JP5407401B2 - Dispersant, and pigment composition and pigment dispersion using the same - Google Patents

Description

  The present invention relates to a dispersant, and more specifically, a dispersant capable of producing a pigment dispersion excellent in non-aggregability, fluidity, and storage stability, which is suitable for the fields of paints and colored resin compositions, and the like. The present invention also relates to a pigment composition and a pigment dispersion using the same.

  Generally, when manufacturing ink etc., it is known that it is difficult to disperse | distribute a pigment stably at high concentration, and it is known that it will cause various problems with respect to a manufacturing process or the product itself. For example, dispersions containing pigments composed of fine particles often exhibit high viscosity, making it difficult to remove and transport the product from the disperser, and if the increase in viscosity is significant, the May become difficult to use. Furthermore, regarding the surface of the color-extended product, a state failure such as a decrease in gloss and a leveling failure occurs. When different types of pigments are mixed and used, color unevenness due to aggregation or phenomena such as sedimentation may cause uneven color and a marked decrease 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 types of dispersants are used according to the surface state of the pigment to be dispersed, but basic dispersants are generally used for pigments having an acid-biased surface. is there. In this case, the basic functional group becomes the adsorption site of the pigment. Dispersants having an amino group as a basic functional group are described in, for example, Patent Literature 1, Patent Literature 2, Patent Literature 3, Patent Literature 4, Patent Literature 5, Patent Literature 6, and the like.

  However, in Patent Documents 1 and 2, although the dispersing ability is possessed, in these pigment dispersants, the polyester component and polyamines contained in the molecular chain are bonded by an amide bond. However, a compound having an amide bond has a very high cohesive force and has a drawback that it is difficult to dissolve in many coating solvents when used as a pigment dispersant. Further, since the portion of the nitrogen atom bonded to the amide has extremely low basicity, the nitrogen of the amide bond does not exhibit adsorptivity to the pigment. Furthermore, if a large amount of polyester chain is grafted to polyamines for the purpose of forming an effective steric repulsion layer on the pigment surface and improving the dispersion stability of the pigment, the amount of adsorbing groups will decrease and conversely the dispersibility. There was a problem that would decrease.

  In Patent Document 3, although the dispersion ability is possessed, there is a problem that the stability of the dispersant is poor in the heat aging test because the Michael addition reaction is used. Further, Patent Document 4, Patent Document 5, and Patent Document 6 have a certain degree of dispersion ability, but it was necessary to increase the amount of use in order to produce a stable dispersion with low viscosity. 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.

  Patent Documents 7, 8, and 9 describe a dispersant obtained by reacting an isocyanate with a polyester, polyacrylate, polyalkyl ether, and a diamine having a primary amine and a tertiary amine. Sufficient dispersibility was not obtained with respect to pigments having an acid-biased surface due to the absence of primary amine.

Japanese Patent Laid-Open No. 9-169821 JP 2004-089787 A JP-A-9-194585 JP-A-1-236930 Japanese Patent Laid-Open No. 3-103478 Japanese Patent Laid-Open No. 16-344795 Special table 2003-506538 gazette Japanese Patent Laid-Open No. 10-300923 JP-A-6-154574

  An object of the present invention is to provide a dispersant for obtaining a pigment dispersion which is excellent in dispersibility, fluidity and storage stability at a low use amount and is not limited by a binder resin or a solvent. Furthermore, the present invention is suitable for offset ink, gravure ink, resist ink for color filters, ink jet ink, paint, and colored resin composition, and can impart dispersibility and stability excellent in non-aggregability and fluidity. It is an object of the present invention to provide a dispersant, a method for producing the dispersant, and a pigment composition and pigment dispersion using the dispersant.

The problem is
Polymer formed by reacting hydroxyl group or primary amino group of polymer (A) having one hydroxyl group or primary amino group in one terminal region with at least one isocyanate group of polyisocyanate (B) ( A) an isocyanate group of (poly) isocyanate (E) having at least one moiety;
A primary and / or secondary amino group of a polyamine (C) having at least two primary and / or secondary amino groups;
A dispersant having a primary amino group obtained by reacting
This can be solved by a dispersant characterized by an amine value of 1 to 107.15 mg KOH / g.

In a preferred embodiment of the dispersant according to the invention,
The polymer (A) having one hydroxyl group or primary amino group in one end region is represented by the following general formula (1).

  General formula (1):

[In general formula (1),
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 ¹ is —O—, —S—, or —N (R ⁰ ) — (where R ⁰ 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 ² —O—,
G ² is a repeating unit represented by —C (═O) —R ³ —O—,
R ² is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms,
R ³ is a linear or branched alkylene group having 1 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms,
R ¹ is R ² or —C (═O) R ³ —,
m1 is an integer from 0 to 100;
m2 is an integer of 0 to 100,
However, m1 + m2 is an integer from 1 to 200,
The arrangement of the repeating units G ¹ and G ² in the general formula (1) does not limit the order,
In the polymer represented by the general formula (1), the repeating units G ¹ and G ² are included in any order between X ¹ and R ¹ ,
Further, the repeating units G ¹ and G ² may be either random type or block type, respectively. ]

In a preferred embodiment of the dispersant according to the present invention, Y ¹ in the general formula (1) is a linear or branched alkyl group having 1 to 18 carbon atoms. It is an agent.

In a preferred embodiment of the dispersant according to the present invention, the polyamine (C) is a polyamine having two or more primary amino groups, or has two primary and / or secondary amino groups at both ends. and, furthermore, is the dispersion agent characterized Oh Rukoto a polyamine having a secondary amino group in addition to both ends.

  In a preferred embodiment of the dispersant according to the present invention, the polymer (A) having one hydroxyl group or primary amino group in one terminal region has a weight average molecular weight of 500 to 30,000. The dispersant.

In a preferred embodiment of the dispersant according to the present invention, the dispersant has a weight average molecular weight of 1,000 to 100,000.
In a preferred embodiment of the dispersant according to the present invention, the dispersant is characterized in that m2 in the general formula (1) is an integer of 3 to 70.
In a preferred embodiment of the dispersant according to the present invention, the dispersant is characterized in that m1 in the general formula (1) is an integer of 2 to 20.

The present invention also provides
One or more kinds of cyclic compounds selected from the group consisting of alkylene oxides, lactones, and lactides with one or more kinds of compounds selected from the group consisting of monoalcohols, primary monoamines, secondary monoamines, and monothiols as initiators. A first step of producing a polymer (A) having one hydroxyl group in one terminal region by ring-opening polymerization;
It has one polymer (A) site obtained by reacting the hydroxyl group of the polymer (A) having one hydroxyl group in the one terminal region with at least one isocyanate group of the polyisocyanate (B) ( A second step of producing a poly) isocyanate (E), and
A polymer (a third step of reacting an isocyanate group of (poly) isocyanate (E) having at least one A moiety with a primary and / or secondary amino group of an amine compound containing at least polyamine (C)); ,
The manufacturing method of the dispersing agent containing this.

The present invention also provides
One or more kinds of cyclic compounds selected from the group consisting of alkylene oxides, lactones, and lactides with one or more kinds of compounds selected from the group consisting of monoalcohols, primary monoamines, secondary monoamines, and monothiols as initiators. A first step of ring-opening polymerization and further reductive amination of the hydroxyl group at one end region thereof to produce a polymer (A) having one primary amino group at one end region;
A polymer (A) site formed by reacting the primary amino group of the polymer (A) having one primary amino group in the one terminal region with at least one isocyanate group of the polyisocyanate (B); A second step of producing one (poly) isocyanate (E), and
Third step of reacting an isocyanate group of (poly) isocyanate (E) having at least one polymer (A) site with a primary and / or secondary amino group of an amine compound containing at least polyamine (C) When,
The manufacturing method of the dispersing agent containing this.

  In the present invention, the first step, the second step, and / or the third step are carried out in a solvent, and the solvent is diethylene glycol diethyl ether. About.

  The present invention also relates to a pigment composition comprising the dispersant and a pigment.

  Further, the present invention provides at least one dye derivative selected from the group of dye derivatives having an acidic substituent represented by the following general formula (2), the following general formula (3), and the following general formula (4). The pigment composition comprising:

General formula (2):
PZ ²
(In general formula (2), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. Z ² is a sulfonic acid group or a carboxyl group, which is a kind of organic dye residue selected from the group consisting of a series, a perinone series, a flavanthrone series, a pyranthrone series, and an anthrapyrimidine series.

General formula (3):
(PZ ³ ) [N ⁺ (R ⁴ , R ⁵ , R ⁶ , R ⁷ )]
(In the general formula (3), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. R ⁴ is an alkyl group having 5 to 20 carbon atoms, R ⁵ , R ⁵ , R ⁵ , R ⁵ , R ⁴ , R ⁴ , R ⁴ , R ⁵ , R ^{5 6,} and R ⁷ are each independently a hydrogen atom or an alkyl group having a carbon number of 1 to 20, Z ³ is SO ₃ ^- or COO ^- and is).

General formula (4):
(P−Z ⁴ ) M ⁺
(In the general formula (4), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. Is an organic dye residue selected from the group consisting of a series, a perinone series, a flavanthrone series, a pyranthrone series, and an anthrapyrimidine series, M is Na or a K atom, and Z ⁴ is SO ₃ ^- or COO ^- it can be).

  Furthermore, the present invention relates to a pigment dispersion obtained by dispersing the pigment composition in a varnish.

  In addition, the present invention relates to the pigment dispersion, wherein the varnish contains diethylene glycol diethyl ether as a solvent.

  By using the dispersant of the present invention, it was possible to provide a pigment composition having dispersibility, fluidity and storage stability, which was not obtained conventionally. Furthermore, it is suitable for offset ink, gravure ink, resist ink for color filters, inkjet ink, paint, and colored resin composition, etc., has excellent dispersibility and stability with excellent non-aggregability and fluidity, and high storage stability A pigment dispersion having high temporal stability could be provided.

  In general, a pigment dispersant has a structure of a part that adsorbs to a pigment and a part that has a high affinity for a solvent that is a dispersion medium, and the performance of the dispersant is determined by the balance of these two parts. That is, in order to develop dispersibility, both the ability of the dispersant to adsorb to the pigment and the affinity to the solvent as the dispersion medium are very important.

  The present invention does not limit the pigment carrier (binder resin, etc.) and the dispersion medium (organic solvent, etc.), and disperses a pigment having an acid-biased surface, resulting in a pigment dispersion excellent in fluidity and storage stability. The object is to provide an unprecedented dispersant that can be produced.

The dispersant of the present invention is
Polymer formed by reacting hydroxyl group or primary amino group of polymer (A) having one hydroxyl group or primary amino group in one terminal region with at least one isocyanate group of polyisocyanate (B) ( A) an isocyanate group of (poly) isocyanate (E) having at least one moiety;
A primary and / or secondary amino group of a polyamine (C) having at least two primary and / or secondary amino groups;
A dispersant having a primary amino group obtained by reacting
A dispersant having an amine value of 1 to 107.15 mgKOH / g.

More specifically, the dispersant of the present invention is
One or more kinds of cyclic compounds selected from the group consisting of alkylene oxides, lactones, and lactides with one or more kinds of compounds selected from the group consisting of monoalcohols, primary monoamines, secondary monoamines, and monothiols as initiators. A first step of producing a polymer (A) having one hydroxyl group in one terminal region by ring-opening polymerization;
It has one polymer (A) site formed by reacting the hydroxyl group of the polymer (A) having one hydroxyl group in the one terminal region with at least one isocyanate group of the polyisocyanate (B) ( A second step of producing a poly) isocyanate (E), and
A third step of reacting an isocyanate group of (poly) isocyanate (E) having one polymer (A) site with a primary and / or secondary amino group of an amine compound containing at least polyamine (C); ,
It is synthesized through.

Alternatively, the dispersant of the present invention is
One or more kinds of cyclic compounds selected from the group consisting of alkylene oxides, lactones, and lactides with one or more kinds of compounds selected from the group consisting of monoalcohols, primary monoamines, secondary monoamines, and monothiols as initiators. A first step of ring-opening polymerization and further reductive amination of the hydroxyl group at one end region thereof to produce a polymer (A) having one primary amino group at one end region;
A polymer (A) site formed by reacting the primary amino group of the polymer (A) having one primary amino group in the one terminal region with at least one isocyanate group of the polyisocyanate (B); A second step for producing one (poly) isocyanate (E), and
A third step of reacting an isocyanate group of (poly) isocyanate (E) having one polymer (A) site with a primary and / or secondary amino group of an amine compound containing at least polyamine (C); ,
It is synthesized through.

  Each component of the dispersant of the present invention will be described.

  In the present application, “(meth) acryloyl”, “(meth) acryl”, “(meth) acrylic acid”, “(meth) acrylate”, “(meth) acryloyloxy”, or “(meth) acrylamide” When expressed, unless otherwise specified, “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, “acryloyl”, respectively. It shall represent “oxy and / or methacryloyloxy” or “acrylamide and / or methacrylamide”.

<< Polymer (A) having one hydroxyl group or primary amino group in one end region >>
As a preferred form of the polymer (A) having one hydroxyl group or primary amino group in one terminal region (hereinafter sometimes abbreviated as polymer (A)), first, the following general formula (1): What is shown.

  General formula (1):

[In general formula (1),
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 ¹ is —O—, —S—, or —N (R ⁰ ) — (where R ⁰ 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 ² —O—,
G ² is a repeating unit represented by —C (═O) —R ³ —O—,
R ² is a linear or branched alkylene group having 2 to 8 carbon atoms, or a cycloalkylene group having 3 to 8 carbon atoms,
R ³ is a linear or branched alkylene group having 1 to 8 carbon atoms, or a cycloalkylene group having 4 to 8 carbon atoms,
R ¹ is R ² or —C (═O) R ³ —,
m1 is an integer from 0 to 100;
m2 is an integer of 0 to 100,
However, m1 + m2 is an integer from 1 to 200,
The arrangement of the repeating units G ¹ and G ² in the general formula (1) does not limit the order,
In the polymer represented by the general formula (1), the repeating units G ¹ and G ² are included in any order between X ¹ and R ¹ ,
Further, the repeating units G ¹ and G ² may be either random type or block type, respectively. ]
In the general formula (1), 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 (1), Y ¹ preferably has an ethylenically unsaturated double bond. In this case, active energy ray curability can be imparted to the dispersant.

  In the general formula (1), m2 is preferably an integer of 3 to 70 from the viewpoints of lowering the viscosity and storage stability of the pigment dispersion.

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

  Among the polymers (A) represented by the general formula (1), a polymer having a hydroxyl group at one end (POH) can be produced by a known method, and includes a monoalcohol, a primary monoamine, and a secondary monoamine. And a compound selected from the group consisting of monothiol as an initiator, and can be easily obtained by ring-opening polymerization of a cyclic compound selected from the group consisting of alkylene oxide, lactone, and lactide.

  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-octyldecanol, 2 An aliphatic monoalcohol such as octyldodecanol, 2-hexyldecanol, behenyl alcohol or oleyl alcohol;
A monoalcohol having an aromatic ring such as benzyl alcohol, phenoxyethyl alcohol, or paracumylphenoxyethyl alcohol; or
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 monopropyl ether, diethylene glycol monobutyl ether, Ethylene 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 monohexyl 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 monomer 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 monoethyl ether, tetrapropylene glycol monopropyl A And alkylene glycol monoalkyl ethers such as tetrapropylene glycol monobutyl ether, tetrapropylene glycol monohexyl ether, tetrapropylene glycol mono-2-ethylhexyl ether, and tetradiethylene 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.

  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 monoalcohols having one ethylenically unsaturated double bond include:
2-hydroxyethyl (meth) acrylate, 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 ether, or 4-hydroxy Examples include butyl vinyl ether.

Examples of monoalcohols having two ethylenically unsaturated double bonds include:
Examples 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. 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 ² .

  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 primary monoamines include:
Methylamine, ethylamine, 1-propylamine, isopropylamine, 1-butylamine, isobutylamine, tert-butylamine, 1-pentylamine, isopentylamine, 3-pentylamine, 1-hexylamine, cyclohexylamine, 4-methyl- 2-pentylamine, 1-heptylamine, 1-octylamine, isooctylamine, 2-ethylhexylamine, 1-nonylamine, isononylamine, 1-decylamine, 1-dodecylamine, 1-myristylamine, cetylamine, 1- Aliphatic primary monoamines such as stearylamine, isostearylamine, 2-octyldecylamine, 2-octyldodecylamine, 2-hexyldecylamine, behenylamine, or oleylamine;
3-methoxypropylamine, 3-ethoxypropylamine, 3-propoxypropylamine, 3-butoxypropylamine, 2-ethylhexyloxypropylamine, 3-isobutyroxypropylamine, 3-decyloxypropylamine, or 3- Alkoxyalkyl primary monoamines such as myristyloxypropylamine; or
Aromatic primary monoamines such as benzylamine are listed.

Examples of secondary monoamines include:
Dimethylamine, diethylamine, di-1-propylamine, diisopropylamine, di-1-butylamine, diisobutylamine, di-1-pentylamine, diisopentylamine, 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) amine, N-methylethylamine, N Methylbutylamine, N- methyl isobutyl amine, N- methyl-propylamine, N- methyl hexylamine, piperazine, or include aliphatic secondary monoamine such as an alkyl-substituted piperazines.

As monothiol, for example,
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-octyldecylthiol, 2-hexyldecylthiol, behenylthiol, or olei Aliphatic mono thiols thiols such; or,
Alkyl thioglycolates such as methyl thioglycolate, octyl thioglycolate, methoxybutyl thioglycolate, methyl mercaptopropionate, octyl mercaptopropionate, methoxybutyl mercaptopropionate, or alkyl mercaptopropionate such as tridecyl mercaptopropionate Examples include esters.

  The compound selected from the group consisting of monoalcohol, primary monoamine, secondary monoamine, and monothiol as 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 portion other than the hydroxyl group, primary amino group, secondary amino group, or thiol group of monoalcohol, primary monoamine, secondary monoamine, or monothiol, respectively, represents Y ¹ in the general formula (1). Configure.

Opening one or more cyclic compounds selected from the group consisting of alkylene oxide, lactone, and lactide using the compound selected from the group consisting of the monoalcohol, primary monoamine, secondary monoamine, and monothiol exemplified above as an initiator It can superpose | polymerize and can manufacture that whose Z < ¹ > is -OH among the polymers shown by the said General formula (1).

Here, the reaction order of the one or more cyclic compounds selected from the group consisting of alkylene oxide, lactone, and lactide may be any order. For example, after polymerizing alkylene oxide on the initiator as the first step, Lactone can also be polymerized in the second 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. In the production method of the present invention, as an initiator for producing a polymer represented by the general formula (1) described below, among the polymers represented by the general formula (1), Z ¹ is Also includes -OH. Similarly, a polymer represented by the general formula (1) described later, wherein Z ¹ is —NH ₂ , can also serve as an initiator.

  The reaction order of the cyclic compound is not limited to the combination of the first-stage alkylene oxide and the second-stage lactone, and the alkylene oxide and the lactone (and / or lactide) may be combined in any order, one or more. It can be carried out over a number of times. Alternatively, with respect to the combination of alkylene oxide and lactone (and / or lactide), ring-opening polymerization can be carried out by selecting any cyclic compound from them without carrying out all ring-opening polymerization.

Examples of alkylene oxide include:
Ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3-, or 1,3-butylene oxide, or a combination of two or more of these is used. When two or more kinds of alkylene oxide are used in combination, the bond 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 (1), Z ¹ is —OH, and it can be used as it is as a raw material for the dispersant of the present invention as having only G ¹ among the repeating units of G ^{1 to} G ^2. .

Specific examples of the commercial products are as follows:
UNIOX M-400, M-550, M-2000, M-4000, 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, and the like.

Here, the alkylene group of the alkylene oxide constitutes R ² in the repeating unit G ¹ in the general formula (1).

Examples of lactones include:
β-butyrolactone, γ-butyrolactone, γ-valerolactone, δ-valerolactone, δ-caprolactone, ε-caprolactone, alkyl-substituted ε-caprolactone, etc.
Of these, δ-valerolactone, ε-caprolactone, or alkyl-substituted ε-caprolactone is preferably used from the viewpoint of ring-opening polymerizability.

  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 (5) are preferable (including glycolide).

  General formula (5):

[In general formula (5),
R ⁸ and R ⁹ are each independently a hydrogen atom or a saturated or unsaturated linear or branched alkyl group having 1 to 20 carbon atoms,
R ¹⁰ and R ¹¹ 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. ]
As a raw material for the dispersant of the present invention, particularly preferred lactide is lactide (3,6-dimethyl-1,4-dioxane-2,5-dione) or glycolide (1,4-dioxane-2,5-dione). It is. Of the lactones or lactides, lactones are preferably used as raw materials for the dispersant of the present 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.
Quaternary ammonium such as tetramethylammonium chloride, tetrabutylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium iodide, tetrabutylammonium iodide, benzyltrimethylammonium chloride, benzyltrimethylammonium bromide, or benzyltrimethylammonium iodide salt;
Tetramethylphosphonium chloride, tetrabutylphosphonium chloride, tetramethylphosphonium bromide, tetrabutylphosphonium bromide, tetramethylphosphonium iodide, tetrabutylphosphonium iodide, benzyltrimethylphosphonium chloride, benzyltrimethylphosphonium bromide, benzyltrimethylphosphonium iodide, tetraphenylphosphonium chloride, Quaternary phosphonium salts such as tetraphenylphosphonium bromide or tetraphenylphosphonium iodide;
Phosphorus compounds such as triphenylphosphine;
Organic carboxylates such as potassium acetate, sodium acetate, potassium benzoate, or sodium benzoate;
Alkali metal alcoholates such as sodium alcoholate or potassium alcoholate;
Alternatively, tertiary amines; organotin compounds; organoaluminum compounds; organotitanate compounds; or zinc compounds such as zinc chloride.

  The amount of the catalyst used is 0.1 ppm to 3000 ppm, preferably 1 ppm to 1000 ppm, based on 1 part by weight of one or more cyclic compounds selected from the group consisting of alkylene oxide, lactone, and lactide. 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, such as 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 ³ in the repeating unit G ² in the general formula (1).

Among the polymers (A) represented by the general formula (1), a polymer (PNH ₂ ) having a primary amino group at one end can be produced by a known method, and the general formula (1) A hydroxyl group at one end of a polymer having a hydroxyl group at one end (POH), which is a ring-opening polymer of a cyclic compound selected from the group consisting of alkylene oxide, lactone, and lactide represented by Obtained by.

  The production method of an alkylene oxide polymer having a primary amino group at one end will be described as an example. A (co) polymer of lactone and / or lactide having a primary amino group at one end, an alkylene oxide, and a lactone and / or lactone copolymer are synthesized in the same manner.

  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. Among the polymers represented by (1), Z ¹ is —NH ₂ , and it can be used as it is as a raw material for the dispersant of the present invention as having only G ¹ among the repeating units of G ^{1 to} G ² . Specific examples of commercially available products include Jeffamine XTJ-475, XTJ-436, XTJ-505, XTJ-506, XTJ-507, or M-2070, or Surfonamine B-60, L-100, B- 200, L-207, L-300, B-30, or B-100.

  When a monoalcohol, dicarboxylic acid anhydride, or epoxide having an ethylenically unsaturated double bond is used when producing the polymer represented by the general formula (1), it is preferable to use a polymerization inhibitor. .

  As the polymerization inhibitor, for example, hydroquinone, methylhydroquinone, hydroquinone monomethyl ether, p-benzoquinone, 2,4-dimethyl-6-t-butylphenol, or phenothiazine are preferable, and these are used alone or in combination as a reference for the dispersant. Thus, it is used in the range of 0.01% to 6% by weight, preferably 0.05% to 1.0% by weight.

<Polymerization solvent>
In the case of solution polymerization, ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, diethylene glycol diethyl ether, or the like is used as the polymerization solvent, but these are particularly limited. is not. These polymerization solvents may be used as a mixture of two or more kinds, but are preferably used for final use.

<Weight average molecular weight of polymer (A)>
The weight average molecular weight (Mw) in terms of polystyrene by GPC of the polymer (A) having one hydroxyl group or primary amino group in one terminal region is preferably 500 to 30,000, 1,000 More preferably, it is ˜15,000, particularly preferably 1,000 to 8,000. When the weight average molecular weight is less than 500, the effect of steric repulsion by the solvent affinity part is reduced, and it becomes difficult to prevent aggregation of the pigment, and dispersion stability may be insufficient. On the other hand, if it exceeds 30,000, the absolute amount of the solvent affinity part increases, and the dispersibility effect itself may be lowered. Further, the viscosity of the dispersion may increase.

  When the weight average molecular weight is 500 to 30,000, it is advantageous to suppress an increase in viscosity of the pigment dispersion by preventing aggregation of the pigment.

<Polyisocyanate (B)>
As the polyisocyanate (B) used in the present invention, conventionally known ones can be used. Examples of the bifunctional diisocyanate include diisocyanates (b1) having an aromatic group and diisocyanates (b2) having an aliphatic group. ), A diisocyanate (b3) having an aromatic group and an aliphatic group, or a diisocyanate (b4) having an alicyclic group.

  Examples of the diisocyanate (b1) having an aromatic group include xylylene diisocyanate, 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4- Examples include tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4′-toluidine diisocyanate, naphthylene diisocyanate, or 1,3-bis (isocyanatomethyl) benzene.

  Examples of the diisocyanate (b2) having an aliphatic group include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), pentamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, and 1,3-butylene. Examples thereof include diisocyanate, dodecamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate.

  Examples of the diisocyanate (b3) having an aromatic group and an aliphatic group include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate. Examples include -1,4-diethylbenzene, 1,4-tetramethylxylylene diisocyanate, or 1,3-tetramethylxylylene diisocyanate.

  Examples of the diisocyanate (b4) having an alicyclic group include 3-isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (IPDI), 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4- Examples include cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, or methyl-2,6-cyclohexane diisocyanate.

  As mentioned above, the listed polyisocyanate (B) is not necessarily limited to these, and two or more kinds can be used in combination.

  A trimethylolpropane adduct of the above diisocyanate or a trimer having an isocyanurate ring can also be used in combination. Polyphenylmethane polyisocyanate (PPI) and these polyisocyanate modified products can be used. As the polyisocyanate-modified product, a carbodiimide group, a uretdione group, a uretoimine group, a burette group reacted with water, a group of isocyanurate groups, or a modified product having two or more of these groups can be used. A reaction product of a polyol and a diisocyanate can also be used as the polyisocyanate (B).

  Isocyanurates include isocyanurate of tolylene diisocyanate (TDI) (Sumidur IL), isocyanurate of hexamethylene diisocyanate (HDI) (Sumidur N3500), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate ( IPD) isocyanurate (Desmodur Z4470). These can be obtained from the sources indicated in the examples.

  The polyisocyanate (B) used in the present invention is particularly preferably trifunctional or higher.

  Isocyanate oligomers must have more than two average functional groups, meaning that the isocyanate molecules contain, on average, at least three free isocyanate groups. In contrast to the absolute number of isocyanate groups, the average functionality is used because the isocyanate is obtained as an isomeric mixture of isocyanates having 3, 4, 5 or more functional groups. By titrating to determine the weight percent of isocyanate, measuring the number average molecular weight (“Mn”) of the oligomer (as by gel permeation chromatography “GPC”), and then calculating the average number of isocyanate groups The average functional group can be measured experimentally.

<Polyamine (C)>
The polyamine (C) used in the present invention is a compound having at least two primary and / or secondary amino groups, and is used for reacting with an isocyanate group to form a urea bond. A diamine (c1) is mentioned as such an amine.

As the diamine (c1) having two primary amino groups, known ones can be used, and specifically,
Ethylenediamine, propylenediamine [alias: 1,2-diaminopropane or 1,2-propanediamine], trimethylenediamine [alias: 1,3-diaminopropane or 1,3-propanediamine], tetramethylenediamine [alias: 1 , 4-diaminobutane], 2-methyl-1,3-propanediamine, pentamethylenediamine [alias: 1,5-diaminopentane], hexamethylenediamine [alias: 1,6-diaminohexane], 2,2- Aliphatic diamines such as dimethyl-1,3-propanediamine, 2,2,4-trimethylhexamethylenediamine, or tolylenediamine;
Cycloaliphatic diamines such as isophorone diamine or dicyclohexylmethane-4,4′-diamine; or
Examples thereof include aromatic diamines such as phenylenediamine and xylylenediamine.

Moreover, as diamine (c1) which has two secondary amino groups, a well-known thing can be used, Specifically,
N, N-dimethylethylenediamine, N, N-diethylethylenediamine, or N, N′-di-tert-butylethylenediamine can be used.

Moreover, as diamine (c1) which has a primary and secondary amino group, a well-known thing can be used, Specifically,
N-methylethylenediamine [alias: methylaminoethylamine], N-ethylethylenediamine [alias: ethylaminoethylamine], N-methyl-1,3-propanediamine [alias: N-methyl-1,3-diaminopropane or methylamino Propylamine], N, 2-methyl-1,3-propanediamine, N-isopropylethylenediamine [alias: isopropylaminoethylamine], N-isopropyl-1,3-diaminopropane [alias: N-isopropyl-1,3- Propanediamine or isopropylaminopropylamine], or N-lauryl-1,3-propanediamine [alias: N-lauryl-1,3-diaminopropane or laurylaminopropylamine].

  The polyamine of the present invention is a compound having at least two primary and / or secondary amino groups, and the primary and / or secondary amine reacts with an isocyanate group to form a urea group, and this urea group serves as a pigment adsorption site. However, when the polyamine (C) is a compound having two primary and / or secondary amino groups at both ends and further having a secondary and / or tertiary amino group at both ends, This is particularly preferable because the adsorptivity to the acidic pigment is improved.

  Examples of such polyamine (C) include polyamines having two primary and / or secondary amino groups at both ends as shown below, and further having secondary and / or tertiary amino groups at both ends. c2).

As polyamine (c2),
Methyliminobispropylamine [alias N, N-bis (3-aminopropyl) methylamine], lauryliminobispropylamine [alias N, N-bis (3-aminopropyl) laurylamine], iminobispropylamine [alias] N, N-bis (3-aminopropyl) amine], N, N′-bisaminopropyl-1,3-propylenediamine, N, N′-bisaminopropyl-1,4-butylenediamine, etc. Can
Methyliminobispropylamine and lauryliminobispropylamine having two primary amino groups and one tertiary amino group are preferable because they can easily control the reaction with diisocyanate.

  An iminobispropylamine having two primary amino groups and one secondary amino group is preferable because of its good adsorptivity to pigments.

  As the polyamine (C) of the present invention, a polymer (c3) having two or more primary and / or secondary amino groups can also be used.

  Examples of the polymer (c3) having a primary and / or secondary amino group include an ethylenically unsaturated monomer having a primary amino group and an ethylenically unsaturated monomer having a secondary amino group, such as vinylamine and allylamine. Homopolymers (so-called polyvinylamine and polyallylamine), copolymers thereof with other ethylenically unsaturated monomers, ring-opening polymers of ethyleneimine, and polycondensates of ethylene chloride and ethylenediamine Or a ring-opening polymer of oxazolidone-2 (so-called polyethyleneimine). The content of primary and / or secondary amino groups in the polymer is preferably 10 to 100% by weight, more preferably 20 to 100% by weight, in terms of monomer units, based on the polymer. If the content is 10% by weight or more, it is effective for preventing aggregation of pigments and suppressing an increase in viscosity.

As an ethylenically unsaturated monomer copolymerizable with an ethylenically unsaturated monomer having a primary amino group or an ethylenically unsaturated monomer having a secondary amino group, for example,
Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, itaconic acid, maleic acid or fumaric acid;
Aromatic vinyl compounds such as styrene, α-methylstyrene, p-hydroxystyrene, chloromethylstyrene, indene, or vinyltoluene;
(Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, or 2-ethylhexyl (meth) acrylate;
(Meth) acrylic acid alkylaryl esters such as benzyl (meth) acrylate;
(Meth) acrylic acid-substituted alkyl ester having a functional group such as glycidyl (meth) acrylate or 2-hydroxyethyl (meth) acrylate;
(Meth) acrylic acid-substituted alkyl ester having a tertiary amino group such as dimethylaminoethyl (meth) acrylate or dimethylaminopropyl (meth) acrylate;
Alkyl (meth) acrylamides such as (meth) acrylamide, dimethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, n-butyl (meth) acrylamide, tert-butyl (meth) acrylamide, or tert-octyl (meth) acrylamide ;
Substituted alkyl (meth) acrylamides such as dimethylaminoethyl (meth) acrylamide or dimethylaminopropyl (meth) acrylamide;
Diene compounds such as 1,3-butadiene or isoprene;
Polymerizable oligomers (macromonomers) such as one-end methacryloylated polymethyl methacrylate oligomer, one-end methacryloylated polystyrene oligomer, or one-end methacryloylated polyethylene glycol; or
And vinyl cyanide.

  The polymer having a primary and / or secondary amino group has a polystyrene-equivalent weight average molecular weight (Mw) by GPC (gel permeation chromatography), preferably 300 to 75,000, 300 to 20, 000 is more preferable, and 500 to 5,000 is particularly preferable. When the weight average molecular weight is 300 to 75,000, it is effective to suppress the viscosity increase of the pigment dispersion by preventing the aggregation of the pigment.

《Monoamine (D)》
As the amine compound constituting the dispersant of the present invention, in addition to the polyamine (C), a monoamine (D) can also be used. The monoamine (D) is a monoamine compound having one primary amino group or one secondary amino group in the molecule. Used as a reaction terminator to suppress excessive molecular weight. The monoamine (D) may have a polar functional group other than the primary amino group or the secondary amino group in the molecule. Examples of such a polar functional group include a hydroxyl group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, a cyano group, and a nitroxyl group.

As the monoamine (D), conventionally known ones can be used. Specifically,
Aminomethane, aminoethane, 1-aminopropane, 2-aminopropane, 1-aminobutane, 2-aminobutane, 1-aminopentane, 2-aminopentane, 3-aminopentane, isoamylamine, N-ethylisoamylamine, 1-amino Hexane, 1-aminoheptane, 2-aminoheptane, 2-octylamine, 1-aminononane, 1-aminodecane, 1-aminododecane, 1-aminotridecane, 1-aminohexadecane, stearylamine, aminocyclopropane, aminocyclobutane Aminocyclopentane, aminocyclohexane, aminocyclododecane, 1-amino-2-ethylhexane, 1-amino-2-methylpropane, 2-amino-2-methylpropane, 3-amino-1-propene, 3-amino Methyl heptane, -Isopropoxypropylamine, 3-butoxypropylamine, 3-isobutoxypropylamine, 2-ethylhexyloxypropylamine, 3-decyloxypropylamine, 3-lauryloxypropylamine, 3-myristoxypropylamine, 2 -Aminomethyltetrahydrofuran, dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, disec-butylamine, N-ethyl- 1,2-Dimethylpropylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-Piperidinmethanol, Pipecolic Acid Isonipecotic acid, methyl isonipecotate, ethyl isonipecotate, 2-piperidine ethanol, 4-piperidine ethanol, 4-piperidine butyric acid hydrochloride, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3- Pyrrolidinol, indoline, aniline, N-butylaniline, o-aminotoluene, m-aminotoluene, p-aminotoluene, o-benzylaniline, p-benzylaniline, 1-anilinonaphthalene, 1-aminoanthraquinone, 2-amino Anthraquinone, 1-aminoanthracene, 2-aminoanthracene, 5-aminoisoquinoline, o-aminodiphenyl, 4-aminodiphenyl ether, β-aminoethylbenzene, 2-aminobenzophenone, 4-aminobenzophenone, o -Aminoacetophenone, m-aminoacetophenone, p-aminoacetophenone, benzylamine, N-methylbenzylamine, 3-benzylaminopropionic acid ethyl ether, 4-benzylpiperidine, α-phenylethylamine, phenacylamine, p- Examples include methoxyphenesylamine, furfurylamine, p-aminoazobenzene, m-aminophenol, p-aminophenol, allylamine, or diphenylamine.

  Among them, a monoamine compound having only a secondary amino group as an aliphatic amine having no rigidity is preferable because of its good dispersibility.

As an aliphatic monoamine compound having only a secondary amino group,
Dimethylamine, diethylamine, N-methylethylamine, N-methylisopropylamine, N-methylhexylamine, diisopropylamine, di-n-propylamine, di-n-butylamine, disec-butylamine, N-ethyl-1,2-dimethyl Propylamine, Piperidine, 2-Pipecoline, 3-Pipecoline, 4-Pipecoline, 2,4-Lupetidine, 2,6-Lupetidine, 3,5-Lupetidine, 3-piperidinemethanol, 2-piperidineethanol, 4-piperidineethanol, 4-piperidinol, pyrrolidine, 3-aminopyrrolidine, 3-pyrrolidinol, etc. are mentioned.

  In addition, since the tertiary amino group does not have an active hydrogen that reacts with an isocyanate group, a diamine having a primary or secondary amino group and a tertiary amino group can be used as a monoamine (D). In the present invention, a tertiary amino group having an effect of improving the pigment adsorption ability can be introduced into the polymer terminal of the dispersant.

As a diamine having a primary or secondary amino group and a tertiary amino group,
Primary amino group such as N, N-dimethylethylenediamine, N, N-diethylethylenediamine, N, N-dimethyl-1,3-propanediamine, or N, N, 2,2-tetramethyl-1,3-propanediamine And a diamine having a tertiary amino group; or
Examples thereof include diamines having a secondary amino group and a tertiary amino group such as N, N, N′-trimethylethylenediamine.

  These monoamine compounds may be used alone or in combination. The active hydrogen of the urea bond after the reaction of the primary amine group and the isocyanate group has low reactivity, and under the polymerization conditions of the dispersant of the present invention, it does not react with the isocyanate group any longer and the molecular weight does not increase. .

<< (Poly) isocyanate (E) having one polymer (A) site >>
The (poly) isocyanate (E) having one polymer (A) moiety is composed of a hydroxyl group or primary amino group of the polymer (A) having one hydroxyl group or primary amino group in one terminal region, It is obtained by reacting with one isocyanate group of isocyanate (B).

<Synthetic catalyst (F)>
When synthesizing (poly) isocyanate (E) having one polymer (A) site, a known catalyst (F) can be used, and examples thereof include tertiary amine compounds or organometallic compounds. be able to.

As the tertiary amine compound, for example,
Examples include triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, diazabicycloundecene (DBU), and the like.

  Examples of organometallic compounds include tin compounds and non-tin compounds.

Examples of tin compounds include:
Dibutyltin dichloride, dibutyltin oxide, dibutyltin dibromide, dibutyltin dimaleate, dibutyltin dilaurate (DBTDL), dibutyltin diacetate, dibutyltin sulfide, tributyltin sulfide, tributyltin oxide, tributyltin acetate, triethyltin ethoxide, tributyl Examples thereof include tin ethoxide, dioctyl tin oxide, tributyltin chloride, tributyltin trichloroacetate, and 2-ethylhexanoic acid tin.

Examples of non-tin compounds include:
Titanium systems such as dibutyltitanium dichloride, tetrabutyltitanate, or butoxytitanium trichloride;
Lead systems such as lead oleate, lead 2-ethylhexanoate, lead benzoate, or lead naphthenate;
Iron systems such as iron 2-ethylhexanoate or iron acetylacetonate;
Cobalt-based benzoate or cobalt 2-ethylhexanoate, etc .;
Zinc-based such as zinc naphthenate or zinc 2-ethylhexanoate; or
Zirconium-based compounds such as zirconium naphthenate can be mentioned.

  Among the above catalysts, dibutyltin dilaurate (DBTDL), tin 2-ethylhexanoate or the like is preferable in terms of reactivity and hygiene.

  Catalysts such as the tertiary amine compounds and organometallic compounds can be used alone or in combination depending on the case.

  The organometallic compound catalyst used in the synthesis of the (poly) isocyanate (E) having one polymer (A) site significantly accelerates the reaction even in the further reaction with the amine described below.

<Synthetic solvent>
In the present invention, a known solvent is preferably used when synthesizing (poly) isocyanate (E) having one polymer (A) moiety. The use of a solvent serves to facilitate reaction control.

Examples of the solvent used for this purpose include:
Ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, or diethylene glycol diethyl ether are used, but are not particularly limited thereto. It is not a thing.

  In particular, ethyl acetate, toluene, methyl ethyl ketone, diethylene glycol diethyl ether, or a mixed solvent thereof from the viewpoint of solubility of amine such as solubility of (poly) isocyanate (E) having one polymer (A) moiety and boiling point of solvent Is preferred.

  Further, when the solvent is used, the concentration in the reaction system of the (poly) isocyanate (E) having one polymer (A) site is (poly) isocyanate (E) having one polymer (A) site. In terms of reaction control, it is preferably 30 to 95% by weight, and more preferably 40 to 90% by weight from the viewpoint of viscosity control. If it is less than 30% by weight, the reaction becomes slow and unreacted substances may remain. If it exceeds 95% by weight, the reaction may partially proceed abruptly, and it is difficult to control the molecular weight or the like, which is not preferable.

<Composite conditions>
Polymer (A) site by reacting hydroxyl group or primary amino group of polymer (A) having one hydroxyl group or primary amino group in one terminal region with one isocyanate group of polyisocyanate (B) Various methods can be used for the urethanization or urea formation reaction to produce (poly) isocyanate (E) having one of the following. 1) When the reaction is carried out in the whole amount, 2) Polyisocyanate (B) and, if necessary, a solvent is charged into a flask, and a polymer (A) having one hydroxyl group or primary amino group in one end region is prepared. After dripping, it is divided roughly into the method of adding a catalyst as needed. The reaction temperature for obtaining the (poly) isocyanate (E) having one polymer (A) moiety is preferably 120 ° C. or lower. More preferably, it is 50-110 degreeC. When the temperature is higher than 110 ° C., it becomes difficult to control the reaction rate, and (poly) isocyanate (E) having one polymer (A) site having a predetermined molecular weight and structure cannot be obtained. The urethanization or urea reaction is preferably carried out at 50 to 110 ° C. for 1 to 20 hours in the presence of a catalyst.

  The blending ratio of the polymer (A) having one hydroxyl group or primary amino group in one end region and the polyisocyanate (B) is the number of moles of isocyanate groups per mole of polyisocyanate (B) being an integer β. In this case, the number of moles α of the hydroxyl group or primary amino group of the polymer (A) having one hydroxyl group or primary amino group in one terminal region is 1 <α <β (where 1 <β), Theoretically, (poly) isocyanate (E) having at least an isocyanate group and one polymer (A) site can be synthesized. When α ≧ β, the isocyanate group does not remain and cannot react with the polyamine (C), so that the dispersant of the present invention cannot be synthesized. In addition, when α ≦ 1, unreacted polyisocyanate (B) remains, and in the dispersant of the present invention, excess polyisocyanate (B) -derived polymer constituent units and excess polyisocyanate (B) are added. Since impurities derived from decomposition products are generated, it is not preferable from the viewpoint of pigment dispersibility and stability over time.

<< Production method and synthesis conditions of dispersant >>
The dispersant of the present invention is selected from the group consisting of alkylene oxide, lactone, and lactide with one or more compounds selected from the group consisting of monoalcohol, primary monoamine, secondary monoamine, and monothiol as initiators. A first step of producing a polymer (A) having one hydroxyl group in one terminal region by ring-opening polymerization of one or more kinds of cyclic compounds;
It has at least one polymer (A) site obtained by reacting the hydroxyl group of the polymer (A) having one hydroxyl group at one terminal region with at least one isocyanate group of the polyisocyanate (B). A second step of producing (poly) isocyanate (E), and
A third one in which an isocyanate group of (poly) isocyanate (E) having at least one polymer (A) site and a primary and / or secondary amino group of an amine compound containing at least polyamine (C) are reacted; Process,
Or a method for producing a dispersant containing
One or more kinds of cyclic compounds selected from the group consisting of alkylene oxides, lactones, and lactides with one or more kinds of compounds selected from the group consisting of monoalcohols, primary monoamines, secondary monoamines, and monothiols as initiators. A first step of ring-opening polymerization, and further reductive amination of a hydroxyl group at one terminal region to produce a polymer (A) having one primary amino group at one terminal region;
A polymer (A) site formed by reacting the primary amino group of the polymer (A) having one primary amino group in the one terminal region with at least one isocyanate group of the polyisocyanate (B); A second step of producing (poly) isocyanate (E) having at least one, and
Third step of reacting an isocyanate group of (poly) isocyanate (E) having at least one polymer (A) site with a primary and / or secondary amino group of an amine compound containing at least polyamine (C) When,
It can manufacture with the manufacturing method of the dispersing agent containing.

  In the present invention, the urea reaction for obtaining a polyurethane urea having a primary or secondary amino group at its terminal from (poly) isocyanate (E) having at least one polymer (A) site and polyamine (C) is 1 ) (Poly) isocyanate (E) solution is charged into a flask and polyamine (C) is added dropwise. 2) A solution comprising polyamine (C) and, if necessary, a solvent is charged into a flask, and (poly) isocyanate (E). It is roughly classified into a method of dropping the solution. The synthesis is performed with a stable reaction, but the method 2) is preferable because the molecular weight can be easily controlled. The temperature of the urea reaction of the present invention is preferably 120 ° C. or lower. More preferably, it is 110 degrees C or less. When the temperature is higher than 120 ° C., it is difficult to control the reaction rate, and it is difficult to obtain a urethane urea resin having a predetermined molecular weight and structure.

  Moreover, the compounding ratio with (poly) isocyanate (E) and polyamine (C) is not particularly limited, and is arbitrarily selected depending on the application and required performance.

  The end point of the reaction is judged from the disappearance of the isocyanate peak by the measurement of isocyanate% due to titration and IR measurement.

  The weight average molecular weight (Mw) of the dispersant of the present invention is preferably 1,000 to 100,000, more preferably 1,500 to 50,000, particularly preferably 1,500 to 20,000. . If the weight average molecular weight is less than 1,000, the stability of the pigment composition may decrease. If the weight average molecular weight exceeds 100,000, the interaction between the resins becomes strong and the pigment composition may increase in viscosity. is there. Moreover, it is preferable that the amine value of the obtained dispersing agent is 1-100 mgKOH / g, More preferably, it is 2-50 mgKOH / g, More preferably, it is 3-30 mgKOH / g. If the amine value is less than 1 mgKOH / g, there may be insufficient functional groups to adsorb to the pigment, which may make it difficult to contribute to pigment dispersion. If the amine value exceeds 100 mgKOH / g, aggregation of the pigments occurs, resulting in a decrease in viscosity. Insufficient effects and defects in the appearance of the coating film may occur.

<Pigment composition>
<Pigment>
A pigment composition can be obtained by mixing and dispersing the dispersant of the present invention and a pigment.

The pigment used in the present invention is not particularly limited.
Soluble azo pigments, insoluble azo pigments, phthalocyanine pigments, halogenated phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, isoindoline pigments, perylene pigments, perinone pigments, dioxazine pigments, anthraquinone pigments, dianthraquinonyl pigments, anthrapyrimidine pigments, Ansanthrone pigment, indanthrone pigment, flavanthrone pigment, pyranthrone pigment, diketopyrrolopyrrole pigment, etc.
A more specific example is indicated by the generic name of the color index.
Blue pigments such as Pigment Black 7, Pigment Blue 15, Pigment Blue 15: 1, Pigment Blue 15: 3, Pigment Blue 15: 4, Pigment Blue 15: 6, Pigment Blue 22, Pigment Blue 60, or Pigment Blue 64;
Green pigments such as CI Pigment Green 7, Pigment Green 36, and Pigment Green 58;
Pigment Red 9, Pigment Red 48, Pigment Red 49, Pigment Red 52, Pigment Red 53, Pigment Red 57, Pigment Red 97, Pigment Red 122, Pigment Red 123, Pigment Red 144, Pigment Red 146, Pigment Red 149, Pigment Red 166, Pigment Red 168, Pigment Red 177, Pigment Red 178, Pigment Red 179, Pigment Red 180, Pigment Red 185, Pigment Red 192, Pigment Red 202, Pigment Red 206, Pigment Red 207, Pigment Red 209, Pigment Red 215, Pigment Red 216, Pigment Red 217, Pigment Red 220, Pigment Head 221, Pigment Red 223, Pigment Red 224, Pigment Red 226, Pigment Red 227, Pigment Red 228, Pigment Red 238, Pigment Red 240, Pigment Red 242, a red pigment such as Pigment Red 254 or Pigment Red 255;
Purple pigments such as Pigment Violet 19, Pigment Violet 23, Pigment Violet 29, Pigment Violet 30, Pigment Violet 37, Pigment Violet 40, and Pigment Violet 50;
Pigment Yellow 12, Pigment Yellow 13, Pigment Yellow 14, Pigment Yellow 17, Pigment Yellow 20, Pigment Yellow 24, Pigment Yellow 74, Pigment Yellow 83, Pigment Yellow 86, Pigment Yellow 93, Pigment Yellow 94, Pigment Yellow 95, Pigment Yellow 109, Pigment Yellow 110, Pigment Yellow 117, Pigment Yellow 120, Pigment Yellow 125, Pigment Yellow 128, Pigment Yellow 137, Pigment, Yellow 138, Pigment Yellow 139, Pigment Yellow 147, Pigment Yellow 148, Pigment Yellow 150, Pigment Yellow 151 , Pigment Yellow 153, Pigment I Low 154, Pigment Yellow 155, Pigment Yellow 166, Pigment Yellow 168, Pigment Yellow 180, Pigment Yellow 185, or yellow pigments such as CI Pigment Yellow 213;
Pigment Orange 13, Pigment Orange 36, Pigment Orange 37, Pigment Orange 38, Pigment Orange 43, Pigment Orange 51, Pigment Orange 55, Pigment Orange 59, Pigment Orange 61, Pigment Orange 64, Pigment Orange 71, or Pigment Orange 74, etc. Orange pigment; or
Examples thereof include brown pigments such as Pigment Brown 23, Pigment Brown 25, and Pigment Brown 26.

  If necessary, two or more pigments may be used in combination to perform toning.

  As for carbon black, any carbon black such as neutral, acidic, or basic can be used.

  The pigment concentration used in the inkjet ink of the present invention is preferably 1 to 80% by weight, more preferably 2 to 50% by weight, based on the solid content of the inkjet ink. When it is less than 1% by weight, there is no coloring power, and when it is more than 80% by weight, the storage stability of the ink deteriorates.

<Dye derivative>
Next, the pigment derivative having an acidic substituent used in the present invention will be described. The dye derivative having an acidic substituent used in the present invention is at least one selected from the group of dye derivatives represented by the following general formula (2), the following general formula (3), and the following general formula (4). Can be used. The pigment derivative having an acidic substituent is divided into a pigment derivative having no charge represented by the following general formula (2) and a pigment derivative having a charge represented by the following general formulas (3) and (4). .

General formula (2):
PZ ²
(In general formula (2), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. Z ² is a sulfonic acid group or a carboxyl group, which is a kind of organic dye residue selected from the group consisting of a series, a perinone series, a flavanthrone series, a pyranthrone series, and an anthrapyrimidine series.

General formula (3)
(PZ ³ ) [N ⁺ (R ⁴ , R ⁵ , R ⁶ , R ⁷ )]
(In the general formula (3), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. R ⁴ is an alkyl group having 5 to 20 carbon atoms, R ⁵ , R ⁵ , R ⁵ , R ⁵ , R ⁴ , R ⁴ , R ⁴ , R ⁵ , R ^{5 6,} and R ⁷ are each independently a hydrogen atom or an alkyl group having a carbon number of 1 to 20, Z ³ is SO ₃ ^- or COO ^- and is).

General formula (4)
(P−Z ⁴ ) M ⁺
(In the general formula (4), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. And an organic dye residue selected from the group consisting of perinone, flavanthrone, pyranthrone, and anthrapyrimidine, M is Na or K atom, and Z ⁴ is SO ₃ ⁻ or COO ^−. .)

  P in the pigment derivatives represented by the general formulas (2) to (4) represents an organic dye residue, but it can be used in offset ink, gravure ink, color filter resist ink, ink jet ink, paint, and colored resin composition. The chemical structure of the pigment used does not necessarily match the chemical structure of the organic dye residue, but it can be used to disperse yellow pigments in consideration of the hue of the ink that is finally produced. Pigments that disperse like yellow pigment derivatives, red pigment derivatives when used to disperse red pigments, and blue pigment derivatives when used to disperse blue pigments A pigment dispersion that is excellent in hue can be produced by using the one having a hue close to or colorless.

  The amount of the dye derivative used in the pigment composition of the present invention is preferably 0 to 50% by weight, more preferably 0 to 30% by weight, based on the pigment. When it is more than 50% by weight, the resistance of the ink coating film is deteriorated.

<Other dispersants>
In the present invention, a dispersant other than the dispersant of the present invention may be added in order to improve the dispersibility of the pigment and the storage stability of the pigment composition and the pigment dispersion. Such dispersants include hydroxyl group-containing carboxylic acid esters, salts of long chain polyaminoamides and high molecular weight acid esters, salts of high molecular weight polycarboxylic acids, salts of long chain polyaminoamides and polar acid esters, Saturated acid ester, polymer copolymer, modified polyurethane, modified polyacrylate, polyether ester type anionic activator, naphthalene sulfonic acid formalin condensate salt, aromatic sulfonic acid formalin condensate salt, polyoxyethylene alkyl phosphate ester , Polyoxyethylene nonylphenyl ether, stearylamine acetate, or the like can be used.

  Specific examples of the dispersant include “Anti-Terra-U (polyaminoamide phosphate)”, “Anti-Terra-203 / 204 (high molecular weight polycarboxylate)” manufactured by BYK Chemie, “Disperbyk-101 ( (Salt of long-chain polyaminoamide and polar acid ester), 107 (hydroxyl group-containing carboxylic acid ester), 110, or 111 (copolymerization product containing acid group), 130 (polyamide), or 161, 162, 163, 164 , 165, 166, 170, 180, or 182 (high molecular weight copolymer) "," Bykumen (high molecular weight unsaturated acid ester) "," BYK-P104, or P105 (high molecular weight unsaturated acid polycarboxylic acid) " , "P104S or 240S (high molecular weight unsaturated acid polycarboxylic acid and poly Mixture of hexane) ", or" Lactimon (a mixture of partial amides product and polysiloxanes with long chain amine and an unsaturated acid polycarboxylic acid) "can be mentioned.

  Also, “Efka CHEMICALS” “Efka 44, 46, 47, 48, 49, 54, 63, 64, 65, 66, 71, 701, 764, or 766 (modified polyacrylate)”, “Efka Polymer 100 (modified polyacrylate) ), 150 (aliphatic modified polymer), 400, 401, 402, 403, 450, 451, 452, or 453 (modified polyacrylate), or 745 (copper phthalocyanine-based) ”, manufactured by Kyoeisha Chemical Co., Ltd.“ Floren TG- ” "710 (urethane oligomer)", "Flonon SH-290 or SP-1000 (acrylic copolymer)", "Polyflow No. 50E or No. 300 (acrylic copolymer)", or Enomoto Kasei Made by Dispalon KS-860, 873SN, or 874 (Polymer dispersing agent), # 2150 (aliphatic polyvalent carboxylic acid), or # 7004 (polyether ester type) ”.

  Furthermore, “Demol RN, N (Naphthalenesulfonic acid formalin condensate sodium salt), MS, C, or SN-B (aromatic sulfonic acid formalin condensate sodium salt) and EP” manufactured by Kao Corporation, “Homogenol L-18” (Polycarboxylic acid type polymer) "," Emulgen 920, 930, 931, 935, 950, or 985 (polyoxyethylene nonylphenyl ether) "," Acetamine 24 (coconut amine acetate), or 86 (stearyl amine acetate) "Solspers 5000 (phthalocyanine ammonium salt type), 13940 (polyesteramine type), 17000 (fatty acid amine type) or 24000" manufactured by Lubrizol, "Nikkor T106 (polyoxyethylene sorbitan monooleic acid) manufactured by Nikko Chemical Co., Ltd." G), MYS-IEX (polyoxyethylene monostearate), or Hexagline 4-0 (hexaglyceryl tetraoleate), or “Ajisper PB821 or PB822 (basic dispersant)” manufactured by Ajinomoto Fine-Techno Co., Ltd. Can be mentioned.

  The dispersant is preferably contained in the ink in an amount of 0.1 to 10% by weight.

  The amount of these other dispersants used is preferably 0 to 50% by weight, more preferably 0 to 40% by weight, from the viewpoint of pigment dispersibility, based on the dispersant essential to the present invention. When it is more than 50 weight, the resistance of the ink coating film is deteriorated.

<Organic solvent>
As the organic solvent used in the present invention, organic solvents used in offset ink, gravure ink, color filter resist ink, ink jet ink, paint, and colored resin composition can be widely used. If it supplements, if the dispersing agent of this invention is an organic solvent which melt | dissolves or suspends uniformly, there will be no restriction | limiting in particular.

Specific examples of organic solvents include
Alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, or n-butyl alcohol;
Acetone, methyl ethyl ketone, methyl-n-propyl ketone, methyl isopropyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, methyl-n-amyl ketone, methyl isoamyl ketone, diethyl ketone, ethyl-n-propyl ketone, ethyl isopropyl ketone, ethyl Ketones such as n-butyl ketone, ethyl isobutyl ketone, di-n-propyl ketone, diisobutyl ketone, cyclohexanone, methylcyclohexanone, isophorone;
Esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, octyl acetate, methyl lactate, propyl lactate, or butyl lactate;
Lactones such as γ-butyrolactone and ε-caprolactone;
Glycols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, or dipropylene glycol;
Ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, ethylene glycol monohexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol diethyl ether , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl Ether, dipropylene glycol dipropyl ether, tripropylene glycol monomethyl ether, or glycol ethers such as tetraethylene glycol dimethyl ether;
Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol Glycol acetates such as monobutyl ether acetate or dipropylene glycol monomethyl ether acetate;
saturated hydrocarbons such as n-hexane, isohexane, n-nonane, isononane, dodecane, or isododecane;
Unsaturated hydrocarbons such as 1-hexene, 1-heptene, or 1-octene;
Cyclic saturated hydrocarbons such as cyclohexane, cycloheptane, cyclooctane, cyclodecane, or decalin;
Cyclic unsaturated hydrocarbons such as cyclohexene, cycloheptene, cyclooctene, 1,1,3,5,7-cyclooctatetraene, or cyclododecene;
(N-alkyl) pyrrolidones such as N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, or 2-pyrrolidone;
N-alkyloxazolidinones such as N-methyl-2-oxazolidinone; or
Examples thereof include aromatic hydrocarbons such as benzene, toluene, and xylene.

  These organic solvents may be used singly or as a mixture of two or more, but are preferably used for final use.

  In the pigment composition of the present invention, the dispersant is dissolved or suspended in an organic solvent, and then the pigment and, if necessary, the pigment derivatives represented by the general formulas (2) to (4) are added to the liquid. The mixture is stirred and mixed until uniform with a high-speed mixer, etc., and then dispersed and manufactured using various dispersers such as a bead mill such as a horizontal sand mill, vertical sand mill, or annular sand mill, or a medialess disperser. be able to. In addition, the pigment derivative may be used as a treatment agent for surface-treating the pigment in advance by adding it during the production of the pigment.

<Pigment dispersion>
The pigment composition of the present invention can be used as various printing inks and ink-jet inks, and can be used as a pigment dispersion by adding a varnish in order to impart fixability during color development.

  As the resin, a thermoplastic resin, a thermosetting resin, and a photocurable resin can be used.

  Thermoplastic resins include petroleum resin, casein, shellac, rosin modified maleic resin, rosin modified phenolic resin, rosin ester resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid rubber, phenol Resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride resin, vinylidene chloride resin, ethylene-vinyl acetate resin, vinyl chloride resin, ethylene vinyl acetate resin, acrylic resin, methacrylic resin Resin, polyurethane resin, silicone resin, fluorine resin, drying oil, synthetic drying oil, styrene-maleic acid resin, styrene-acrylic resin, polyamide resin, coumarone indene resin, terpene phenol resin, melamine resin, urea resin, epoxy resin , Cellulo Resins, xylene resins, aliphatic hydrocarbon resins, maleic acid resins and fumaric acid resins, or butyral resin.

  When a thermoplastic resin is used as the binder resin, it is desirable that the resin has an acid value of 10 mgKOH / g or less. The binder resin can improve the coating film resistance of the printed matter and the adhesion when printed on a non-absorbent substrate. However, many high acid number resins having an acid value of 10 mgKOH / g or more have a polar group, and the resulting printed film does not have sufficient resistance to solvents such as alcohol and gasoline.

  As the binder resin, a vinyl chloride resin, an acrylic resin, and a styrene-acrylic resin are preferable from the point of resistance of printed matter, and among them, a vinyl acetate resin that has excellent solubility is particularly preferable. Specific examples of the resin include Yuker Solution vinyl resins VYHD, VYHH, VMCA, VROH, or VYLF-X manufactured by Dow Chemicals, sorbine resins CL, CNL, C5R, or TA5R manufactured by Nissin Chemical Industry, manufactured by Wacker E15 / 45, H14 / 36, H15 / 42, H15 / 50, H11 / 59, H40 / 43, H40 / 50, H40 / 55, H40 / 60, H15 / 45M, E15 / 45M, or E15 / 40A, Mitsubishi Manufactured by Rayon, BR-50, BR-52, MB-2539, BR-60, BR-64, BR-73, BR-75, MB-2389, BR-80, BR-82, BR-83, BR- 84, BR-85, BR-87, BR-88, BR-90, BR-90, BR-95, BR-96, BR-100, BR-101 BR-102, BR-105, BR-106, BR-107, BR-108, BR-110, BR-1122, BR-113, MB-2660, MB-2952, MB-3012, MB-3015, MB- 7033, BR-115, MB-2478, BR-116, BR-117, BR-118, or BR-122, or A-11, A-14, A-21, B-60 manufactured by Wilbur Ellis , B-64, B-66, B-72, B-82, B-44, B-48N, B-67, or B-99N. The resin is preferably contained in the ink in an amount of 0.1 to 20% by weight. These resins may be used alone or in combination of two or more.

  The binder resin has a number average molecular weight of 5,000 or more and 50,000 or less, preferably 10,000 or more and 40,000 or less, more preferably 15,000 or more and 30,000 or less. If the molecular weight is too high, the viscosity of the ink composition increases and sufficient fluidity cannot be obtained. If the molecular weight is too low, the coating film has low resistance and sufficient film resistance cannot be obtained. A weight average molecular weight is calculated | required as a styrene conversion molecular weight by gel permeation chromatography.

  The binder resin has a glass transition point of 50 ° C. or higher. Preferably it is 70 degreeC or more, More preferably, it is 90 degreeC or more. When the glass transition point is too low, the coating film resistance is weak and the printed matter is sticky.

  Examples of the thermosetting resin include an epoxy resin, a phenol resin, a benzoguanamine resin, a melamine resin, and a urea resin.

  As a photocurable resin (photosensitive resin), a reactive polymer such as an isocyanate group, an aldehyde group, and an epoxy group is added to a linear polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, and an amino group. A resin obtained by reacting a (meth) acrylic compound or cinnamic acid and introducing a (meth) acryloyl group and a photocrosslinkable group such as a styryl group into the linear polymer can be used. In addition, a linear polymer containing an acid anhydride such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer is converted into a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A half-esterified product can also be used.

  The pigment dispersion of the present invention has a plasticizer, a surface conditioner, an ultraviolet light inhibitor, a light stabilizer, an antioxidant, an antistatic agent, an antiblocking agent, an antifoaming agent, a viscosity modifier, a wax, depending on the use to be used. Various additives such as a surfactant and a leveling agent can be used.

  The pigment dispersion of the present invention can be used as a radiation curable ink that is cured with ultraviolet rays or electron beams by using a photopolymerizable resin (photosensitive resin) or further containing a polymerizable monomer and / or oligomer. Can be used.

As the polymerizable monomer and oligomer,
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth), tertiary butyl (meth) acrylate, isoamyl (meth) acrylate, octyl (Meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cetyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, iso Linear or branched alkyl (meth) acrylates such as myristyl (meth) acrylate, stearyl (meth) acrylate, or isostearyl (meth) acrylate;
Cyclohexyl (meth) acrylate, Tertiarybutylcyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, Dicyclopentanyloxyethyl (meth) acrylate, Dicyclopentenyl (meth) acrylate, Dicyclopentenyloxyethyl (meth) ) Acrylates or cyclic alkyl (meth) acrylates such as isobornyl (meth) acrylate;
Fluoroalkyl (meth) acrylates such as trifluoroethyl (meth) acrylate, octafluoropentyl (meth) acrylate, perfluorooctylethyl (meth) acrylate, or tetrafluoropropyl (meth) acrylate;
(Meth) acryloxy-modified polydimethylsiloxanes (silicone macromers);
(Meth) acrylates having a heterocyclic ring such as tetrahydrofurfuryl (meth) acrylate or 3-methyl-3-oxetanyl (meth) acrylate;
Benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, paracumylphenoxyethyl (meth) acrylate, paracumylphenoxypolyethylene glycol (meth) acrylate, or nonylphenoxypolyethylene glycol (meth) acrylate, etc. (Meth) acrylates having the following aromatic ring;
2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, 3-methoxybutyl (meth) acrylate, 2-methoxypropyl (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate, diethylene glycol monoethyl ether (meta ) Acrylate, triethylene glycol monomethyl ether (meth) acrylate, triethylene glycol monoethyl ether (meth) acrylate, diethylene glycol mono-2-ethylhexyl ether (meth) acrylate, dipropylene glycol monomethyl ether (meth) acrylate, tripropylene glycol mono (Meth) acrylate, polyethylene glycol monolauryl ether (meth) acrylate, or polyester Glycol monostearyl ether (meth) acrylate of (poly) alkylene glycol monoalkyl ether (meth) acrylates;
(Meth) acrylic acid, acrylic acid dimer, 2- (meth) acryloyloxyethyl phthalate, 2- (meth) acryloyloxypropyl phthalate, 2- (meth) acryloyloxyethyl hexahydrophthalate, 2- (meth) (Meth) acrylates having a carboxyl group such as acryloyloxypropyl hexahydrophthalate, ethylene oxide-modified succinic acid (meth) acrylate, β-carboxyethyl (meth) acrylate, or ω-carboxypolycaprolactone (meth) acrylate;
2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-acryloyloxyethyl-2-hydroxyethyl (meth) Phthalates,
Diethylene glycol mono (meth) acrylate, dipropylene glycol mono (meth) acrylate, polyethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate,
Polytetramethylene glycol mono (meth) acrylate, poly (ethylene glycol-propylene glycol) mono (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) mono (meth) acrylate, poly (propylene glycol-tetramethylene glycol) mono ( (Meth) acrylates having hydroxyl groups such as meth) acrylate or glycerol (meth) acrylate;
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, tri Propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, poly (ethylene glycol-propylene glycol) di (meth) acrylate, poly (ethylene glycol-tetramethylene glycol) di (meth) acrylate, poly (propylene glycol- Tetramethylene glycol) di (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3-butanediol di (Meth) acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, or 2-ethyl, 2-butyl-propanediol di ( (Poly) alkylene glycol di (meth) acrylates such as (meth) acrylate,
Dimethylol dicyclopentane di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, stearic acid modified pentaerythritol di (meth) acrylate, ethylene oxide modified bisphenol A di (meth) acrylate, propylene oxide modified bisphenol A Di (meth) acrylate, tetramethylene oxide modified bisphenol A di (meth) acrylate, ethylene oxide modified bisphenol F di (meth) acrylate, propylene oxide modified bisphenol F di (meth) acrylate, tetramethylene oxide modified bisphenol F di (meth) Acrylate, zinc diacrylate, ethylene oxide-modified phosphate triacrylate, or glycerol di (meth) acrylate Di (meth) acrylate and the like;
(Meth) acrylates having a tertiary amino group such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, dimethylaminopropyl (meth) acrylate, or diethylaminopropyl (meth) acrylate;
Glycerol tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, or dipentaerythritol hexa (meth) acrylate Trifunctional or higher polyfunctional (meth) acrylates such as
Glycerol triglycidyl ether- (meth) acrylic acid adduct, glycerol diglycidyl ether- (meth) acrylic acid adduct, polyglycerol polyglycidyl ether- (meth) acrylic acid adduct, 1,6-butanediol diglycidyl ether, Alkyl glycidyl ether- (meth) acrylic acid adduct, allyl glycidyl ether- (meth) acrylic acid adduct, phenyl glycidyl ether- (meth) acrylic acid adduct, styrene oxide- (meth) acrylic acid adduct, bisphenol A di Glycidyl ether- (meth) acrylic acid adduct, propylene oxide-modified bisphenol A diglycidyl ether- (meth) acrylic acid adduct, bisphenol F diglycidyl ether- (meth) acrylic acid adduct, epichlorohydride -Modified phthalic acid- (meth) acrylic acid adduct, epichlorohydrin-modified hexahydrophthalic acid- (meth) acrylic acid adduct, ethylene glycol diglycidyl ether- (meth) acrylic acid adduct, polyethylene glycol diglycidyl ether- (meta ) Acrylic acid adduct, propylene glycol diglycidyl ether- (meth) acrylic acid adduct, polypropylene glycol diglycidyl ether- (meth) acrylic acid adduct, phenol novolac type epoxy resin- (meth) acrylic acid adduct,
Epoxy (meth) acrylates such as cresol novolac type epoxy resin- (meth) acrylic acid adduct or other epoxy resin- (meth) acrylic acid adduct;
(Meth) acryloyl-modified isocyanurate, (meth) acryloyl-modified polyurethane, (meth) acryloyl-modified polyester, (meth) acryloyl-modified melamine, (meth) acryloyl-modified silicone, (meth) acryloyl-modified polybutadiene, or (meth) acryloyl-modified rosin (Meth) acryloyl-modified resin oligomers such as;
Vinyls such as styrene, α-methylstyrene, vinyl acetate, vinyl (meth) acrylate, or allyl (meth) acrylate;
Vinyl ethers such as hydroxyethyl vinyl ether, ethylene glycol divinyl ether, or pentaerythritol trivinyl ether;
Amides such as (meth) acrylamide, N-hydroxymethyl (meth) acrylamide, or N-vinylformamide; or
Examples include acrylonitrile. These can be used alone or in admixture of two or more.

  When the pigment composition of the present invention is also used as a radiation curable ink that is cured by ultraviolet rays or electron beams, a photopolymerization initiator or the like is added.

As a photopolymerization initiator,
4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2- Such as benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one or 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one An acetophenone photopolymerization initiator;
Benzoin photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal;
Benzophenone photopolymerization initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, or 4-benzoyl-4'-methyldiphenyl sulfide;
A thioxanthone photopolymerization initiator such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, or 2,4-diisopropylthioxanthone;
2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloro) Methyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl (4′-methoxystyryl) -6 Triazine photopolymerization initiators such as triazine;
A borate photopolymerization initiator; a carbazole photopolymerization initiator; or an imidazole photopolymerization initiator or the like is used.

  The photopolymerization initiator can be used in an amount of 5 to 200 parts by weight, preferably 10 to 150 parts by weight, with respect to 100 parts by weight of the pigment in the pigment composition.

  The above photopolymerization initiators are used alone or in combination of two or more. As sensitizers, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl-9,10-phenanthrenequinone are used. , Camphorquinone, ethyl anthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, or 4,4′-diethylaminobenzophenone Can also be used together. The sensitizer can be used in an amount of 0.1 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator.

  The pigment dispersion of the present invention can also be used as a thermosetting ink by using a thermosetting resin or further containing a thermoreactive compound (thermal crosslinking agent).

Examples of the solvent contained in the ink in the present invention include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, or Although diethylene glycol diethyl ether etc. are used, it is not specifically limited to these.
The pigment dispersion of the present invention is particularly preferably used for inkjet inks and color filter resist inks. Therefore, it is preferable to produce a dispersant, a pigment composition, a pigment dispersion, and a varnish using the solvent used in the inkjet ink and the color filter ink. Examples of these solvents include cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, diethylene glycol monoethyl acetate, diethylene glycol monobutyl ether acetate, and diethylene glycol diethyl ether. Among these, diethylene glycol diethyl ether is particularly preferable from the viewpoint of low odor.

  Furthermore, when a nitrogen-containing or lactone-based solvent is added in addition to the main solvent in the ink, the surface of the printing medium can be dissolved, so that fixing properties, weather resistance, and the like can be improved. Examples include 3-methyl-2-oxazolidinone, 3-ethyl-2-oxazolidinone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, or ε-caprolactone. The addition amount is preferably 1 to 20%, preferably 1 to 10%, more preferably 3 to 9%.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, this invention is not specifically limited to an Example. In the examples, “parts” represents “parts by weight” and “%” represents “% by weight”. The number average molecular weight (Mn) and the weight average molecular weight (Mw) are TPCgel column (manufactured by Tosoh Corporation), GPC equipped with RI detector (manufactured by Tosoh Corporation, HLC-8320GPC), and DMF as a developing solvent. This is the molecular weight in terms of polystyrene when used.

Example 1 [Synthesis of Dispersant S1]
A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer is charged with 33.1 parts of 1-decanol, 466.9 parts of ε-caprolactone, and 0.03 part of monobutyltin (IV) oxide as a catalyst. And replaced with nitrogen gas. The mixture was heated and stirred at 120 ° C. for 4 hours. After confirming that 98% had reacted by measuring the solid content, 89.8 parts of Sumidur N3300, 589.6 parts of diethylene glycol diethyl ether and 0.12 part of dibutyltin dilaurate as a catalyst were charged and replaced with nitrogen gas. . Heating and stirring at 100 ° C. for 6 hours gave (poly) isocyanate (A-1) having one polymer (A) moiety. A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 35.0 parts of iminobispropylamine and 868.0 parts of diethylene glycol diethyl ether, and had one polymer (A) site at 100 ° C ( Poly) isocyanate (A-1) was added dropwise over 30 minutes. After completion of the dropwise addition, the mixture was stirred at 100 ° C. for 1 hour to obtain a 30% solid solution of the dispersant (S1). Dispersant S1 had a weight average molecular weight of 25,000 and an amine value of 39.94 mg KOH / g.

(Examples 2 to 10) [Synthesis of dispersants S2 to S10]
The synthesis was performed in the same manner as in Example 1 except that the raw materials and preparation amounts shown in Table 1 were used, and a 30% solid solution of dispersants S2 to S10 was obtained.

Example 11 Synthesis of Dispersant S11
In a reaction vessel equipped with a gas introduction tube, thermometer, condenser, and stirrer, polyoxyethylene monomethyl ether (product name: UNIOX M-2000, manufactured by NOF Corporation) 200 parts, Death Module Z4470BA (Sumitomo Bayer Urethane Co., Ltd.) 94.6 parts by company) 236.7 parts of butyl acetate and 0.06 part of dibutyltin dilaurate as a catalyst were charged and replaced with nitrogen gas. Heating and stirring at 100 ° C. for 6 hours gave (poly) isocyanate (A-11) having one polymer (A) moiety. A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 6.0 parts of iminobispropylamine and 368.3 parts of butyl acetate and had one polymer (A) site at 100 ° C. ) Isocyanate (A-11) was added dropwise over 30 minutes. After completion of dropping, the mixture was stirred at 100 ° C. for 1 hour, diluted with butyl acetate to adjust the solid content, and a 30% solid solution of Dispersant S11 was obtained. Dispersant S11 had a weight average molecular weight of 26,000 and an amine value of 11.22 mg KOH / g.

Example 12 Synthesis of Dispersant S12
In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 200 parts of polyoxyethylene-monomethyl ether (product name: UNIOX M-4000, manufactured by NOF Corporation), Death Module Z4470BA (Sumitomo Bayer Urethane Co., Ltd.) 48.0 parts, 218.6 parts of butyl acetate and 0.05 part of dibutyltin dilaurate as a catalyst were charged and replaced with nitrogen gas. Heating and stirring at 100 ° C. for 6 hours gave (poly) isocyanate (A-12) having one polymer (A) moiety. A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer is charged with 3.7 parts of iminobispropylamine and 319.8 parts of butyl acetate, and has one polymer (A) site at 100 ° C. ) Isocyanate (A-12) was added dropwise over 30 minutes. After completion of dropping, the mixture was stirred at 100 ° C. for 1 hour, diluted with butyl acetate to adjust the solid content, and a 30% solid solution of the dispersant (S12) was obtained. Dispersant S12 had a weight average molecular weight of 26,000 and an amine value of 10.00 mg KOH / g.

(Comparative Example 1) [Synthesis of Comparative Dispersant CS1]
In a reaction flask equipped with a thermometer, a stirrer, a nitrogen inlet and a reflux tube, 10.0 parts of 12-hydroxystearic acid (manufactured by Junsei Chemical) and 190 parts of ε-caprolactone (manufactured by Junsei Chemical) were charged, and nitrogen was added. The temperature was raised to 160 ° C. over 4 hours under an air stream, and after heating at 160 ° C. for 2 hours, heating was performed until the remaining amount of ε-caprolactone was 1% or less. Subsequently, it was cooled to room temperature to obtain polyester (number average molecular weight 2604, acid value 21.5 mgKOH / g). In addition, a mixture of 25.0 parts of xylene and 70 parts of a polyallylamine 10% aqueous solution [“PAA-1LV” manufactured by Nittobo Co., Ltd., number average molecular weight of about 3,000] is stirred at 160 ° C. and a separator is used. Then, while distilling water and returning xylene to the reaction solution, 13.9 parts of the previously obtained polyester was heated to 160 ° C., and reacted at 160 ° C. for 2 hours. . Xylene was replaced with diethylene glycol diethyl ether, and the solid content was adjusted to 30% to obtain a solution of a comparative dispersant (CS1) (number average molecular weight 10,500, amine value 38.5 mg KOH / g).

(Comparative Example 2) [Synthesis of Comparative Dispersant CS2]
“Johncryl 682” (low molecular weight alkali-soluble styrene acrylic copolymer manufactured by SC Johnson; Mn980, Mw1620, acid value 235 mgKOH / g, softening point 110 ° C., glass transition point 50 ° C.) 238.8 parts, "Emulgen 105" [Polyoxyethylene lauryl ether manufactured by Kao Corporation; HLB = 9.7] The mixture was heated to reflux at 0 ° C. for 8 hours, and 9.0 parts of water was distilled off in the Dean-Stark trap.

  The reaction mixture is cooled to 70 ° C., and 35.5 parts of xylene and 21.6 parts of “Epomin SP-006” (Nippon Shokubai Chemical Co., Ltd. polyethyleneimine; Mw 600) are added and heated at 136 to 138 ° C. for 1 hour. Refluxed and distilled off 1.8 parts of water in the Dean-Stark trap.

  The reaction product was cooled to room temperature to obtain a single yellowish brown transparent and viscous resin solution. This resin solution had a nonvolatile content of 49%, an acid value of 38.6 mgKOH / g, an amine value of 25.0 mgKOH / g, a viscosity TU by the Gardner method, and a color number of 8.

  Further, xylene in this resin solution was replaced with diethylene glycol diethyl ether, and the solid content was adjusted to 30% to obtain a comparative dispersant CS2).

(Example 13) <Preparation of pigment composition P1>
Dispersant 1 DEDG synthesized in Example 1 with 8.0 parts of copper-phthalocyanine blue (CI Pigment BLue 15: 4) as a blue pigment, 2.0 parts of monosulfonated phthalocyanine blue as a blue derivative 6.67 parts of solution (2.0 parts of solid content) and 43.33 parts of diethylene glycol diethyl ether were added, 100 parts of 2 mmφ zirconia beads were added, and dispersed with Scandex for 3 hours to prepare pigment composition P1.

(Examples 13 to 24 and Comparative Examples 3 to 4) <Adjustment of Pigment Compositions P1 to P12 and Comparative Pigment Compositions CP1 to CP3>
A pigment composition was prepared in the same manner as in Example 13 except that the composition was changed so that the composition ratio shown in Table 2 was obtained.

Abbreviations (solvents) and derivatives in Table 2 are as shown below.
DEDG: Diethylene glycol diethyl ether PGMac: Propylene glycol monomethyl ether acetate DMM: Dipropylene glycol dimethyl ether IPA: Isopropyl alcohol Blue derivative: Blue dye derivative represented by the following general formula (6) General formula (6):
P- [SO ₃ H · H ₂ N (CH ₂ ) ₁₁ CH ₃ ]
(In general formula (6), P is a copper phthalocyanine residue.)
Red derivative: Red pigment derivative represented by the following general formula (7) General formula (7):
Q- (SO ₃ H)
(In General Formula (7), Q is a diketopyrrolopyrrole residue.)

<Evaluation of Pigment Compositions P1 to P12 and Comparative Pigment Compositions CP1 to CP3>
In order to evaluate the performance of the pigment composition of the present invention, the viscosities of the obtained pigment compositions P1 to P12 and comparative pigment compositions CP1 to CP3 were measured with a B-type viscometer (25 ° C., rotation speed 100 rpm) and haze. Was measured with a haze meter (light transmittance 20%), and the performance of the pigment composition was evaluated based on the initial viscosity and haze (the lower the viscosity, the better the haze, the better the haze). The initial viscosity and haze were measured after standing at room temperature for 1 day after dispersion. The stability over time was determined by measuring the viscosity of the prepared pigment composition after standing at 40 ° C. for one week, and comparing with the initial viscosity, ○ if less than ± 10%, Δ if ± 10-20%, ± 20 When it exceeded%, it was set as x. The results are shown in Table 3.

  As is clear from the above evaluation results, the pigment compositions P1 to P12 of Examples 13 to 24 using the dispersants S1 to S12 of the present invention have a low initial viscosity and are good with almost no increase in viscosity over time. It shows stability. Furthermore, the haze is also low. On the other hand, the pigment composition CP3 of Comparative Example 5 using the comparative dispersant CS2 has a problem in dispersibility due to lack of stability over time, and the pigment compositions of Comparative Examples 3 and 4 using the comparative dispersant CS1. CP1 and CP2 were found to have solvent selectivity and a problem in dispersibility.

(Examples 25 to 36 and Comparative Examples 6 to 8) <Preparation of Pigment Dispersions J1 to J12 and Comparative Pigment Dispersions CJ1 to CJ3>
As shown in Table 4, 20 parts of pigment compositions P1 to P12 and comparative pigment compositions CP1 to CP3, 7 parts of binder resin, 5 parts of 3-methyl-2-oxazolidinone, and 68 parts of diethylene glycol diethyl ether, respectively. Were mixed to prepare pigment dispersions J1 to J12 and comparative pigment dispersions CJ1 to CJ3.

  The pigment dispersions J1 to J12 and the comparative pigment dispersions CJ1 to CJ3 were evaluated as inkjet inks.

  (1) Dispersion particle size: The pigment dispersion was diluted 200 to 1000 times with ethyl acetate and measured with a particle size distribution system Microtrac UPA150 (manufactured by Nikkiso Co., Ltd.).

  (2) Viscosity: The pigment dispersion was adjusted to 25 ° C. and measured with an E-type viscometer RE80 (manufactured by Toki Sangyo Co., Ltd.).

  (3) Viscosity with time: The viscosity of the pigment dispersion after storage at 70 ° C. for 1 week was measured in the same manner as described above. When the viscosity change from the initial stage was 5% or less, ◎, 5 to 10% were marked with ◯, 10 to 30% were marked with △, and more were marked with ×.

  (4) Alcohol resistance: The above pigment dispersion was solid-printed on the vinyl chloride sheet Metamark MD5 with a large-format inkjet printer colorpainter 64S (manufactured by Seiko I Infotech), and the resulting print sample was swabbed with ethanol. Rub 10 round trips. The amount of ink attached to the cotton swab was defined as “A” which was not applied at all, “A” which was slightly attached, “A” which was attached to the cotton swab but the substrate on the printed surface was not visible, and “X” which was removed so that the substrate was visible.

  (5) Abrasion: The amount of ink attached to the kana gold after the printed sample made in the same manner as described above was applied to the Gakushin Tester and made 100 reciprocations with Kanakin No. 3 with a 200 g weight. Not marked ◎, slightly attached ○, attached to kana gold, but the substrate of the stamped ground is not visible Δ, and × is taken so that the substrate is visible.

  (6) Discharge state (appropriate printing): After the above-mentioned pigment dispersion was solid-printed for 10 minutes, the print state of the nozzle check pattern was observed after the large-format inkjet printer colorpainter 64S (manufactured by Seiko I Infotech). For print defects such as nozzle omission and bending, 1% or less was marked as ◎, 1 to 5% as ◯, 5 to 10% as △, and 10% or more as x.

  The evaluation results of (1) to (6) are shown in Table 4 below.

Abbreviations (binder resins) in Table 4 are as follows.
・ Eucer Solution VYHD: UCAR SOLUTION VINYL RESINE VYHD Dow Chemical Co., Ltd. Vinyl chloride-vinyl acetate copolymer (weight ratio 86/14) Weight average molecular weight 22000
・ Eucer Solution VMCA: UCAR SOLUTION VINYL RESINE VMCA manufactured by Dow Chemical Co., Ltd. Vinyl chloride-vinyl acetate-other-copolymer (weight ratio 81/17/2) Weight average molecular weight 22000
・ Solvine CL: SOLBIN CL Vinyl chloride-vinyl acetate copolymer (weight ratio 86/14) manufactured by Nissin Chemical Industry Co., Ltd. Weight average molecular weight 25000
・ Solvine CNL: SOLBIN CNL Vinyl chloride-vinyl acetate copolymer (weight ratio 90/10) manufactured by Nissin Chemical Industry Co., Ltd. Weight average molecular weight 12000
・ Solvine C5R: SOLBIN TA5R manufactured by Nissin Chemical Industry Co., Ltd. Vinyl chloride-vinyl acetate copolymer (weight ratio 79/21) Weight average molecular weight 27000
Solvain TA5R: SOLBIN TA5R manufactured by Nissin Chemical Industry Co., Ltd. Vinyl chloride-vinyl acetate-other-copolymer (weight ratio 88/1/11) Weight average molecular weight 27000
E15 / 45: VINNOL E15 / 45 Vinyl chloride-vinyl acetate copolymer (weight ratio 85/15) manufactured by Wacker, Inc. Weight average molecular weight 45000-55000
H14 / 36: VINNOL E14 / 36 Vinyl chloride-vinyl acetate copolymer (weight ratio 86/14) manufactured by Wacker, Inc. Weight average molecular weight 30000-40000
H15 / 42: VINNOL E15 / 42 Vinyl chloride-vinyl acetate copolymer (weight ratio 86/14) manufactured by Wacker, Inc. Weight average molecular weight 30000-40000
H40 / 43: VINNOL E40 / 43 Vinyl chloride-vinyl acetate copolymer (weight ratio 66/34) manufactured by Wacker, Inc. Weight average molecular weight 40000-50000
H15 / 45M: VINNOL E15 / 45M manufactured by Wacker, Inc. Vinyl chloride-vinyl acetate-other-copolymer (weight ratio 84/15/1) Weight average molecular weight 60000-80000
E15 / 40A: VINNOL E14 / 36 Vinyl chloride-vinyl acetate copolymer (weight ratio 84/16) manufactured by Wacker, Inc. Weight average molecular weight 40000-50000

Claims (15)

Polymer formed by reacting hydroxyl group or primary amino group of polymer (A) having one hydroxyl group or primary amino group in one terminal region with at least one isocyanate group of polyisocyanate (B) ( A) an isocyanate group of (poly) isocyanate (E) having at least one moiety;
A primary and / or secondary amino group of a polyamine (c2) having at least two primary and / or secondary amino groups at both ends and further having a secondary and / or tertiary amino group at both ends ; A dispersant having a primary amino group obtained by reacting
An acidic pigment dispersant having an amine value of 1 to 107.15 mgKOH / g. The acidic pigment dispersant according to claim 1, wherein the polymer (A) having one hydroxyl group or primary amino group in one terminal region is represented by the following general formula (1).
General formula (1):
[In general formula (1),
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 ¹ is —O—, —S—, or —N (R ⁰ ) — (where R ⁰ 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 ² —O—,
G ² is a repeating unit represented by —C (═O) —R ³ —O—,
R ² is a linear or branched alkylene group having 2 to 8 carbon atoms, or 3 to 3 carbon atoms.
8 cycloalkylene groups,
R ³ is a linear or branched alkylene group having 1 to 8 carbon atoms, or 4 to
8 cycloalkylene groups,
R ¹ is R ² or —C (═O) R ³ —,
m1 is an integer from 0 to 100;
m2 is an integer of 0 to 100,
However, m1 + m2 is an integer from 1 to 200,
The arrangement of the repeating units G ¹ and G ² in the general formula (1) does not limit the order,
In the polymer represented by the general formula (1), the repeating units G ¹ and G ² are included in any order between X ¹ and R ¹ ,
Further, the repeating units G ¹ and G ² may be either random type or block type, respectively. ] The acidic pigment dispersant according to claim 2, wherein Y ¹ in the general formula (1) is a linear or branched alkyl group having 1 to 18 carbon atoms. The polyamine (C) is a polyamine having two or more primary amino groups, or has two primary and / or secondary amino groups at both ends, and further has a secondary amino group other than both ends. The acidic pigment dispersant according to claim 1, wherein the acidic pigment dispersant is a polyamine. The acidic pigment dispersion according to any one of claims 1 to 4, wherein the polymer (A) having one hydroxyl group or primary amino group in one terminal region has a weight average molecular weight of 500 to 30,000. Agent. The acidic pigment dispersant according to any one of claims 1 to 5, wherein the weight average molecular weight is 1,000 to 100,000. The acidic pigment dispersant according to any one of claims 2 to 6, wherein m2 in the general formula (1) is an integer of 3 to 70. The acidic pigment dispersant according to any one of claims 2 to 7, wherein m1 in the general formula (1) is an integer of 2 to 20. One or more kinds of cyclic compounds selected from the group consisting of alkylene oxides, lactones, and lactides with one or more kinds of compounds selected from the group consisting of monoalcohols, primary monoamines, secondary monoamines, and monothiols as initiators. A first step of producing a polymer (A) having one hydroxyl group in one terminal region by ring-opening polymerization;
It has at least one polymer (A) site obtained by reacting the hydroxyl group of the polymer (A) having one hydroxyl group at one terminal region with at least one isocyanate group of the polyisocyanate (B). A second step of producing (poly) isocyanate (E), and
It has an isocyanate group of (poly) isocyanate (E) having at least one polymer (A) moiety, at least two primary and / or secondary amino groups at both ends, and secondary at both ends. And / or a third step of reacting a primary and / or secondary amino group of an amine compound containing a polyamine (c2) having a tertiary amino group;
The manufacturing method of the acidic pigment dispersant containing this. One or more kinds of cyclic compounds selected from the group consisting of alkylene oxides, lactones, and lactides with one or more kinds of compounds selected from the group consisting of monoalcohols, primary monoamines, secondary monoamines, and monothiols as initiators. A first step of ring-opening polymerization, and further reductive amination of a hydroxyl group at one terminal region to produce a polymer (A) having one primary amino group at one terminal region;
A polymer (A) site formed by reacting the primary amino group of the polymer (A) having one primary amino group in the one terminal region with at least one isocyanate group of the polyisocyanate (B); A second step of producing (poly) isocyanate (E) having at least one, and
Third step of reacting an isocyanate group of (poly) isocyanate (E) having at least one polymer (A) site with a primary and / or secondary amino group of an amine compound containing at least polyamine (C) When,
The manufacturing method of the acidic pigment dispersant containing this. The acidic pigment dispersant according to claim 9 or 10, wherein the first step, the second step, and / or the third step are performed in a solvent, and the solvent is diethylene glycol diethyl ether. Production method. A pigment composition comprising the acidic pigment dispersant according to claim 1 and an acidic pigment. Furthermore, a dye derivative having an acidic substituent represented by the following general formula (2), a dye derivative having an acidic substituent represented by the following general formula (3), and an acid represented by the following general formula (4) The pigment composition according to claim 12, comprising a dye derivative having one or more kinds of acidic substituents selected from the group consisting of a dye derivative having a substituent.
General formula (2):
PZ ²
(In general formula (2), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. Z ² is a sulfonic acid group or a carboxyl group, which is a kind of organic dye residue selected from the group consisting of a series, a perinone series, a flavanthrone series, a pyranthrone series, and an anthrapyrimidine series.
General formula (3):
(PZ ³ ) [N ⁺ (R ⁴ , R ⁵ , R ⁶ , R ⁷ )]
(In the general formula (3), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. R ⁴ is an alkyl group having 5 to 20 carbon atoms, R ⁵ , R ⁵ , R ⁵ , R ⁵ , R ⁴ , R ⁴ , R ⁴ , R ⁵ , R ^{5 6,} and R ⁷ are each independently a hydrogen atom or an alkyl group having a carbon number of 1 to 20, Z ³ is SO ₃ ^- or COO ^- and is).
General formula (4):
(P−Z ⁴ ) M ⁺
(In the general formula (4), P represents azo, benzimidazolone, phthalocyanine, quinacridone, anthraquinone, dioxazine, diketopyrrolopyrrole, quinophthalone, isoindolinone, isoindoline, perylene. Is an organic dye residue selected from the group consisting of a series, a perinone series, a flavanthrone series, a pyranthrone series, and an anthrapyrimidine series, M is Na or a K atom, and Z ⁴ is SO ₃ ^- or COO ^- it can be). A pigment dispersion obtained by dispersing the pigment composition according to claim 12 or 13 in a varnish. The pigment dispersion according to claim 14, wherein the varnish comprises diethylene glycol diethyl ether as a solvent.