates that the repeating units G ^{1 to} G ³ are included in an arbitrary order, and these repeating units G ^{1 to} G ³ may be either random type or block type, respectively. ]
The present invention also relates to the above pigment composition, wherein Y ¹ is a linear or branched alkyl group having 1 to 18 carbon atoms.

The present invention also relates to the above pigment composition, wherein Y ¹ has an ethylenically unsaturated double bond.

The present invention also relates to the above pigment composition, wherein Y ¹ has two or more ethylenically unsaturated double bonds.

  Moreover, this invention relates to the said pigment composition characterized by m2 being an integer of 3-15.

  The present invention also relates to the above pigment composition, wherein m1 is an integer of 2 to 20, and m2 is an integer of 3 to 15.

Further, the invention is characterized in that when m2 is 2 or more, the plurality of R ¹² are different groups selected from the group consisting of a pentamethylene group, a hexamethylene group, and an alkyl-substituted hexamethylene group. The above-mentioned pigment composition.

In the present invention, the polymer (POH) having a hydroxyl group at one end or the polymer (PNH ₂ ) having a primary amino group at one end is represented by the following general formula (6). The present invention relates to a pigment composition.

General formula (6):

[In General Formula (6), Y ² is a polymerization termination group of the vinyl polymer,
Z ² is —OH or —NH ₂ ;
R ²¹ and R ²² are each independently a hydrogen atom or a methyl group,
One of R ²³ and R ²⁴ is a hydrogen atom, the other is an aromatic group, or —C (═O) —X ⁶ —R ²⁵ (where X ⁶ is —O— or —N (R ²⁶ )-, and R ²⁵ and R ²⁶ are hydrogen atoms or linear or branched alkyl groups having 1 to 18 carbon atoms, which can have an aromatic group as a substituent,
X ⁴ is —O—R ²⁷ — or —S—R ²⁷ —, wherein R ²⁷ is a linear or branched alkylene group having 1 to 18 carbon atoms,
n is 2-50. ]
The present invention also relates to the above pigment composition, wherein the tricarboxylic anhydride or tetracarboxylic dianhydride is an aromatic tricarboxylic anhydride or an aromatic tetracarboxylic dianhydride.

Moreover, this invention relates to the pigment dispersion formed by disperse | distributing the said pigment composition to a varnish.

  By using a specific dispersant and a specific synergist, it was possible to provide a pigment dispersion excellent in dispersibility, fluidity, and storage stability.

  The pigment composition according to the present invention includes a pigment and a synergist (Y) having a basic group (hereinafter sometimes referred to as a basic synergist (Y)) and a dispersant (S), and the basic synergist (Y). Can adsorb on the surface of the pigment and make the surface basic even with pigments that are not neutral to basic. On the other hand, the dispersant (S) has a specific structure having two or three carboxyl groups, and this structure and the basic group of the basic synergist (Y) (present on the pigment surface) Have an electrostatic interaction, and the polymer part present in the dispersant (S) has affinity for the solvent as the dispersion medium, so that the pigment can be stably present in the dispersion medium.

  Examples of the pigment that can be used in the pigment composition of the present invention include various pigments used in inks and the like. Examples of organic pigments include soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidines. Pigment, Anthanthrone pigment, Indanthrone pigment, Flavanthrone pigment, Pyranthrone pigment, Diketopyrrolopyrrole pigment, etc. More specific examples are shown by generic names of color index, for example, Pigment Black 7, Pigment Blue 15, 15: 1, 15: 3, 15: 4, 15: 6, 60, Pigment Green 7, 36, Pigment Red 9, 48, 49, 52, 53, 57, 97, 122, 144, 146, 149, 166, 168, 177, 1 8, 179, 185, 206, 207, 209, 220, 221, 238, 242, 254, 255, pigment violet 19, 23, 29, 30, 37, 40, 50, pigment yellow 12, 13, 14, 17, 20, 24, 74, 83, 86, 93, 94, 95, 109, 110, 117, 120, 125, 128, 137, 138, 139, 147, 148, 150, 151, 154, 155, 166, 168, 180, 185, pigment orange 13, 36, 37, 38, 43, 51, 55, 59, 61, 64, 71, 74, and the like.

  Further, the pigment composition of the present invention includes metal oxides such as titanium dioxide, iron oxide, antimony pentoxide, zinc oxide, silica, cadmium sulfide, calcium carbonate, barium carbonate, barium sulfate, clay, talc, chrome lead, Inorganic pigments such as carbon black can also be used.

The pigment composition of the present invention is not limited to the pigments exemplified above, and any pigment composition may be used as long as it is in the form of fine powder.

The basic synergist (Y) that can be contained in the pigment dispersion of the present invention includes “a pigment derivative having a basic group”, “anthraquinone derivative having a basic group”, “acridone derivative having a basic group”, And “a triazine derivative having a basic group”.

  Examples of the basic group include at least one group selected from the group consisting of the groups represented by the general formula (1), the general formula (2), the general formula (3), and the general formula (4). be able to.

In the general formula (1) to the general formula (4),
J is independently in the general formula (1) and the general formula _{(4), -SO 2 -,} - CO -, - CH 2 NHCOCH 2 -, - CH 2 -, or a direct bond,
f represents an integer of 1 to 10,
R ¹ and R ² are each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ¹ and R ² in the formula Together with a nitrogen atom, a nitrogen atom, an oxygen atom, or a sulfur atom, which represents an optionally substituted heterocyclic residue,
R ³ represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group;
R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. ,
K represents —NR ⁸ —Z—NR ⁹ — or a direct bond,
R ⁸ and R ⁹ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group;
Z represents an alkylene group which may be substituted, an alkenylene group which may be substituted, or a phenylene group which may be substituted;
W represents a substituent represented by the general formula (1) or a substituent represented by the general formula (3), and Q represents a hydroxyl group, an alkoxyl group, or a substituent represented by the general formula (1). Or a substituent represented by the general formula (3).

In a preferred form as the substituent represented by the general formula (1), J is —SO ₂ — or —CO—, f is 1 to 5 (more preferably 2 to 4), and R ¹ and R ² Are each independently a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, an iso-butyl group, or R ¹ and R ² are combined with a nitrogen atom in the formula In this case, morpholine is formed.

A preferable form of the substituent represented by the general formula (2) is that R ¹ and R ² are each independently a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, or an iso-butyl group. This is the case.

A preferred form of the substituent represented by the general formula (3) is that J is —CH ₂ NHCOCH ₂ —, and R ³ is a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, or an n-butyl group. Or it is an iso-butyl group, and R < ⁴ > -R < ⁷ > is a case of a hydrogen atom.

In a preferred form as the substituent represented by the general formula (4), J is a direct bond or —SO ₂ —, K is a direct bond or —NH—Z—NH—, Z is a phenylene group, Q is a hydroxyl group, a methoxy group, an ethoxy group, a propoxy group or a butoxy group, W is a substituent represented by the general formula (1), and J in the W is —SO ₂ — or —CO—. F in the W is 1 to 5 (more preferably 2 to 4), and R ¹ and R ² in the W are each independently a methyl group, an ethyl group, an n-propyl group, or an iso-propyl group. , N-butyl group, and iso-butyl group.

  Examples of amine compounds used to form the substituents represented by the general formula (1) to the general formula (4) include secondary or tertiary monoamines, diamines, cyclic amines, and carboxyl group-containing cyclic amines. , Hydroxyl group-containing cyclic amines, and cyclic diamines. Specifically, dimethylamine, diethylamine, methylethylamine, N, N-ethylisopropylamine, N, N-ethylpropylamine, N, N-methylbutylamine, N, N-methylisobutylamine, N, N-butylethylamine N, N-tert-butylethylamine, diisopropylamine, dipropylamine, N, N-sec-butylpropylamine, dibutylamine, di-sec-butylamine, diisobutylamine, N, N-isobutyl-sec-butylamine, diamylamine , Diisoamylamine, dihexylamine, dicyclohexylamine, di (2-ethylhexyl) amine, dioctylamine, N, N-methyloctadecylamine, didecylamine, diallylamine, N, N-ethyl-1,2-dimethylpro Ruamine, N, N-methylhexylamine, dioleylamine, distearylamine, N, N-dimethylaminomethylamine, N, N-dimethylaminoethylamine, N, N-dimethylaminoamylamine, N, N-dimethylaminobutylamine N, N-diethylaminoethylamine, N, N-diethylaminopropylamine, N, N-diethylaminohexylamine, N, N-diethylaminobutylamine, N, N-diethylaminopentylamine, N, N-dipropylaminobutylamine, N, N-dibutylaminopropylamine, N, N-dibutylaminoethylamine, N, N-dibutylaminobutylamine, N, N-diisobutylaminopentylamine, N, N-methyl-laurylaminopropylamine, N, N-ethyl-hex Ruaminoethylamine, N, N-distearylaminoethylamine, N, N-dioleylaminoethylamine, N, N-distearylaminobutylamine, piperidine, 2-pipecoline, 3-pipecoline, 4-pipecoline, 2,4-lupetidine 2,6-lupetidine, 3,5-lupetidine, 3-piperidinemethanol, pipecolic acid, isonipecotic acid, methyl isonicopetinate, ethyl isonicopetinate, 2-piperidineethanol, pyrrolidine, 3-hydroxypyrrolidine, N-aminoethylpiperidine, N-aminoethyl-4-pipecholine, N-aminoethylmorpholine, N-aminopropylpiperidine, N-aminopropyl-2-pipecholine, N-aminopropyl-4-pipecoline, N-aminopropylmorpholine, N-methylpipecoline Razine, N-butylpiperazine, N-methylhomopiperazine, 1-cyclopentylpiperazine, 1-amino-4-methylpiperazine, 1-cyclopentylpiperazine and the like can be mentioned.

  Examples of the “pigment portion constituting the pigment derivative having a basic group” include diketopyrrolopyrrole dyes, azo dyes such as azo, disazo and polyazo, phthalocyanine dyes, diaminodianthraquinone, anthrapyrimidine, and flavantrons. Anthraquinone dyes such as anthrone, indanthrone, pyranthrone, violanthrone, quinacridone dyes, dioxazine dyes, perinone dyes, perylene dyes, thioindigo dyes, isoindoline dyes, isoindolinone dyes, quinophthalone dyes Derived from organic dyes such as selenium dyes and metal complex dyes. Further, “anthraquinone derivative having a basic group” or “acridone derivative having a basic group” includes, on the anthraquinone ring or acridone ring, in addition to the basic group, an alkyl group such as a methyl group or an ethyl group, an amino group It may have a substituent such as a group, a nitro group, a hydroxyl group, an alkoxy group such as a methoxy group or an ethoxy group, or a halogen such as chlorine.

  Further, the triazine moiety constituting the “triazine derivative having a basic group” includes, in addition to the basic group, an alkyl group (for example, methyl group, ethyl group, butyl group, etc.), an amino group, an alkylamino group (for example, Dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro group, hydroxyl group, alkoxy group (eg methoxy group, ethoxy group, butoxy group etc.), halogen atom (eg chlorine atom, bromine atom etc.), phenyl group (For example, an alkyl group, an amino group, an alkylamino group, a nitro group, a hydroxyl group, an alkoxy group, a halogen atom and the like may be substituted) and a phenylamino group (for example, an alkyl group, an amino group, an alkylamino group, It may have a substituent such as a nitro group, a hydroxyl group, an alkoxy group, or a halogen atom. Preferred triazine moieties are derived from 1,3,5-triazine.

The “pigment derivative having a basic group”, “anthraquinone derivative having a basic group”, and “acridone derivative having a basic group” used in the present invention can be synthesized by various known synthesis methods by known methods. it can. For example, after introducing a substituent represented by the following formula (7) to the following formula (10) into an organic dye, anthraquinone or acridone, it reacts with these substituents to give the above general formula (1) to the above general formula ( 4) Amine compounds capable of forming the substituent represented by, for example, N, N-dimethylaminopropylamine, N-methylpiperazine, diethylamine or 4- [4-hydroxy-6- [3- (dibutylamino) Propylamino] -1,3,5-triazin-2-ylamino] aniline and the like can be obtained.
Formula (7): —SO ₂ Cl
Formula (8): -COCl
Formula (9): —CH ₂ NHCOCH ₂ Cl
Formula (10): —CH ₂ Cl
When the organic dye is an azo dye, the substituent represented by the general formula (1) to the general formula (4) is previously converted to a diazo component (for example, a compound having a diazo group) or a coupling component (for example, Azo pigment derivatives can also be produced by introducing them into a compound having an acetamide group) and then performing a coupling reaction.

  The “triazine derivative having a basic group” used in the present invention can be synthesized by a known method through various synthetic routes. For example, starting from cyanuric chloride, an amine compound that forms a substituent represented by the general formula (1) to the general formula (4) on at least one chlorine atom of cyanuric chloride, for example, N, N-dimethyl It can be obtained by reacting aminopropylamine or N-methylpiperazine or the like and then reacting the remaining chlorine atom of cyanuric chloride with various amine compounds or alcohol compounds.

  In the pigment composition of the present invention, the amount of the basic synergist is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and most preferably 5 to 25 parts by weight with respect to 100 parts by weight of the pigment. When the basic synergist is less than 1 part by weight with respect to 100 parts by weight of the pigment, the dispersibility may be deteriorated, and when it exceeds 50 parts by weight, the heat resistance and / or light resistance may be deteriorated.

The dispersant (S) of the present invention comprises a polymer having a hydroxyl group at one end (POH) or a polymer having a primary amino group at one end (PNH ₂ ), a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride. Can be obtained by reaction.

As a preferred form of the polymer having a hydroxyl group at one end (POH) or the polymer having a primary amino group at one end (PNH ₂ ), the one represented by the general formula (5) is first mentioned.

In the general formula (5), Y ¹ is preferably a linear or branched alkyl group having 1 to 18 carbon atoms from the viewpoint of lowering the viscosity of the pigment dispersion and storage stability.

As another form, in the general formula (5), Y ¹ preferably has an ethylenically unsaturated double bond. In this case, active energy ray curability can be imparted to the dispersant (S).

  In the general formula (5), m2 is preferably an integer of 3 to 15 from the viewpoints of lowering the viscosity and storage stability of the pigment dispersion.

In the general formula (5), when m2 = 0 and m3 = 0, Y ¹ is a linear or branched alkyl group having 1 to 7 carbon atoms, or an ethylenically unsaturated divalent group. It preferably has a double bond.

  The polymer (POH) having a hydroxyl group at one end represented by the general formula (5) can be produced by a known method, and is selected from the group consisting of monoalcohol, primary monoamine, secondary monoamine, and monothiol. It can be easily obtained by ring-opening polymerization of a cyclic compound selected from the group of alkylene oxide, lactone, lactide, dicarboxylic anhydride, and epoxide, using the compound as an initiator.

  The monoalcohol may be any compound as long as it is a compound having one hydroxyl group. For example, methanol, ethanol, 1-propanol, isopropanol, 1-butanol, isobutanol, tert-butanol, 1-pentanol, isopentanol, 1-hexanol, cyclohexanol, 4-methyl-2-pentanol, 1 -Heptanol, 1-octanol, isooctanol, 2-ethylhexanol, 1-nonanol, isononanol, 1-decanol, 1-dodecanol, 1-myristyl alcohol, cetyl alcohol, 1-stearyl alcohol, isostearyl alcohol, 2-octyldeca Nol, 2-octyldodecanol, 2-hexyldecanol, behenyl alcohol, oleyl alcohol and other aliphatic monoalcohols, benzyl alcohol, phenoxyethyl alcohol, paracumi Aromatic ring-containing monoalcohols such as phenoxyethyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, ethylene glycol mono-2-ethylhexyl ether, propylene glycol Monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monohexyl ether, propylene glycol mono-2-ethylhexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol Propyl ether, diethylene glycol monobutyl ether, diethylene glycol monohexyl ether, diethylene glycol mono-2-ethylhexyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monobutyl ether, dipropylene glycol mono Hexyl ether, dipropylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monopropyl ether, triethylene glycol monobutyl ether, triethylene glycol monohexyl ether, triethylene glycol mono − 2-ethylhexyl ether, tripropylene glycol monomethyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monopropyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monohexyl ether, tripropylene glycol mono-2-ethylhexyl ether, tetraethylene Glycol monomethyl ether, tetraethylene glycol monoethyl ether, tetraethylene glycol monopropyl ether, tetraethylene glycol monobutyl ether, tetraethylene glycol monohexyl ether, tetraethylene glycol mono-2-ethylhexyl ether, tetrapropylene glycol monomethyl ether, tetrapropylene glycol Mo Ethyl ether, tetrapropylene glycol monopropyl ether, tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, and alkylene glycol monoalkyl ethers such as tetramethyl diethylene glycol monomethyl ether.

  A monoalcohol having an ethylenically unsaturated double bond may be used as the monoalcohol. In this case, active energy ray curing performance can be imparted to the produced dispersant (S).

  Examples of the group having an ethylenically unsaturated double bond include a vinyl group or a (meth) acryloyl group (hereinafter referred to as “(meth) acryloyl” or “(meth) acrylate”). Each represents “acryloyl and / or methacryloyl” or “methacrylate and / or acrylate”, with a (meth) acryloyl group being preferred. The type of the group having a double bond may be one type or a plurality of types.

  As the monoalcohol having an ethylenically unsaturated double bond, a compound containing one, two, and three or more ethylenically unsaturated double bonds can be used. Examples of the monoalcohol having one ethylenically unsaturated double bond include 2-hydroxyethyl (meth) acrylate (in the case of “(meth) acrylate”, acrylate and / or methacrylate). The same shall apply hereinafter.), 3-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 2-hydroxybutyl (Meth) acrylate, ethyl 2- (hydroxymethyl) acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 1,4-cyclohexanedimethanol mono (meth) acrylate, 2-hydroxyethyl vinyl ether, diethylene glycol monovinyl ester Ether, 4-hydroxybutyl vinyl ether. Examples of the monoalcohol having two ethylenically unsaturated double bonds include 2-hydroxy-3-acryloyloxypropyl methacrylate and glycerin di (meth) acrylate. Examples of the monoalcohol having 3 ethylenically unsaturated double bonds include pentaerythritol triacrylate, and examples of the monoalcohol having 5 ethylenically unsaturated double bonds include dipentaerythritol pentaacrylate. Is mentioned.

Of these, pentaerythritol triacrylate and dipentaerythritol pentaacrylate are obtained as a mixture of pentaerythritol tetraacrylate and dipentaerythritol hexaacrylate, respectively. Therefore, in order to control the molecular weight of the produced dispersant, HPLC (high speed It is necessary to determine the ratio of monoalcohols by liquid chromatography) method or hydroxyl value measurement. This is because the molecular weight of the dispersant is determined by the number of monoalcohols and the ratio of raw materials forming G ^{1 to} G ³ .

  Among the above-mentioned monoalcohols, those having two or more ethylenically unsaturated double bonds are preferable in the case of use in an active energy ray-curable pigment composition in terms of curability.

  Examples of the primary monoamine include methylamine, ethylamine, 1-propylamine, isopropylamine, 1-butylamine, isobutylamine, tert-butylamine, 1-pentylamine, isopentylamine, 3-pentylamine, and 1-hexylamine. , Cyclohexylamine, 4-methyl-2-pentylamine, 1-heptylamine, 1-octylamine, isooctylamine, 2-ethylhexylamine, 1-nonylamine, isononylamine, 1-decylamine, 1-dodecylamine, 1 Aliphatic primary monoamines such as myristylamine, cetylamine, 1-stearylamine, isostearylamine, 2-octyldecylamine, 2-octyldecylamine, 2-hexyldecylamine, behenylamine, oleylamine 3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 2-ethylhexyloxypropylamine, 3-isobutyroxypropylamine, 3-decyloxypropylamine, 3 -Alkoxyalkyl primary monoamines such as myristyloxypropylamine and aromatic primary monoamines such as benzylamine. Examples of secondary monoamines include dimethylamine, diethylamine, di-1-propylamine, diisopropylamine, di-1-butylamine, diisobutylamine, di-1-pentylamine, diisopentylamine, and di-1-hexylamine. , Dicyclohexylamine, di- (4-methyl-2-pentyl) amine, di-1-heptylamine, di-1-octylamine, isooctylamine, di- (2-ethylhexyl) amine, di-1-nonylamine, Diisononylamine, di-1-decylamine, di-1-dodecylamine, di-1-myristylamine, dicetylamine, di-1-stearylamine, diisostearylamine, di- (2-octyldecyl) amine, di- (2 -Octyldodecyl) amine, di- (2-hexyldecyl) a Emissions, N- methylethylamine, N- methylbutylamine, N- methyl isobutyl amine, N- methyl-propylamine, N- methyl hexylamine, piperazine, aliphatic secondary monoamine such as alkyl-substituted piperazines.

  Examples of the monothiol include methylthiol, ethylthiol, 1-propylthiol, isopropylthiol, 1-butylthiol, isobutylthiol, tert-butylthiol, 1-pentylthiol, isopentylthiol, 3-pentylthiol, 1- Hexylthiol, cyclohexylthiol, 4-methyl-2-pentylthiol, 1-heptylthiol, 1-octylthiol, isooctylthiol, 2-ethylhexylthiol, 1-nonylthiol, isononylthiol, 1-decylthiol, 1- Dodecylthiol, 1-myristylthiol, cetylthiol, 1-stearylthiol, isostearylthiol, 2-octyldecylthiol, 2-octyldodecylthiol, 2-hexyldecylthiol Aliphatic monothiols such as behenyl thiol and oleyl thiol, methyl thioglycolate, octyl thioglycolate, thioglycolic acid alkyl esters such as methoxybutyl thioglycolate, methyl mercaptopropionate, octyl mercaptopropionate, methoxybutyl mercaptopropionate And mercaptopropionic acid alkyl esters such as mercaptopropionic acid tridecyl.

  The compound selected from the group of monoalcohol, primary monoamine, secondary monoamine, and monothiol referred to in the present invention is not limited to the above examples, but is a hydroxyl group, primary amino group, secondary amino group, or thiol. Any compound can be used as long as it is a compound having one group, and it may be used alone or in combination of two or more.

Here, the portions other than the hydroxyl group, primary amino group, secondary amino group, or thiol group of monoalcohol, primary monoamine, secondary monoamine, or monothiol, respectively, represent Y ¹ in the general formula (5). Constitute.

From the group consisting of alkylene oxides, lactones, lactides, and combinations of dicarboxylic acid anhydrides and epoxides, with the compound selected from the group of the exemplified monoalcohols, primary monoamines, secondary monoamines, and monothiols as initiators. The selected cyclic compound can be subjected to ring-opening polymerization to produce a polymer represented by the general formula (5) in which Z ¹ is —OH. However, the dicarboxylic acid anhydride and the epoxide are always used at the same time and are alternately polymerized.

Here, the reaction order of the cyclic compound selected from the group consisting of alkylene oxide, lactone, lactide, and a combination of dicarboxylic anhydride and epoxide may be any, for example, the initiator as the first step After the alkylene oxide is polymerized, the lactone can be polymerized in the second stage, and the dicarboxylic acid anhydride and the epoxide can be alternately polymerized in the third stage. In this example, the initiator for polymerizing the lactone in the second stage is an alkylene oxide polymer having a hydroxyl group at one end polymerized in the first stage. The initiator for alternately polymerizing dicarboxylic acid anhydrides and epoxides in the third stage is a block copolymer of an alkylene oxide polymer having a hydroxyl group at one end and a lactone polymer polymerized by the second stage. It becomes a polymer. In the production method of the present invention, Z ^{1 in the} polymer represented by the general formula (5) is used as an initiator in the production of the polymer represented by the general formula (5) described below. Also includes -OH. Similarly, a polymer represented by the general formula (5) described later, wherein Z ¹ is —NH ₂ , or a polymer represented by the general formula (6) can also serve as an initiator.

  The reaction sequence of the cyclic compound is not limited to the combination of the first-stage alkylene oxide, the second-stage lactone, and the third-stage dicarboxylic anhydride and epoxide, but the alkylene oxide, lactone (and / or lactide). , And a combination of a dicarboxylic acid anhydride and an epoxide can be carried out in any order one to several times. Alternatively, for any combination of alkylene oxide, lactone (and / or lactide), and dicarboxylic anhydride and epoxide, without performing any ring-opening polymerization, any cyclic compound is selected from them, Ring-opening polymerization can also be carried out.

  As the alkylene oxide, for example, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide and a combination system of two or more thereof are used. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. As for the polymerization mole number of the alkylene oxide with respect to 1 mol of initiators, 0-100 are preferable.

The polymerization of the alkylene oxide can be carried out in a known manner, for example, in the presence of an alkali catalyst at a temperature of 100 to 200 ° C. under a pressurized state. Alkylene oxide polymers having a hydroxyl group at one end obtained by polymerizing alkylene oxide to the hydroxyl group of monoalcohol are commercially available, for example, Niox series manufactured by Nippon Oil & Fats, Blenmer series manufactured by Nippon Oils & Fats, Among the polymers represented by the general formula (5), Z ¹ is —OH, and it is used as a raw material for the dispersant (S) of the present invention as having only G ¹ among the repeating units of G ^{1 to} G ^3. You can also Specific examples of commercially available products include UNIOX M-400, M-550, M-2000, BLEMMER PE-90, PE-200, PE-350, AE-90, AE-200, AE-400, PP- 1000, PP-500, PP-800, AP-150, AP-400, AP-550, AP-800, 50PEP-300, 70PEP-350B, AEP series, 55PET-400, 30PET-800, 55PET-800, AET Series, 30PPT-800, 50PPT-800, 70PPT-800, APT series, 10PPB-500B, 10APB-500B, etc.

Here, the alkylene group of the alkylene oxide constitutes R ¹¹ in the repeating unit G ¹ in the general formula (5).

  Specific examples of lactones include β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, and alkyl-substituted ε-caprolactone, of which δ- Use of valerolactone, ε-caprolactone, or alkyl-substituted ε-caprolactone is preferable from the viewpoint of ring-opening polymerization.

  In the production method of the present invention, the lactone can be used without being limited to the above examples, and may be used alone or in combination of two or more. Use of two or more types in combination is preferable in terms of workability and compatibility with other resins, since the crystallinity may decrease and become liquid at room temperature.

As the lactide, those represented by the following general formula (11) are preferable (including glycolide).
General formula (11):

[In general formula (11),
R ³¹ and R ³² are each independently a hydrogen atom, a saturated or unsaturated linear or branched alkyl group having 1 to 20 carbon atoms,
R ³³ and R ³⁴ are each independently a hydrogen atom, a halogen atom, or a saturated or unsaturated linear or branched lower alkyl group having 1 to 9 carbon atoms. ]
Particularly suitable lactide as a raw material for the dispersant (S) of the present invention is lactide (3,6-dimethyl-1,4-dioxane-2,5-dione) and glycolide (1,4-dioxane-2,5- Dione). Moreover, it is preferable that lactone is used among the said lactone or lactide as a raw material of the dispersing agent (S) of this invention.

  The ring-opening polymerization of lactone and / or lactide can be carried out in a known manner, for example, by charging an initiator, lactone and / or lactide, and a polymerization catalyst into a reactor connected to a dehydrating tube or a condenser and under a nitrogen stream. . When a monoalcohol having a low boiling point is used, the reaction can be carried out under pressure using an autoclave. Moreover, when using what has an ethylenically unsaturated double bond in monoalcohol, it is preferable to add a polymerization inhibitor and to react under a dry air flow.

  The number of moles of lactone and / or lactide polymerized per mole of initiator is preferably in the range of 1 to 60 moles, more preferably 2 to 20 moles, and most preferably 3 to 15 moles.

  As the polymerization catalyst, a known catalyst can be used without limitation. For example, tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, Quaternary ammonium salts such as benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, benzyltrimethylammonium iodide, tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide , Benzyltrimethylphosphonium chloride, benzyltrime In addition to quaternary phosphonium salts such as ruphosphonium bromide, benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, tetraphenylphosphonium bromide, tetraphenylphosphonium iodide, phosphorus compounds such as triphenylphosphine, potassium acetate, sodium acetate, potassium benzoate In addition to organic carboxylates such as sodium benzoate, alkali metal alcoholates such as sodium alcoholate and potassium alcoholate, tertiary amines, organic tin compounds, organic aluminum compounds, organic titanate compounds, zinc compounds such as zinc chloride, etc. Can be mentioned. The catalyst is used in an amount of 0.1 ppm to 3000 ppm, preferably 1 ppm to 1000 ppm. When the amount of the catalyst exceeds 3000 ppm, the resin may be intensely colored. On the contrary, if the amount of the catalyst used is less than 0.1 ppm, the rate of ring-opening polymerization of lactone and / or lactide is extremely slow, which is not preferable.

  The polymerization temperature of the lactone and / or lactide is 100 ° C. to 220 ° C., preferably 110 ° C. to 210 ° C. When the reaction temperature is less than 100 ° C., the reaction rate is very slow, and when it exceeds 220 ° C., side reactions other than the addition reaction of lactone and / or lactide, for example, depolymerization of lactone adducts to lactone monomers, cyclic lactone dimers and trimers Generation is likely to occur.

Here, a portion other than the ester group of lactone or lactide constitutes R ¹² in the repeating unit G ² in the general formula (5).

  Examples of the dicarboxylic acid anhydride include succinic anhydride, maleic anhydride, phthalic anhydride, itaconic anhydride, glutaric anhydride, dodecenyl succinic anhydride, and chlorendec anhydride.

  Examples of the epoxide include methyl glycidyl ether, ethyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, phenyl glycidyl ether, p-tertiary butyl phenyl glycidyl ether, 2,4-dibromophenyl glycidyl ether, Examples include 3-methyl-dibromophenyl glycidyl ether (wherein the bromo substitution position is arbitrary), allyl glycidyl ether, ethoxyphenyl glycidyl ether, glycidyl (meth) acrylate, glycidyl phthalimide, and styrene oxide.

Dicarboxylic anhydride and epoxide are used simultaneously for the initiator and react alternately. At this time, the hydroxyl group, primary amino group, secondary amino group, or thiol group of the initiator first reacts with the acid anhydride group of the dicarboxylic acid anhydride to form a carboxyl group, and then the epoxide is added to the carboxyl group. The epoxy group reacts to form a hydroxyl group. Further, the reaction similar to the above can be sequentially proceeded so that the acid anhydride group of the dicarboxylic acid anhydride reacts with this hydroxyl group. The number of moles of polymerization of dicarboxylic anhydride and epoxide with respect to 1 mole of initiator is preferably 0 to 30 moles. Moreover, the reaction ratio ([D] / [E]) of dicarboxylic acid anhydride and epoxide is:
0.8 ≦ [D] / [E] ≦ 1.0
([D] is the number of moles of dicarboxylic anhydride, and [E] is the number of moles of epoxide)
It is preferable that If it is less than 0.8, the epoxide remains undesirably, and if it exceeds 1.0, a polymer having a hydroxyl group at one end cannot be obtained, and a polymer having a carboxyl group at one end is formed, which is not preferable.

  The alternating polymerization of the dicarboxylic acid anhydride and the epoxide is preferably performed in the range of 50 ° C to 180 ° C, more preferably 60 ° C to 150 ° C. When the reaction temperature is less than 50 ° C or exceeds 180 ° C, the reaction rate is extremely slow.

Here, the portion other than the dicarboxylic anhydride group of the dicarboxylic anhydride constitutes R ¹³ in the repeating unit G ³ in the general formula (5), and the portion other than the oxygen atom forming the cyclic ether of epoxide is the above-mentioned general portion. R ¹⁴ in the repeating unit G ³ in the formula (5) is constituted.

On the other hand, a polymer (PNH ₂ ) having a primary amino group at one end represented by the general formula (5) can also be produced by a known method. For example, an alkylene oxide can be opened using a monoalcohol as an initiator. It is obtained by ring polymerization to produce an alkylene oxide polymer having a hydroxyl group at one end and reductive amination of the hydroxyl group.

  The method for producing an alkylene oxide polymer having a hydroxyl group at one end is as described above, and the conditions and raw materials are also as described above. This alkylene oxide polymer having a hydroxyl group at one end is used as a precursor, for example, in the presence of ammonia, hydrogen and a catalyst, the reaction is carried out for 0.15 to 2 hours under high temperature conditions of a pressure of 5 to 30 MPa and 170 to 250 ° C. It is obtained by doing. In this way, an alkylene oxide polymer having a primary amino group at one end can be obtained by reductive amination of the hydroxyl group. As the catalyst for reductive amination, Raney nickel / aluminum catalyst is preferable.

Polyether polymers having a primary amino group at one end are commercially available, for example, commercially available from Mitsui Chemicals Fine Company or Huntsman Corporation under the trade name Jeffamine or Surfonamin. Of the polymers represented by (5), Z ¹ is —NH ₂ and it may be used as it is as a raw material for the dispersant (S) of the present invention as having only G ¹ among the repeating units of G ^{1 to} G ^3. it can. Specific examples of commercially available products include Jeffamine XTJ-475, XTJ-436, XTJ-505, XTJ-506, XTJ-507, M-2070, Surfonamin B-60, L-100, B-200, L- 207, L-300, B-30, B-100, and the like.

  When a monoalcohol, dicarboxylic anhydride, or epoxide having an ethylenically unsaturated double bond is used when producing the polymer represented by the general formula (5), a polymerization inhibitor may be used. preferable. As the polymerization inhibitor, for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6-t-butylphenol, phenothiazine and the like are preferable, and these may be used alone or in combination from 0.01% to 6%. %, Preferably in the range of 0.05% to 1.0%.

As another preferred structure of the polymer having a hydroxyl group at one end (POH) or the polymer having a primary amino group at one end (PNH ₂ ), a polymer represented by the general formula (6) can be mentioned. You can also. The polymer represented by the general formula (6) is a vinyl polymer obtained by polymerizing an ethylenically unsaturated monomer.

The part of the repeating unit of the polymer represented by the general formula (6), that is, {-[C (R ²¹ ) (R ²³ ) -C (R ²² ) (R ²⁴ )] _n- } is mutually identical. (Homopolymer) made of a different material or (copolymer) made of a different material. In a preferred form of the polymer represented by the general formula (6), one of R ²¹ and R ²² is a hydrogen atom, the other is a methyl group, and one of R ²³ and R ²⁴ is either A hydrogen atom, the other is —C (═O) —O— (CH ₂ ) ₃ CH ₃ and / or —C (═O) —O—CH ₂ —Ar (Ar is an aromatic group), and X ^This is the case where ⁴ is —S—CH ₂ CH ₂ —.

Y ² in the general formula (6), that is, the polymerization termination group of the vinyl polymer is an arbitrary known polymerization termination introduced when the polymerization of a normal ethylenically unsaturated monomer is carried out by a usual method. And is obvious to those skilled in the art. Specifically, it can be, for example, a group derived from a polymerization initiator, a group derived from a chain transfer agent, a group derived from a solvent, or a group derived from an ethylenically unsaturated monomer. Even if Y ² has any of these chemical structures, the dispersant of the present invention can exert its effect without being influenced by the polymerization termination group Y ² .

Among the polymers represented by the general formula (6), those in which Z ² is —OH can be produced by a known method, for example, a compound having a hydroxyl group and a thiol group and an ethylenically unsaturated monomer. Can be obtained by mixing and heating.

  Examples of the compound having a hydroxyl group and a thiol group in the molecule include mercaptomethanol, 2-mercaptoethanol, 3-mercapto-1-propanol, 1-mercapto-2-butanol, and 2-mercapto-3-butanol. It is done.

  Preferably, bulk polymerization or solution polymerization is performed using a compound having 1 to 30 parts by weight of a hydroxyl group and a thiol group with respect to 100 parts by weight of the ethylenically unsaturated monomer. The reaction temperature is preferably 40 to 150 ° C., more preferably 50 to 110 ° C., and the reaction time is preferably 3 to 30 hours, more preferably 5 to 20 hours.

Among the polymers represented by the general formula (6), those in which Z ² is —NH ₂ can be produced by a known method, for example, a compound having a primary amino group and a thiol group or a primary amino group It can be obtained by mixing and heating a compound having a group and a hydroxyl group and an ethylenically unsaturated monomer.

  Examples of the compound having a primary amino group and a thiol group include 2-aminoethanethiol, 6-amino-2-mercaptobenzothiazole, 3-amino-5-mercapto-1,2,4-triazole, 4- Amino-3-mercapto-4H-1,2,4-triazole, 4-amino-3-mercapto-5-methyl-4H-1,2,4-triazole, 4-amino-2-mercaptopyrimidine, 2-amino -5-mercapto-1,3,4-thiadiazole, 3-amino-5-mercapto-1,2,4-thiazole, 5-amino-2-mercaptobenzimidazole and the like. Of these, 2-aminoethanethiol is preferably used.

  Examples of the compound having a primary amino group and a hydroxyl group in the molecule include 2-aminoethanol, 3-aminopropanol, and 4-aminobutanol.

  Among these compounds, compounds having a primary amino group and a thiol group in the molecule have a higher chain transfer constant and are less likely to remain as an unreacted product after the production of the polymer. Therefore, the compounds have a primary amino group and a hydroxyl group in the molecule. Is also preferable.

  Preferably, bulk polymerization or solution polymerization is performed using 1 to 30 parts by weight of a compound having a primary amino group and a thiol group with respect to 100 parts by weight of the ethylenically unsaturated monomer.

  Since the thiol group becomes a radical generating group for polymerizing the ethylenically unsaturated monomer, another polymerization initiator is not necessarily required for the polymerization, but it can also be used. When using this polymerization initiator, 0.001-5 weight part is preferable with respect to 100 weight part of ethylenically unsaturated monomers. As the polymerization initiator, for example, an azo compound and an organic peroxide can be used. Examples of the azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2′-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like. Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like. These polymerization initiators can be used alone or in combination of two or more.

  Examples of the ethylenically unsaturated monomer include acrylic monomers and monomers other than acrylic monomers. Examples of the acrylic monomer include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t -Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth ) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate (Meth) acrylates such as ethoxypolyethylene glycol (meth) acrylate, (meth) acrylamide (note that “(meth) acrylamide” represents acrylamide and / or methacrylamide. The same)), N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and (meth) acrylamides such as acryloylmorpholine, Examples include amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate.

  Examples of the monomer other than the acrylic monomer include styrenes such as styrene and α-methylstyrene, and vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether. And fatty acid vinyls such as vinyl acetate and vinyl propionate. The monomer other than the acrylic monomer can be used in combination with the acrylic monomer.

  Moreover, a carboxyl group-containing ethylenically unsaturated monomer can be used alone or in combination with the monomer. Examples of the carboxyl group-containing ethylenically unsaturated monomer include acrylic acid, methacrylic acid, ε-couplerlactone-added acrylic acid, ε-couplerlactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid. 1 type (s) or 2 or more types can be selected from these.

  In the step of producing the polymer represented by the general formula (6), no solvent or a solvent may be used depending on the case. Examples of the solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, and cyclohexanone, but are not particularly limited thereto. Two or more kinds of these polymerization solvents may be mixed and used.

  The amount of the solvent used is preferably 0 to 300 parts by weight, more preferably 0 to 100 parts by weight, based on 100 parts by weight of the ethylenically unsaturated monomer. The solvent used can be removed by an operation such as distillation after completion of the reaction, or can be used as it is as a part of the product of the dispersant.

Next, the process of reacting “polymer (POH) or polymer (PNH ₂ ) having a hydroxyl group at one end” with a tricarboxylic acid anhydride or tetracarboxylic dianhydride will be described.

A hydroxyl group of the “polymer having a hydroxyl group at one end (POH)”, or a primary amino group of the “polymer having a primary amino group at one end (PNH ₂ )”; and a tricarboxylic acid anhydride or The dispersant (S) of the present invention can be obtained by reacting with the anhydride group of tetracarboxylic dianhydride.

  Examples of the tricarboxylic acid anhydride include an aliphatic tricarboxylic acid anhydride or an aromatic tricarboxylic acid anhydride.

  Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid- 1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride, etc. are mentioned.

  Examples of the aromatic tricarboxylic acid include benzenetricarboxylic acid anhydride (1,2,3-benzenetricarboxylic acid anhydride, trimellitic acid anhydride (1,2,4-benzenetricarboxylic acid anhydride), etc.), naphthalenetricarboxylic acid, and the like. Acid anhydride (1,2,4-naphthalenetricarboxylic acid anhydride, 1,4,5-naphthalenetricarboxylic acid anhydride, 2,3,6-naphthalenetricarboxylic acid anhydride, 1,2,8-naphthalenetricarboxylic acid anhydride Products), 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride, 2,3,2 ′ -Biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, 3,4,4'-biphenyl Sulfonic tricarboxylic acid anhydrides.

  When using a tricarboxylic acid anhydride, an aromatic tricarboxylic acid anhydride is preferable among the above.

  Examples of tetracarboxylic dianhydrides include aliphatic tetracarboxylic dianhydrides, aromatic tetracarboxylic dianhydrides, and polycyclic tetracarboxylic dianhydrides.

  Examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, and 1,3-dimethyl. -1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 2, 3,5,6-tetracarboxycyclohexane dianhydride, 2,3,5,6-tetracarboxynorbornane dianhydride, 3,5,6-tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4 , 5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, Cyclo [2,2,2] - such oct-7-ene-2,3,5,6-tetracarboxylic acid dianhydride can be mentioned.

  Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3, 3 ', 4,4'-benzophenone tetracarboxylic dianhydride, 2,2', 3,3'-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4'-biphenylsulfone tetracarboxylic dianhydride 2,2 ′, 3,3′-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride Anhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiph Nylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4′- Bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxy) Phenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidene diphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthal Acid) phenylphosphine oxide dianhydride, p-phenylene-bis (triphenylphthalic acid) dianhydride, M-phenylene-bis (triphenylphthalic acid) dianhydride Bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) Fluorene dianhydride, 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, and the like can be given.

  Examples of the polycyclic tetracarboxylic dianhydride include 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride and 3,4-dicarboxy-1,2 , 3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride and the like.

  When tetracarboxylic dianhydride is used, aromatic tetracarboxylic dianhydride is preferable among the above.

  The tricarboxylic acid anhydride or tetracarboxylic dianhydride used in the present invention is not limited to the compounds exemplified above, and may have any structure. These may be used alone or in combination. What is preferably used in the present invention is an aromatic tricarboxylic acid anhydride or an aromatic tetracarboxylic acid dianhydride from the viewpoint of reducing the viscosity of the pigment dispersion or various inks. Furthermore, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride, 2, 3,6,7-Naphthalenetetracarboxylic dianhydride, ethylene glycol ditrimellitic anhydride ester and trimellitic anhydride are preferred.

The number of moles of the hydroxyl group of the polymer (POH) or the primary amino group of the polymer (PNH ₂ ) is <H>, and the number of moles of the carboxylic acid anhydride group of the tricarboxylic anhydride or tetracarboxylic dianhydride is <N. >, The reaction ratio is preferably 0.5 <H> / <N><1.2, more preferably 0.7 <H> / <N><1.1, and most preferably <H This is a case where> / <N> = 1. When the reaction is carried out with <H> / <N><1, the remaining acid anhydride may be hydrolyzed with a necessary amount of water and used.

A catalyst may be used for the reaction of the polymer (POH) or polymer (PNH ₂ ) with the tricarboxylic acid anhydride or tetracarboxylic dianhydride. As the catalyst, for example, a tertiary amine compound can be used, for example, triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-. Examples include undecene and 1,5-diazabicyclo- [4.3.0] -5-nonene.

The reaction of the polymer (POH) or polymer (PNH ₂ ) with the tricarboxylic acid anhydride or tetracarboxylic dianhydride may be performed without a solvent, or an appropriate dehydrated organic solvent may be used. After completion of the reaction, the solvent used in the reaction can be removed by an operation such as distillation, or can be used as it is as a part of the product of the dispersant.

The reaction temperature between the polymer (POH) or the polymer (PNH ₂ ) and the tricarboxylic acid anhydride or tetracarboxylic dianhydride is preferable when using a “polymer having a hydroxyl group at one end (POH)”. Is performed in the range of 80 ° C to 180 ° C, more preferably 90 ° C to 160 ° C. When the reaction temperature is less than 80 ° C., the reaction rate is slow. When the reaction temperature exceeds 180 ° C., the acid anhydride that has reacted and opened a ring may form a cyclic anhydride again, and the reaction may be difficult to complete. Also, when using the "polymer having a primary amino group at one terminal (PNH _2)" preferably in a range of 0 to 150 ° C., more preferably 10 ° C. to 100 ° C.. If it is less than 0 ° C., the reaction may not proceed, and if it exceeds 150 ° C., imidation may occur.

  In the pigment composition of the present invention, the compounding amount of the synergist (Y) having a basic group is preferably 1 to 50 parts by weight, more preferably 3 to 30 parts by weight, and most preferably 5 to 5 parts by weight with respect to 100 parts by weight of the pigment. 25 parts by weight. When the synergist (Y) having a basic group with respect to 100 parts by weight of the pigment is less than 1 part by weight, the dispersibility may be deteriorated, and when it exceeds 50 parts by weight, the heat resistance and light resistance may be deteriorated. The blending amount of the dispersant (S) is preferably 0.1 to 100 parts by weight, more preferably 0.5 to 75 parts by weight, and most preferably 1.0 to 50 parts by weight with respect to 100 parts by weight of the pigment. is there. When the dispersant (S) is less than 0.1 part by weight with respect to 100 parts by weight of the pigment, the dispersibility may be deteriorated, and when it exceeds 100 parts by weight, the dispersibility may be deteriorated.

 The pigment composition of the present invention is dispersed in a varnish by mixing various solvents, resins, additives, etc. as necessary, and dispersing with a horizontal sand mill, vertical sand mill, annular bead mill, attritor or the like. A pigment dispersion can be prepared. The pigment, the synergist having a basic group (Y), the dispersant (S), other resins and additives may be dispersed after mixing all the components. Only synergists having a group (Y), only synergists having a basic group (Y) and a dispersant (S), or synergists having a pigment and a basic group (Y) and a dispersant (S) It is also possible to disperse only and then add another component to carry out dispersion again.

  Also, before dispersing with a horizontal sand mill, vertical sand mill, annular bead mill, attritor, etc., pre-dispersion using a kneader mixer such as a kneader, three-roll mill, etc., solid dispersion with a two-roll mill, etc., or pigment You may process the synergist (Y) and / or dispersing agent (S) which have a basic group to (P). In addition, any disperser or mixer such as a high speed mixer, a homomixer, a ball mill, a roll mill, a stone mill, or an ultrasonic disperser can be used for producing the dispersion of the present invention. Examples of various solvents that can be used in the pigment dispersion of the present invention include organic solvents and water. Moreover, when using for an active energy ray hardening-type composition, you may use an active energy ray-curable liquid monomer and liquid oligomer as a medium instead of a solvent.

  Examples of resins that can be used in the pigment dispersion of the present invention include petroleum resin, casein, shellac, rosin-modified maleic resin, rosin-modified phenol resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, Rubber, oxidized rubber, hydrochloric acid rubber, phenol resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylic resin, methacrylic resin, polyurethane Examples include resins, silicone resins, fluororesins, drying oils, synthetic drying oils, styrene-modified maleic acid, polyamide resins, chlorinated polypropylene, butyral resins, and vinylidene chloride resins.

  The pigment dispersion of the present invention can be used in non-aqueous, aqueous or solvent-free paints, gravure inks, offset inks, ink jet inks, color filter inks, digital paper inks, plastic colorants, and the like.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not particularly limited to the examples. In the examples, “part” represents “part by weight”.

[Production Example 1 of Dispersant (S)]
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and monobutyltin (IV) oxide 0 as a catalyst
. After charging 1 part and replacing with nitrogen gas, the mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by solid content measurement, 36.6 parts of pyromellitic anhydride was added here, and it was made to react at 120 degreeC for 2 hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and the reaction was completed to obtain a dispersant (S1). The acid value of the obtained dispersant was 49 mgKOH / g.

[Production Examples 2 to 7 of Dispersant (S)]
In the same apparatus, catalyst, and reaction operation as in Production Example 1 of Dispersant (S), a monoalcohol, an alkylene oxide polymer, a lactone, and tetracarboxylic dianhydride are reacted in a composition as shown in Table 1. Each dispersant was obtained.

* Hydroxyl value: 65.8 mgKOH / g (mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate)
Abbreviated name methoxy PEG400 in Table 1 ... one-end methoxylated polyethylene glycol (molecular weight 400, hydroxyl value: 140 mgKOH / g)
Blemmer PP-500 ... Polypropylene glycol monomethacrylate (Nippon Yushi Co., Ltd. product name: Blenmer PP-500, hydroxyl value: 95.1 mgKOH / g)
PMA ... pyromellitic dianhydride BPDA ... 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride BPAF ... 9,9-bis (3,4-dicarboxyphenyl) fluorene Diacid anhydride NPDA ... 2,3,6,7-naphthalenetetracarboxylic dianhydride TMEG ... Ethylene glycol ditrimellitic anhydride (manufactured by Nippon Nippon Chemical Co., Ltd .: trade name Ricacid TMEG-100)
TMA--trimellitic anhydride DMBA--dimethylbenzylamine However, with respect to Production Examples 3, 5, and 6 of Dispersant (S), the inside of the reaction vessel is not replaced with nitrogen gas, but with dry air. Replaced. Further, water in Production Example 6 of the dispersant (S) was added after completion of the reaction between the tetracarboxylic dianhydride and the hydroxyl group of the polymer having a hydroxyl group at one end to hydrolyze the remaining acid anhydride. Is.

[Production Example 8 of Dispersant (S)]
In the same reaction vessel as in Example 1, Jeffamine XTJ-506 (Mitsui Chemicals Fine Co., Ltd .: one-end methoxylated polyoxyethylene polyoxypropyleneamine, number average molecular weight 1000, amine value 56 mgKOH / g) 350.0 And 71.8 parts of ethylene glycol ditrimellitic anhydride ester (manufactured by Shin Nippon Rika Co., Ltd .: trade name Ricacid TMEG-100) were added and reacted at 50 ° C. for 3 hours. By measuring the acid value, it was confirmed that 97% or more of the acid anhydride was half-esterified, and the reaction was completed to obtain a dispersant (S8). The acid value of the obtained dispersant was 49 mgKOH / g.

[Production Example 9 of Dispersant (S)]
A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin (IV) oxide as a catalyst. After replacing with nitrogen gas, the mixture was heated and stirred at 120 ° C. for 4 hours. It was confirmed that 98% had reacted by solid content measurement. Thereafter, 33.6 parts of succinic anhydride, 62.5 parts of 2-ethylhexyl glycidyl ether, and 2.0 parts of N, N-dimethylbenzylamine were added and reacted at 80 ° C. for 8 hours.
28.8 parts of pyromellitic dianhydride was added to the reaction product and reacted at 100 ° C. for 5 hours. The acid value was measured to confirm that 97% or more of the acid anhydride was half-amidated, and the reaction was completed to obtain a dispersant (S9). The acid value of the obtained dispersant was 40 mgKOH / g.

[Production Example 10 of Dispersant (S)]
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 100 parts of n-butyl methacrylate, 100 parts of benzyl methacrylate and 10 parts of 2-mercaptoethanol and replaced with nitrogen gas. The reaction vessel was heated to 80 ° C. and reacted for 12 hours. It was confirmed that 95% had reacted by solid content measurement.
To the above reaction product was added 14.0 parts of pyromellitic dianhydride, 95.9 parts of cyclohexanone, and 0.40 part of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst, The reaction was carried out at 130 ° C. for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride had been half-esterified, and 128 parts of cyclohexanone was added to complete the reaction to obtain a dispersant (S10). The obtained dispersant had a solid content of 50% by weight and an acid value of 27 mgKOH / g.

[Comparative dispersant 1]
Disperbyk-111 (phosphoric acid-containing dispersant manufactured by BYK Chemie)
[Comparative dispersant 2]
Solspers 41000 (Avicia's phosphoric acid-containing dispersant)

[Production Example of Comparative Dispersant 3]
26.6 parts of phosphorus oxychloride was dissolved in 70 parts of tetrahydrofuran, placed in a reaction vessel, and cooled to -50 ° C. 100 parts of a compound obtained by adding 4 mol of ε-caprolactone to 2-hydroxyethyl methacrylate (Placcel FM4: manufactured by Daicel Chemical Industries), 16.7 parts of triethylamine and 0.1 part of hydroquinone monomethyl ether are dissolved in 150 parts of tetrahydrofuran, and a dropping funnel is added. Put in. While blowing dry nitrogen gas, the phosphorus oxychloride solution was stirred and the solution was added dropwise. During the dropping, the temperature was kept at −45 to −50 ° C. and kept at −45 ° C. for 1 hour after the dropping. Thereafter, the temperature was raised to 0 ° C., and a solution obtained by dissolving 15 parts of water and 37.9 parts of triethylamine in 100 parts of tetrahydrofuran was added dropwise. After completion of the dropwise addition, the mixture was stirred for 15 hours under ice cooling to complete the hydrolysis of the P—Cl bond. Thereafter, the precipitated triethylammonium chloride was filtered off, and tetrahydrofuran was removed under reduced pressure at a temperature of 30 ° C. or lower. The obtained solid was washed with 0.3N hydrochloric acid aqueous solution. Next, after washing several times with toluene, it was dried under reduced pressure at room temperature to obtain Comparative Dispersant 3.

[Production Example 1 of Synergist (Y) Having Basic Group]
After 50 parts of copper phthalocyanine as a pigment component was chlorosulfonated, it was reacted with 14 parts of N, N-dimethylaminopropylamine as an amine component to obtain 62 parts of synergist (Y1) having a basic group.
Synergists with basic groups (Y1)

ＣｕＰｃは、銅フタロシアニン残基を表す。

CuPc represents a copper phthalocyanine residue.

[Production Example 2 of Synergist (Y) Having Basic Group]
After chloromethylating 50 parts of copper phthalocyanine as a pigment component, it was reacted with 40 parts of dibutylamine as an amine component to obtain 95 parts of synergist (Y2) having a basic group.
Synergists with basic groups (Y2)

ＣｕＰｃは、銅フタロシアニン残基を表す。

CuPc represents a copper phthalocyanine residue.

[Production Example 3 of Synergist (Y) Having Basic Group]
After chloroacetamidomethylation of 50 parts of quinacridone as a pigment component, it was reacted with 40 parts of N-methylpiperazine as an amine component to obtain 103 parts of synergist (Y3) having a basic group.
Synergists with basic groups (Y3)

[Production Example 4 of Synergist (Y) Having Basic Group]
By using diphenyl diketopyrrolopyrrole as a dye component and N-aminopropylmorpholine as an amine component, a synergist (Y4) having a basic group was obtained in the same manner as in Production Example 1.
Synergists with basic groups (Y4)

[Production Examples 5-10 of Synergists (Y) Having Basic Groups]
The following pigment derivatives, anthraquinone derivatives, acridone derivatives or triazine derivatives were obtained by the same method as in Production Examples 1 to 4 of the synergists (Y) having the basic group.

塩基性基を有するシナジスト（Ｙ５）


塩基性基を有するシナジスト（Ｙ６）



塩基性基を有するシナジスト（Ｙ７）

Synergists with basic groups (Y5)


Synergists with basic groups (Y6)



Synergists with basic groups (Y7)

  As described above, by reacting a pigment component, anthraquinone, acridone or triazine with an amine component in the same manner as in Production Examples 1 to 10 of synergists having a basic group, a coupling reaction of a compound having an amine component By synthesizing the dye, synergists (Y) having various basic groups constituting the present invention can be produced.

9 parts of Pigment Blue 15: 3 as a pigment, 1 part of a synergist (Y1) having a basic group, 1 part of a dispersant (S1), 29 parts of an alkyd resin (“Phtalkid 133-60” manufactured by Hitachi Chemical Co., Ltd.) Charge 10 parts of melamine resin (Hitachi Chemical Co., Ltd. “Melan 20”) and 50 parts of thinner (mixed solvent consisting of cyclohexanone / xylene / n-butanol = 6/2/2 (weight ratio)) into a mayonnaise bottle, After preliminary dispersion, 250 parts of zirconia beads having a diameter of 0.5 mm were charged as dispersion media, and main dispersion was performed with a paint shaker to obtain a pigment dispersion.
The viscosity of the obtained paint was measured with a B-type viscometer, and the performance of the dispersion was evaluated by the viscosity and TI value (= viscosity at 6 rpm ÷ viscosity at 60 rpm). The viscosity at 6 rpm was 300 mPa · s, the viscosity at 60 rpm was 270 mPa · s, and the TI value was 1.11. The obtained pigment composition was stored in a thermostat at 50 ° C. for 1 week and accelerated with time, and the change in viscosity of the pigment dispersion before and after aging was measured. The viscosity at 6 rpm was 290 mPa · s, and the rate of change was −3%.

Examples 2-16
In the same manner as in Example 1, pigment dispersions were obtained with the blending ratios (weight ratios) shown in Table 2, respectively. Moreover, it evaluated by the method similar to Example 1 (The viscosity is so favorable that a viscosity is low, and TI value is so good that it is close to 1). When the rate of change in viscosity before and after storage at 50 ° C. for 1 week was within ± 10%, it was rated as ○, and when it exceeded ± 10%, it was marked as ×. The results are shown in Table 3.

Comparative Examples 1-20
In the same manner as in Example 1, pigment dispersions were obtained according to the blending ratios (weight ratios) shown in Table 4. Moreover, it evaluated by the method similar to Example 1 (The viscosity is so favorable that a viscosity is low, and TI value is so good that it is close to 1). When the rate of change in viscosity before and after storage at 50 ° C. for 1 week was within ± 10%, it was rated as ○, and when it exceeded ± 10%, it was marked as ×. The results are shown in Table 5.

  In Examples 1 to 7 and 21 using Pigment Blue 15: 3, seven points (S1) to (S6) and (S10) were used as the dispersant, but the viscosity was low and the viscosity stability was good. I know that there is. On the other hand, in Comparative Example 1 in which no dispersant (S) is used, the viscosity is high, and Comparative Example 2 in which neither a synergist (Y) having a basic group nor a dispersant (S) is used has a basic group. In Comparative Example 3 in which no synergist (Y) was used, the viscosity was increased at the time of dispersion with a paint shaker, and separation from the beads was impossible. Further, Comparative Example 4 using a phosphate ester-based comparative dispersant 1 instead of the dispersant (S1) of Example 1 has a reduced viscosity as compared with Comparative Example 1 having no dispersant. The nature was bad. Also in Examples 8 to 20 and Comparative Examples 5 to 20 using other pigments, the superiority of the pigment dispersion of the present invention is clear.

  Further, the pigment dispersions obtained in Example 1, Example 8, Example 9, Example 11, Example 12, Comparative Example 4, Comparative Example 8, Comparative Example 12, Comparative Example 14, and Comparative Example 15 were used. Each was coated on an aluminum plate with a bar coater # 5, baked at 180 ° C. for 1 hour, and then immersed in a 5% strength saline solution for 24 hours. As a result, only the coated product of the comparative example produced a blister. .

Claims (12)

Pigments,
A synergist (Y) having at least one basic group selected from the group consisting of a pigment derivative having a basic group, an anthraquinone derivative having a basic group, an acridone derivative having a basic group, and a triazine derivative having a basic group;
A pigment composition comprising a dispersant (S),
The dispersant (S) comprises a polymer having a hydroxyl group at one end (POH) or a polymer having a primary amino group at one end (PNH ₂ ), a tricarboxylic acid anhydride or a tetracarboxylic acid dianhydride. A pigment composition obtained by reacting. The basic group of the synergist (Y) having a basic group is at least selected from the group represented by the following general formula (1), the following general formula (2), the following general formula (3), and the following general formula (4). The pigment composition according to claim 1, wherein the pigment composition is one.

General formula (1):

General formula (2):


General formula (3):

General formula (4):

[In General formula (1)-General formula (4),
Each J independently represents —SO ₂ —, —CO—, —CH ₂ NHCOCH ₂ —, —CH ₂ —, or a direct bond;
f represents an integer of 1 to 10,
R ¹ and R ² are each independently an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R ¹ and R ² in the formula Together with a nitrogen atom, a nitrogen atom, an oxygen atom, or a sulfur atom, which represents an optionally substituted heterocyclic residue,
R ³ represents an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group;
R ⁴ , R ⁵ , R ⁶ , and R ⁷ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. ,
K represents —NR ⁸ —Z—NR ⁹ — or a direct bond,
R ⁸ and R ⁹ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group;
Z represents an alkylene group which may be substituted, an alkenylene group which may be substituted, or a phenylene group which may be substituted;
W represents a substituent represented by the general formula (1) or a substituent represented by the general formula (3), and Q represents a hydroxyl group, an alkoxyl group, or a substituent represented by the general formula (1). Or a substituent represented by the general formula (3). ] The polymer (POH) having a hydroxyl group at one end or the polymer (PNH ₂ ) having a primary amino group at one end is represented by the following general formula (5). Pigment composition.
General formula (5):

[In general formula (5),
Y ¹ is a monovalent terminal group having 1 to 20 carbon atoms, 0 to 12 oxygen atoms, and 0 to 3 nitrogen atoms,
X ² is —O—, —S—, or —N (R ^b ) — (where R ^b is a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms),
Z ¹ is —OH or —NH ₂ ;
G ¹ is a repeating unit represented by —R ¹¹ O—,
G ² is a repeating unit represented by —C (═O) R ¹² O—,
G ³ is a repeating unit represented by —C (═O) R ¹³ C (═O) —OR ¹⁴ O—,
R ¹¹ is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms,
R ¹² is a linear or branched alkylene group having 1 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms,
R ¹³ is a linear or branched alkylene group having 2 to 6 carbon atoms, a linear or branched alkenylene group having 2 to 6 carbon atoms, a cycloalkylene group having 3 to 20 carbon atoms, or carbon An arylene group having 6 to 20 atoms,
R ¹⁴ is represented by —CH (R ¹⁵ ) —CH (R ¹⁶ ) —,
One of R ¹⁵ and R ¹⁶ is a hydrogen atom, and the other is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkyl group The alkyloxymethylene group having 1 to 20 carbon atoms in the moiety, the alkenyloxymethylene group having 2 to 20 carbon atoms in the alkenyl moiety, the aryl moiety having 6 to 20 carbon atoms in the aryl moiety, and optionally substituted with a halogen atom An aryloxymethylene group, an N-methylene-phthalimide group,
R ¹⁷ is R ¹¹ , —C (═O) R ¹² —, or —C (═O) R ¹³ C (═O) —OR ¹⁴ —,
m1 is an integer of 0 to 100, m2 is an integer of 0 to 60, m3 is an integer of 0 to 30, provided that m1 + m2 + m3 is 1 or more and 100 or less,
The arrangement of the repeating units G ^{1 to} G ^{3 in} the general formula (5) does not limit the order thereof, and in the polymer represented by the general formula (5), between the group X ² and the group R ^17. Indicates that the repeating units G ^{1 to} G ³ are included in an arbitrary order, and these repeating units G ^{1 to} G ³ may be either random type or block type, respectively. ] The pigment composition according to claim 3, wherein Y ¹ is a linear or branched alkyl group having 1 to 18 carbon atoms. The pigment composition according to claim 3, wherein Y ¹ has an ethylenically unsaturated double bond. The pigment composition according to claim 3, wherein Y ¹ has two or more ethylenically unsaturated double bonds. m2 is an integer of 3-15, The pigment composition as described in any one of Claims 3-6 characterized by the above-mentioned. m1 is an integer of 2-20, m2 is an integer of 3-15, The pigment composition as described in any one of Claims 3-6 characterized by the above-mentioned. 9. When m2 is 2 or more, the plurality of R ¹² are different groups selected from the group consisting of a pentamethylene group, a hexamethylene group, and an alkyl-substituted hexamethylene group. Any one of the pigment compositions. The polymer (POH) having a hydroxyl group at one end or the polymer (PNH ₂ ) having a primary amino group at one end is represented by the following general formula (6): Pigment composition.
General formula (6):

[In General Formula (6), Y ² is a polymerization termination group of the vinyl polymer,
Z ² is —OH or —NH ₂ ;
R ²¹ and R ²² are each independently a hydrogen atom or a methyl group,
One of R ²³ and R ²⁴ is a hydrogen atom, the other is an aromatic group, or —C (═O) —X ⁶ —R ²⁵ (where X ⁶ is —O— or —N (R ²⁶ )-, and R ²⁵ and R ²⁶ are hydrogen atoms or linear or branched alkyl groups having 1 to 18 carbon atoms, which can have an aromatic group as a substituent,
X ⁴ is —O—R ²⁷ — or —S—R ²⁷ —, wherein R ²⁷ is a linear or branched alkylene group having 1 to 18 carbon atoms,
n is 2-50. ]   The pigment composition according to any one of claims 1 to 10, wherein the tricarboxylic acid anhydride or tetracarboxylic dianhydride is an aromatic tricarboxylic acid anhydride or an aromatic tetracarboxylic dianhydride.   A pigment dispersion obtained by dispersing the pigment composition according to any one of claims 1 to 11 in a varnish.