WO2018030506A1 - Pigment composition, coating material containing said pigment composition, and dispersant - Google Patents

Abstract

A pigment composition which contains a pigment, water and a neutralized product of an acidic group-containing dispersant (S) and a basic compound, and wherein the acidic group-containing dispersant (S) contains the resin (S1) or (S2) described below. (S1) A resin which is a reaction product of an acid anhydride group of a tricarboxylic acid anhydride and/or a tetracarboxylic acid dianhydride and a hydroxyl group of a polymer (A) that has a hydroxyl group and an acidic group. (S2) A resin which is a polymer obtained by polymerizing an ethylenically unsaturated monomer (C) containing an acidic group-containing ethylenically unsaturated monomer (c1) in the presence of a reaction product of an acid anhydride group of a tricarboxylic acid anhydride and/or a tetracarboxylic acid dianhydride and a hydroxyl group of a compound (B) having a hydroxyl group.

Description

Pigment composition, paint containing the pigment composition, and dispersant

The embodiment of the present disclosure relates to an aqueous pigment composition particularly suitable for an aqueous composition. Other embodiment of this indication is related with the coating material containing the said pigment composition. Yet another embodiment of the present disclosure relates to a dispersant.

The industry that uses colorants such as paints and inks has a strong tendency to become water-based because it has no toxicity problems such as fire hazard and mutagenicity, or has excellent characteristics that these problems can be further reduced. .

Color materials used as colorants are roughly classified into dyes and pigments. When a pigment is used as the color material, the printed material has excellent characteristics such as water fastness and light fastness as compared with the case of using a dye as the color material. On the other hand, pigments have problems of low transparency and low color developability in comparison with dyes. In addition, in a dispersion using a dye, a dye which is a color material is used after being dissolved in a medium, whereas in a pigment dispersion, a pigment which is a color material is used by being dispersed in the medium.

In order to disperse a pigment used in an aqueous colorant in an aqueous medium, a method of dispersing a powder pigment using a surfactant or a water-soluble resin is generally used, and this method is still widely used today. Yes. However, a paint containing a pigment dispersed using a surfactant has a problem that the resulting coating film has extremely poor water resistance and can be used only for limited applications. Also, it is generally more difficult to disperse a pigment in an aqueous medium containing a water-soluble resin than when a pigment is dispersed in an organic solvent medium. Therefore, it is difficult to finely disperse the pigment in an aqueous medium at a high level and keep the state stable.

Small organic particle color pigments generally have poor pigment dispersibility and tend to be energetically stable even after being dispersed in a paint. Therefore, the organic coloring pigment aggregates in the paint, and the size of the particles changes or the adsorption to other pigments easily occurs. These phenomena are various even in a state where the paint is formed into a coating film. May cause performance degradation.

In order to improve the pigment dispersibility, the pH of the aqueous dispersion of the pigment finely dispersed using a resin having a carboxyl group neutralized with a basic compound is neutral or acidic using an acidic compound. By making the resin hydrophobic, the resin is firmly fixed to the pigment (hereinafter, this step is referred to as “acid precipitation”), and then, if necessary, the aqueous dispersion after acid precipitation is filtered and washed with water. Thereafter, a method of producing an aqueous pigment dispersion by neutralizing a carboxyl group again with a basic compound and redispersing it in water is known. According to this method, it is possible to prepare an aqueous pigment dispersion in which the pigment is finely dispersed to an extent sufficient to exhibit gloss, color developability, and coloring power, and also has excellent storage stability (patent) References 1, 2).

Also known is a method of obtaining a powder or solid pigment by performing acid precipitation using a limited resin such as a relatively high molecular weight acrylic resin (Patent Document 3).

Furthermore, as a dispersant capable of finely dispersing a pigment at a high level, a dispersant as described in Patent Document 4 is known. However, this dispersant is excellent in dispersibility when the dispersion medium is a solvent, but cannot be applied when the dispersion medium is water.

In recent years, a paint color having a high pigment concentration may be set in accordance with a demand for a paint color having excellent design and vivid high saturation. However, when the coating color is constituted by using an organic coloring pigment having poor dispersibility, there is a limit in coating film performance. Furthermore, since solvent type paints are concerned about environmental impacts, conversion to water-based paints is required.

JP-A-9-31360 Japanese Patent Laid-Open No. 50-122528 JP 11-199783 A WO2008 / 007776

The problem to be solved by the present invention is to provide a pigment composition that is excellent in dispersibility and excellent in hue, water resistance, haze value, and flip-flop properties, which cannot be achieved by the above-described conventional technology. It is in. Moreover, it is providing the water-based coating material which is excellent in the designability using the said pigment composition.

Embodiments of the present invention relate to the following, but are not limited thereto.
An embodiment of the present invention is a pigment composition containing a neutralized product of an acidic group-containing dispersant (S) and a basic compound, a pigment and water, wherein the acidic group-containing dispersant (S) is: The present invention relates to a pigment composition containing the resin (S1) or (S2).
(S1) A resin which is a reaction product of the hydroxyl group of the polymer (A) having a hydroxyl group and an acidic group and the acid anhydride group of a tricarboxylic acid anhydride and / or tetracarboxylic dianhydride.
(S2) In the presence of the reaction product of the hydroxyl group of the compound (B) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride, an acidic group-containing ethylenically unsaturated monomer A resin which is a polymer obtained by polymerizing an ethylenically unsaturated monomer (C) containing a monomer (c1).

In one embodiment, the polymer (A) having a hydroxyl group and an acidic group in the resin (S1) is an acidic group-containing ethylene in the presence of a compound (b1) having two hydroxyl groups and one thiol group in the molecule. The polymer (a1) obtained by polymerizing the ethylenically unsaturated monomer (C) containing the polymerizable unsaturated monomer (c1) is preferable.

In one embodiment, the content of the acidic group-containing ethylenically unsaturated monomer (c1) is preferably 3% by mass to 30% by mass with respect to the total amount of the ethylenically unsaturated monomer (C). .

In one embodiment, the acidic group-containing dispersant (S) preferably has a weight average molecular weight of 7,000 to 25,000 and an acid value of 20 to 130.

In one embodiment, the content of the acidic group-containing dispersant (S) is preferably 10% by mass to 30% by mass with respect to the total amount of the pigment.

In one embodiment, the basic compound is preferably an organic amine.

In one embodiment, the organic amine is preferably an alkanolamine.

In one embodiment, the pH of the pigment composition is preferably 8-11.

In one embodiment, the pigment is preferably at least one selected from the group consisting of diketopyrrolopyrrole, quinacridone and perylene.

Other embodiment of this invention is related with the coating material containing the pigment composition of the said embodiment, and binder resin.

In one embodiment, the binder resin preferably includes an acrylic resin and a melamine resin.

Other embodiment of this invention is related with the coated material formed by apply | coating the coating material of the said embodiment on a base material.

Another embodiment of the present invention is a dispersant that is a neutralized product of an acidic group-containing dispersant (S) and a basic compound, wherein the acidic group-containing dispersant (S) is the following (S1) or ( The present invention relates to a dispersant containing the resin S2).
(S1) A resin which is a reaction product of the hydroxyl group of the polymer (A) having a hydroxyl group and an acidic group and the acid anhydride group of a tricarboxylic acid anhydride and / or tetracarboxylic dianhydride.
(S2) In the presence of the reaction product of the hydroxyl group of the compound (B) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride, an acidic group-containing ethylenically unsaturated monomer A resin which is a polymer obtained by polymerizing an ethylenically unsaturated monomer (C) containing a monomer (c1).

According to the embodiment of the present invention, a pigment composition having excellent dispersibility and good hue can be provided. Moreover, the coating material which is excellent in design property can be provided.
The disclosure of the present application is related to the subject matter described in Japanese Patent Application No. 2016-157992 and Japanese Patent Application No. 2017-132462, the entire disclosures of which are incorporated herein by reference.

Hereinafter, embodiments of the present invention will be described in detail. However, embodiments of the present invention are not limited to the following, and include various embodiments.
<Pigment composition>
The pigment composition according to the first embodiment of the present invention is a liquid obtained by dispersing a pigment in a liquid medium containing water as a main component. The pigment composition is composed of an acidic group-containing dispersant (S) and a basic compound. It is a pigment composition containing a hydrate, a pigment, and water. The “neutralized product of the acidic group-containing dispersant (S) and the basic compound” described in the present specification means that the acidic group in the acidic group-containing dispersant (S) is sufficient by the basic compound in the pigment composition. In other words, it means that it is in a completely neutralized state. That is, prior to the preparation of the pigment composition, the step of forming a neutralized product of the acidic group-containing dispersant (S) and the basic compound is not essential. A sufficient amount of the basic compound may be used to completely neutralize the acidic group of the agent (S). In one embodiment, the pH of the pigment composition is preferably 6 or more, and more preferably 8 or more. When the pH of the pigment composition is adjusted to 6 or more, it becomes easy to sufficiently neutralize the acidic groups of the acidic group-containing dispersant (S). By neutralizing the acidic group, charge repulsion necessary for pigment dispersion can be secured. On the other hand, the upper limit of the pH is not particularly limited, but in one embodiment, the pH is preferably 11 or less from a practical viewpoint. In one embodiment, the pH of the pigment composition is preferably in the range of 8 to 11 because it becomes easy to completely neutralize the acidic group.

<Acid group-containing dispersant (S)>
The resins (S1) and (S2) contained in the acidic group-containing dispersant (S) are mainly 2 of the polymerization reaction of ethylenically unsaturated double bonds and the esterification reaction of a hydroxyl group and an acid anhydride group. It has a complicated structure obtained by two reactions, and cannot be represented by a general formula (structure) or is not realistic. Therefore, it describes according to a manufacturing method about the said resin.
In the pigment composition, the acidic group-containing dispersant (S) contains the following resin (S1) or (S2). In one embodiment, the acidic group-containing dispersant (S) preferably consists essentially of the following resin (S1) or (S2), and more preferably comprises the following resin (S1) or (S2). .
(S1) A resin which is a reaction product of the hydroxyl group of the polymer (A) having a hydroxyl group and an acidic group and the acid anhydride group of a tricarboxylic acid anhydride and / or tetracarboxylic dianhydride.
(S2) In the presence of the reaction product of the hydroxyl group of the compound (B) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride, an acidic group-containing ethylenically unsaturated monomer A resin which is a polymer obtained by polymerizing an ethylenically unsaturated monomer (C) containing a monomer (c1).

[Resin (S1)]
The resin (S1) can be produced by a known method such as WO2008 / 007776 and JP2008-029901. The polymer (A) having a hydroxyl group and an acidic group is preferably a polymer having a hydroxyl group at the terminal and an acidic group in the side chain. For example, the polymer (A) is obtained by polymerizing an ethylenically unsaturated monomer (C) containing an acidic group-containing ethylenically unsaturated monomer (c1) in the presence of a compound (B) having a hydroxyl group. It may be the polymer (a1) obtained. The compound (B) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule as described later. Especially, since it is preferable that there are two or more terminal hydroxyl groups, the compound (b1) which has two hydroxyl groups and one thiol group in a molecule | numerator is used suitably.

That is, a more preferable example of the polymer (A) is a polymer having two hydroxyl groups at one end. This polymer is an ethylenically unsaturated monomer containing an acidic group-containing ethylenically unsaturated monomer (c1) in the presence of a compound (b1) having two hydroxyl groups and one thiol group in the molecule. It can be obtained as a polymer (a1) obtained by polymerizing (C). While the hydroxyl group of the polymer (A) having a hydroxyl group and an acidic group reacts with an acid anhydride group of a tricarboxylic acid anhydride and / or tetracarboxylic dianhydride to form an ester bond, an acid anhydride ring Carboxylic acid groups are formed by ring opening of the structure.

[Resin (S2)]
The resin (S2) can be produced by a known method such as JP 2010-185934 A. For example, the hydroxyl group of the compound (B) having a hydroxyl group, a tricarboxylic anhydride and / or a tetracarboxylic dianhydride A polymer obtained by polymerizing an ethylenically unsaturated monomer (C) containing an acidic group-containing ethylenically unsaturated monomer (c1) in the presence of a reaction product with an acid anhydride group of the product. It may be. In particular, in the presence of a reaction product of the hydroxyl group of the compound (b1) having two hydroxyl groups and one thiol group in the molecule and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride. In addition, a polymer obtained by polymerizing an ethylenically unsaturated monomer (C) containing an acidic group-containing ethylenically unsaturated monomer (c1) is preferable.

The difference between the resins (S1) and (S2) is that the introduction of the polymer site by polymerization of the ethylenically unsaturated monomer (C) including the acidic group-containing ethylenically unsaturated monomer (c1) Or only later. Therefore, although the molecular weight and the like may be slightly different depending on various conditions, the same resin can be theoretically obtained if the raw materials and the reaction conditions are the same. Although not particularly limited, the resin (S1) is more preferable from the viewpoint of stable production. Hereinafter, the starting materials used for producing the resins (S1) and (S2) will be specifically described.

[Production of polymer (A) having a hydroxyl group and an acidic group]
As described above, the polymer (A) having a hydroxyl group and an acidic group in the resin (S1) is preferably a polymer having a hydroxyl group at a terminal and an acidic group in a side chain. As a more preferable example of the polymer (A), an acidic group-containing ethylenically unsaturated monomer (c1) is included in the presence of a compound (b1) having two hydroxyl groups and one thiol group in the molecule. A polymer (a1) obtained by polymerizing the ethylenically unsaturated monomer (C) is exemplified.

In the production of the polymer (A), the ratio of 1 to 30 parts by weight of the compound (b1) having two hydroxyl groups and one thiol group with respect to 100 parts by weight of the ethylenically unsaturated monomer (C). It is preferable to perform bulk polymerization or solution polymerization. The proportion of the compound (b1) is more preferably 3 to 12 parts by weight, still more preferably 4 to 12 parts by weight, and particularly preferably 5 to 9 parts by weight. By making the said ratio into the said range, the favorable balance as an affinity site | part with respect to a pigment carrier and a solvent can be maintained, and dispersibility and pigment aggregation suppression can be made compatible.

The weight average molecular weight of the polymer (A) is preferably 1,000 to 10,000, more preferably 2,000 to 8,000, still more preferably 2,000 to 6,000, and particularly preferably 3,000 to 10,000. 5,000. The site | part with respect to this polymer (A) becomes an affinity site | part with respect to a pigment carrier and a solvent. It is easy to adjust the weight average molecular weight of the polymer (A) within the above range, and the polymer (A) within the above range can easily obtain good affinity for the solvent.

In the above polymerization, 0.001 to 5 parts by weight of a polymerization initiator can be arbitrarily used with respect to 100 parts by weight of the ethylenically unsaturated monomer (C). As the polymerization initiator, an azo compound and an organic peroxide can be used.
Examples of azo compounds include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 1,1′-azobis (cyclohexane 1-carbonitrile), 2 , 2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethyl-4-methoxyvaleronitrile), dimethyl 2,2'-azobis (2-methylpropionate) 4,4′-azobis (4-cyanovaleric acid), 2,2′-azobis (2-hydroxymethylpropionitrile), 2,2′-azobis [2- (2-imidazolin-2-yl) Propane] and the like.
Examples of organic peroxides include benzoyl peroxide, t-butyl perbenzoate, cumene hydroperoxide, diisopropyl peroxydicarbonate, di-n-propyl peroxydicarbonate, di (2-ethoxyethyl) peroxy Examples thereof include dicarbonate, t-butyl peroxyneodecanoate, t-butyl peroxybivalate, (3,5,5-trimethylhexanoyl) peroxide, dipropionyl peroxide, diacetyl peroxide and the like.
These polymerization initiators can be used alone or in combination of two or more.

In the case of solution polymerization, the polymerization solvents are ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol mono Ethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and the like are used, but are not particularly limited thereto. Two or more kinds of these polymerization solvents may be mixed and used. The solvent (polymerization solvent) used for the polymerization reaction can be removed by an operation such as distillation after the completion of the reaction. Alternatively, the polymerization solvent can be used as it is as a solvent for the next step or as part of a product.

The reaction temperature is preferably 40 to 150 ° C, more preferably 50 to 110 ° C.

Also, the polymerization reaction of the ethylenically unsaturated monomer (C) including the acidic group-containing ethylenically unsaturated monomer (c1) in the resin (S2) is performed in the same manner as described above.

[Compound having hydroxyl group (B)]
The compound (B) having a hydroxyl group in the resin (S2) preferably contains a compound having a hydroxyl group and a thiol group in the molecule. The compound having a hydroxyl group and a thiol group in the molecule is not limited as long as it has a hydroxyl group and a thiol group.
As such a compound, for example, a compound having two hydroxyl groups and one thiol group in a molecule described later may be used. As another example,
Compounds having one hydroxyl group and one thiol group in the molecule, such as mercaptoethanol;
Compounds having one hydroxyl group and two thiol groups in the molecule, such as 1,2-dimercapto-3-propanol and 1,3-dimercapto-2-propanol;
Compounds having one hydroxyl group and three or more thiol groups in the molecule, such as pentaerythritol tris (3-mercaptoacetate) and dipentaerythritol pentakis (3-mercaptopropionate);
Compounds having two hydroxyl groups and two thiol groups in the molecule, such as 1,2-dimercapto-1,2-ethanediol;
Compounds having three or more hydroxyl groups and two thiol groups in the molecule, such as dimercaptodipentaerythritol;
Compounds having two or more hydroxyl groups and three or more thiol groups in the molecule such as trimercaptodipentaerythritol;
Compounds having three or more hydroxyl groups and one thiol group in the molecule such as 1-mercapto-1,2,2′-ethanetriol;
Etc.
Among the exemplified compounds, the compound (b1) having two hydroxyl groups and one thiol group in the molecule is preferable.

(Compound (b1) having two hydroxyl groups and one thiol group in the molecule)
Examples of the compound having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, and 3-mercapto-1,2-propane. Diol (hereinafter abbreviated as thioglycerin or thioglycerol), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3 -Propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, etc. It is done. Of these, 3-mercapto-1,2-propanediol is preferable.

The compound (B) having a hydroxyl group in the resin (S2) may contain a compound other than the compound having a hydroxyl group and a thiol group in the molecule exemplified above.
For example, polyhydric alcohols such as ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, or hexanetriol;
Polyether glycols such as polyoxyethylene glycol, polyoxypropylene glycol, or polyoxyethylene polyoxypropylene polyoxytetramethylene glycol;
Modified polyether polyols obtained by ring-opening polymerization of the polyhydric alcohols with (cyclic) ether bond-containing compounds such as ethylene oxide, propylene oxide, or allyl glycidyl ether;
Polyester polyols obtained by co-condensation of one or more of the above polyhydric alcohols with polyvalent carboxylic acids, wherein the polyvalent carboxylic acids are succinic acid, adipic acid, or 2,5,7-naphthalene Polyols such as tricarboxylic acid;
Lactone polyester polyols obtained by polycondensation reaction of one or more of the above polyhydric alcohols with lactones such as ε-caprolactone, δ-valerolactone or 3-methyl-δ-valerolactone;
Lactone modified polyester polyols obtained by polycondensation reaction of the above polyhydric alcohols, polycarboxylic acids and various lactones;
Various epoxy compounds such as bisphenol A type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, glycidyl ethers of monohydric and / or polyhydric alcohols, or glycidyl esters of monobasic acids and / or polybasic acids, polyesters Epoxy-modified polyester polyols obtained by combining one or more of the polyols during synthesis;
Polyester polyamide polyol, polycarbonate polyol, polybutadiene polyol, polypentadiene polyol,
Castor oil, castor oil derivative, hydrogenated castor oil, hydrogenated castor oil derivative,
Examples include a hydroxyl group-containing acrylic copolymer, a hydroxyl group-containing fluorine-containing compound, or a hydroxyl group-containing silicon resin.

[Ethylenically unsaturated monomer (C)]
In the resin (S2), the ethylenically unsaturated monomer (C) includes an acidic group-containing ethylenically unsaturated monomer (c1).

(Acid group-containing ethylenically unsaturated monomer (c1))
Examples of the acidic group-containing ethylenically unsaturated monomer (c1) include ethylenically unsaturated monomers having a carboxyl group such as acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid;
From an ethylenically unsaturated monomer having a carboxylic anhydride group such as maleic anhydride and itaconic anhydride, and an ethylenically unsaturated monomer having sulfonic acid, phosphoric acid, fluoric acid, etc. Species or two or more can be selected. In particular, from the viewpoint of dispersibility of the pigment, an ethylenically unsaturated monomer having a carboxyl group is preferable.

Moreover, as an example of a monomer that can be used in combination with the acidic group-containing ethylenically unsaturated monomer (c1),
Methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2- Alkyl (meth) acrylates such as ethylhexyl (meth) acrylate, stearyl (meth) acrylate, and lauryl (meth) acrylate;
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, 1-adamantyl (meth) acrylate, 2- Cycloaliphatic alkyl (meth) acrylates such as methyl-2-adamantyl (meth) acrylate and 2-2 ethyladamantyl (meth) acrylate;
Heterocyclic (meth) acrylates such as tetrahydrofurfuryl (meth) acrylate and 3-methyloxetanyl (meth) acrylate;
(Meth) acrylates having an aromatic substituent such as phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethylene oxide-modified (meth) acrylate, and paracumylphenoxyethylene oxide-modified (meth) acrylate;
Alkoxyalkylene (meth) acrylates such as methoxyethyl (meth) acrylate, methoxypropyl (meth) acrylate, ethoxyethyl (meth) acrylate;
Alkoxypolyalkylene glycol (meth) acrylates such as methoxypolypropylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) acrylate and ethoxypolyethylene glycol (meth) acrylate;
(Meth) acrylamide and N-substituted types such as N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, and acryloylmorpholine ( (Meth) acrylamides;
Amino group-containing (meth) acrylates such as N, N-dimethylaminoethyl (meth) acrylate and N, N-diethylaminoethyl (meth) acrylate;
Nitriles such as (meth) acrylonitrile; styrenes such as styrene and α-methylstyrene;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether;
Ethylenically unsaturated monomers having a phenolic hydroxyl group such as N-hydroxyphenylmaleimide;
Fatty acid vinyls such as vinyl acetate and vinyl propionate; and
A mixture is mentioned from these 2 or more types.

Among the other monomers exemplified above, two or more selected from the group consisting of alkyl (meth) acrylates, (meth) acrylates having an aromatic substituent, and alkoxyalkylene (meth) acrylates These monomers are preferably used in combination. In one embodiment, at least three monomers selected from the group consisting of methoxyethyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, benzyl (meth) acrylate, and t-butyl (meth) acrylate It is preferable to use it. The methyl (meth) acrylate content is preferably 15% by mass to 80% by mass and more preferably 30% by mass to 50% by mass with respect to the total amount of the ethylenically unsaturated monomer (C). More preferred.

From the viewpoint of dispersibility of the pigment, the content of the acidic group-containing ethylenically unsaturated monomer (c1) is 3% by mass to 30% by mass with respect to the total amount of the ethylenically unsaturated monomer (C). Is preferred. In one embodiment, the content is more preferably 4% by mass to 25% by mass.

The hydroxyl group of the polymer (A) in the resin (S1) or the hydroxyl group of the compound (B) in the resin (S2) is an acid containing a tricarboxylic acid anhydride and / or a tetracarboxylic dianhydride described below. An ester bond is formed by reaction with an anhydride. Hereinafter, the acid anhydride will be described.
[Tricarboxylic anhydride]
Examples of the tricarboxylic acid anhydride include aliphatic tricarboxylic acid anhydrides or aromatic tricarboxylic acid anhydrides.
Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric acid anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid- 1,2-anhydride, 1,3,4-cyclopentanetricarboxylic acid anhydride and the like.
Examples of the aromatic tricarboxylic acid include benzene tricarboxylic acid anhydride (1,2,3-benzene tricarboxylic acid anhydride, trimellitic acid anhydride [1,2,4-benzene tricarboxylic acid anhydride], etc.), naphthalene tricarboxylic acid, and the like. Acid anhydrides (1,2,4-naphthalene tricarboxylic acid anhydride, 1,4,5-naphthalene tricarboxylic acid anhydride, 2,3,6-naphthalene tricarboxylic acid anhydride, 1,2,8-naphthalene tricarboxylic acid anhydride 3,4,4′-benzophenone tricarboxylic acid anhydride, 3,4,4′-biphenyl ether tricarboxylic acid anhydride, 3,4,4′-biphenyl tricarboxylic acid anhydride, 2,3,2 ′ -Biphenyltricarboxylic acid anhydride, 3,4,4'-biphenylmethanetricarboxylic acid anhydride, or 3,4,4'-biphenylsulfo Tricarboxylic anhydride and the like.
In one embodiment, it is preferable to use an aromatic tricarboxylic acid anhydride from the viewpoint of adsorptivity to the pigment.

[Tetracarboxylic dianhydride]
Examples of the tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2 , 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6- Tricarboxynorbornane-2-acetic acid dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5- (2,5-dioxotetrahydrofural) -3-methyl-3-cyclohexene-1, 2-dicarboxylic dianhydrides or aliphatic tetracarboxylic dianhydrides such as bicyclo [2,2,2] -oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, and Pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride ester, propylene glycol ditrimellitic anhydride ester, butylene glycol ditrimellitic anhydride ester, 3,3 ', 4,4'-benzophenone tetracarboxylic dianhydride 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride Anhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3 ′, 4,4 '-Tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis (3,4-dicarbo Ciphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylpropane dianhydride 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride P-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, Bis (triphenylphthalic acid) -4,4'-diphenylmethane dianhydride, 9,9-bis (3,4-dicarboxyphenyl) fluorene dianhydride 9,9-bis [4- (3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride Or aromatic tetracarboxylic dianhydrides such as 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride.
In one embodiment, it is preferable to use an aromatic tetracarboxylic anhydride from the viewpoint of adsorptivity to the pigment.

The tetracarboxylic dianhydride is not limited to the compounds exemplified above, and may have two carboxylic anhydride groups in the molecule and may have any structure. These compounds may be used alone or in combination.

The tricarboxylic acid anhydride and tetracarboxylic acid dianhydride in the resins (S1) and (S2) are preferably tetracarboxylic acid dianhydrides and more preferably aromatic tetracarboxylic acid dianhydrides from the viewpoint of adsorptivity to the pigment. . Of these, pyromellitic dianhydride is more preferable. When the aromatic carboxylic dianhydride is used, the pigment adsorbing ability is higher than that of the aliphatic carboxylic dianhydride.

[Synthesis of acidic group-containing dispersant (S)]
The resin (S1) is obtained by the reaction (polyester synthesis) of the hydroxyl group of the polymer (A) having the hydroxyl group and acidic group described above with the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride. be able to.
In addition, the resin (S2) is obtained by reacting the hydroxyl group of the above-described compound (B) having a hydroxyl group with the acid anhydride group of tricarboxylic acid anhydride and / or tetracarboxylic dianhydride (polyester synthesis). It can be obtained by polymerizing an ethylenically unsaturated monomer (C) containing an acidic group-containing ethylenically unsaturated monomer (c1) in the presence of a reaction product.
The polyester synthesis can be carried out as follows. The polymerization in the resin (S2) is as described above.
(Reaction solvent)
Polyester synthesis can be carried out using only the raw materials exemplified above, but it is preferable to carry out using a solvent in order to avoid problems such as high viscosity and non-uniform reaction. There is no limitation in particular as a solvent which can be used at the time of a synthesis | combination, You may be a well-known solvent. For example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, toluene, xylene, acetonitrile and the like can be mentioned. The solvent used in the synthesis can be removed by an operation such as distillation after the completion of the reaction. Alternatively, the reaction solvent can be used as it is as the solvent for the next step or as part of the product.

(Reaction catalyst)
As a catalyst used for polyester synthesis, a known catalyst can be used. The catalyst is preferably a tertiary amine compound. For example, triethylamine, triethylenediamine, N, N-dimethylbenzylamine, N-methylmorpholine, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0 ] -5-nonene and the like.

(Reaction temperature)
The reaction temperature of the polyester synthesis is 50 ° C to 180 ° C, preferably 80 ° C to 140 ° C. When the reaction temperature is 50 ° C. or lower, the reaction rate is slow, and when the reaction temperature is 180 ° C. or higher, the carboxyl group and the hydroxyl group may undergo an esterification reaction, resulting in a decrease in acid value or gelation. Ideally, the reaction is stopped by reacting until the absorption of acid anhydride disappears by infrared absorption. However, the reaction may be stopped when the acid value of the polyester falls within the range of 5 to 200, or when the hydroxyl value falls within the range of 20 to 200.

(Molecular weight)
The weight average molecular weight of the acidic group-containing dispersant (S) is preferably 7,000 to 25,000, more preferably 10,000 to 20,000. If the weight average molecular weight is less than 7,000, the stability of the pigment composition may be lowered, and if it exceeds 25,000, the interaction between the resins becomes strong and the viscosity may increase.

(Acid value)
The acid value of the obtained acidic group-containing dispersant (S) is preferably 20 to 130. More preferably, it is 30 to 120. In one embodiment, the acid value is more preferably 60 to 110.

<Pigment>
The pigment used in the pigment composition can be arbitrarily selected from conventionally known various organic pigments and inorganic pigments, and is not particularly limited in terms of hue or structure. In one embodiment, a pigment composition using an organic pigment as the pigment is preferred. Examples of organic pigments include phthalocyanine, dioxazine violet, indanthrene blue, perylene, quinacridone, diketopyrrolopyrrole, azo, anthraquinone, quinophthalone, isoindoline, quinoxaline and These metal complex pigments can be mentioned. Moreover, the organic pigment represented by the general formula known as a superordinate concept of these organic pigments can also be applied. Hereinafter, specific pigments that can be used are exemplified.

[Phthalocyanine]
Examples of the phthalocyanine pigment include C.I. I. Pigment Blue (hereinafter abbreviated as PB) 1, PB2, PB14, PB16, PB15: 1, PB15: 2, PB15: 3, PB15: 4, PB15: 5, PB15: 6, aluminum phthalocyanine, C.I. I. Pigment green (hereinafter abbreviated as PG) 1, PG2, PG3, PG4, PG7, PG36, PG45, PG58, PG62, and the like.

[Dioxazine violet series]
Examples of the dioxazine violet pigment include C.I. I. Pigment violet (hereinafter abbreviated as PV) 1, PV2, PV3, PV4, PV12, PV23, PV27, PV39, PV50 and the like.

[Indanthrene Blue]
Examples of indanthrene blue pigments include PB60 and PB64.

[Perylene]
Examples of perylene pigments include C.I. I. Pigment red (hereinafter abbreviated as PR) 123, PR149, PR178, PR179, PR190, PV29, and the like.

[Quinacridone series]
Examples of the quinacridone pigment include PR122, PR202, PR206, PR207, PR209, PV19, PV42, and the like.

[Diketopyrrolopyrrole]
Examples of the diketopyrrolopyrrole pigment include PR254, PR255, PR264, C.I. I. Pigment orange (hereinafter abbreviated as PO) 71, PO73, and the like.

[Azo]
As the azo pigments, PR1, PR3, PR5, PR9, PR17, PR48: 1, PR48: 2, PR48: 3, PR57: 1, PR112, PR114, PR116, PR139, PR144, PR146, PR150, PR170, PR185, PR187, PR188, PR221, PR242, PO5, PO13, PO16, PO31, PO34, PO36, PO38, C.I. I. Pigment yellow (hereinafter abbreviated as PY) 14, PY74, PY83, PY93, PY150, and the like.

[Anthraquinone]
Examples of the anthraquinone pigments include PR168, PR177, and PO40.

[Kinophthalone series]
PY138 is mentioned as a quinophthalone pigment.

[Isoindoline series]
Examples of isoindoline pigments include PY139, PY185, PO66, PO69, PR260 and the like.

[Quinoxaline]
PY213 is mentioned as a quinoxaline pigment.

[Metal complex system]
Examples of the metal complex pigment include PY117, PY129, PY150, PY153, and the like.

In one embodiment, the pigment constituting the pigment composition is preferably phthalocyanine, dioxazine violet, indanthrene blue, perylene, quinacridone, diketopyrrolopyrrole, azo and anthraquinone. Is at least one selected from the group consisting of More preferred is at least one organic pigment selected from the group consisting of diketopyrrolopyrrole, quinacridone and perylene, and particularly preferred is a perylene pigment.

In the case of forming a paint using a pigment composition, a pigment composition is prepared by selecting a pigment from the above exemplified pigments so as to match a target hue. Any pigment may be used alone in each color paint, or two or more pigments may be mixed and used. Of course, the pigments that can be used in the pigment composition are not limited to the above pigments. It is also possible to use newly produced pigments.

<Basic compound>
Examples of the basic compound used in the pigment composition include organic amines such as aqueous ammonia, dimethylaminoethanol, ethanolamine, diethanolamine, triethanolamine, aminemethylpropanol, and triethylamine; sodium hydroxide, lithium hydroxide, hydroxide It may be an inorganic alkali agent of an alkali metal hydroxide such as potassium; an organic acid or a mineral acid.
Among these, organic amines and inorganic alkali agents are preferable, and organic amines are more preferable. Examples of the organic amine include dimethylaminoethanol, diethylaminoethanol, ethanolamine, diethanolamine, and triethanolamine. Among them, alkanolamines such as dimethylaminoethanol and ethanolamine are particularly preferable.

<Water>
The water used in the pigment composition is preferably ion-exchanged water (deionized water), not general water containing various ions.

<Preparation of pigment composition>
The pigment composition can be produced by mixing a pigment, an acidic group-containing dispersant (S), a basic compound, water, and other resins and additives as necessary, and then dispersing. The dispersion treatment can be carried out using various conventionally known dispersers such as a three-roll mill, a two-roll mill, a kneader, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor. In addition, a pigment composition in which several types of pigments are separately dispersed can be mixed and used.

In the pigment composition, the acidic group-containing dispersant (S) can finely and stably disperse the pigment. Therefore, the resin composition is excellent in dispersibility and hue. In addition, since the acidic group-containing dispersant (S) is also excellent in compatibility with other resins, by using the pigment composition and the binder resin, it is excellent in dispersibility and hue. A paint having an excellent design can be produced.

The blending amount of the acidic group-containing dispersant (S) is preferably 5 to 120% by mass, more preferably 10 to 100% by mass, and further preferably 10 to 50% by mass with respect to the total amount of the pigment. Particularly preferred is 10 to 30% by mass. By making the said compounding quantity into the said range, coexistence with a pigment dispersion effect and a coating film or an ink film characteristic is attained.

In the preparation of the pigment composition, the acidic group-containing dispersant (S) is neutralized by a basic compound and dispersed or dissolved in an aqueous liquid medium. Finally, the pH of the pigment composition is preferably adjusted to 6 to 11, more preferably the pH is adjusted to 8 to 11. In one embodiment, the basic compound facilitates water-solubilization of the resin with respect to the acid value of the combined carboxyl group and ring-opened acid anhydride group contained in the acidic group-containing dispersant (S), and From the viewpoint of improving pigment dispersibility, it is preferably used at a ratio of 1.0 equivalent or more.
The pigment composition can be prepared by mixing and dispersing each component in one step as described above. Alternatively, the method for producing the pigment composition includes a step of producing a neutralized product of the acidic group-containing dispersant (S) and the basic compound in water (preferably ion-exchanged water), Next, the obtained solution may have a step of adding and mixing a pigment, and if necessary, other resins and additives, followed by dispersion treatment. In the pigment composition, the neutralized product of the acidic group-containing dispersant (S) and the basic compound functions as a pigment dispersant. Therefore, one embodiment is a pigment dispersant which is a neutralized product of an acidic group-containing dispersant (S) and a basic compound, wherein the acidic group-containing dispersant (S) is the following (S1) or ( The present invention relates to a pigment dispersant containing the resin of S2).
(S1) A resin which is a reaction product of the hydroxyl group of the polymer (A) having a hydroxyl group and an acidic group and the acid anhydride group of a tricarboxylic acid anhydride and / or tetracarboxylic dianhydride.
(S2) In the presence of the reaction product of the hydroxyl group of the compound (B) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride, an acidic group-containing ethylenically unsaturated monomer A resin which is a polymer obtained by polymerizing an ethylenically unsaturated monomer (C) containing a monomer (c1).

In the pigment composition, the content of solids other than the pigment (mainly the dispersant (S)) is preferably 10% by mass or more, and more preferably 60% by mass or less, based on the total amount of the pigment composition. In one embodiment, the content is preferably 10 to 60% by mass, more preferably 20 to 50% by mass, and further preferably 30 to 40% by mass. By adjusting the content to 10% by mass or more, it becomes easy to suppress appearance defects such as sagging and unevenness due to low viscosity. On the other hand, by adjusting the content to 60% by mass or less, it becomes easy to suppress appearance defects such as yuzu skin and armpits due to high viscosity.
In the pigment composition, the content of the pigment is preferably 5% by mass or more and more preferably 70% by mass or less based on the total amount of the pigment composition. In one embodiment, the content is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, and still more preferably 20 to 50% by mass. By adjusting the content to 5% by mass or more, excellent coloring power can be obtained, and it becomes easy to improve the concealability of the base. On the other hand, by adjusting the content to 70% by mass or less, it becomes easy to suppress poor appearance due to high viscosity and deterioration of weather resistance.

<Other additives>
In addition to water, a water-soluble solvent miscible with water may be added to the pigment composition. Further, various additives may be added. For example, antifoaming agents, preservatives, pigment derivatives, other pigments, and the like can be added. These are not particularly limited as long as they do not hinder the dispersibility of the pigment, but are preferably those that dissolve in water. By using a dispersion aid, the dispersibility of the pigment can be improved, and re-aggregation of the pigment after dispersion can be more effectively prevented.

As the antifoaming agent, an acetylene glycol surfactant and / or an acetylene alcohol surfactant is preferable. Examples of acetylene glycol surfactants and / or acetylene alcohol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol and 2,4,7,9-tetramethyl- Selected from alkylene oxide adducts of 5-decin-4,7-diol, 2,4-dimethyl-5-decyn-4-ol and alkylene oxide adducts of 2,4-dimethyl-5-decyn-4-ol 1 or more types are preferable.

Preservatives are added for the purpose of preventing generation of soot and bacteria in the recording solution, and include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, zinc pyridinethione-1-oxide, 1,2- Benzisothiazolin-3-one, amine salt of 1-benzisothiazolin-3-one, and the like are used. These are preferably contained in the recording liquid in the range of 0.05 to 1.0% by mass.

<Dye derivative>
In one embodiment, the pigment composition may further contain a dye derivative in order to improve the dispersibility of the pigment. Examples of the dye derivative include a compound in which a phthalimidomethyl group which may have a basic substituent and / or an acidic substituent is introduced into an organic pigment such as anthraquinone, acridone or triazine. For example, compounds described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, etc. These can be used alone or in combination of two or more.
When using a dye derivative, a compound having an azo skeleton, a naphthol azo skeleton, a diketopyrrolopyrrole skeleton, an anthraquinone skeleton, a quinophthalone skeleton, and a perylene skeleton is preferable from the viewpoints of brightness and dispersibility.

When a pigment derivative is used, all components including the pigment derivative may be mixed and dispersed. Alternatively, initially only the pigment and dye derivative, or only the dye derivative and acidic group-containing dispersant (S), or only the pigment, dye derivative and acidic group-containing dispersant (S) are dispersed, Other components may be added and dispersed again.

The blending amount of the pigment derivative is preferably 0.5% by mass or more, more preferably 1% by mass or more based on the total amount of the additive pigment (100% by mass) from the viewpoint of improving the dispersibility of the additive pigment. From the viewpoint of heat resistance and light resistance, the total amount of the additive pigment is preferably 40% by mass or less and more preferably 5% by mass or less, based on the total amount (100% by mass).

By adding an organic pigment derivative, it is considered that the pigment is adsorbed by the pigment to be dispersed and imparts polarity, thereby giving a dispersion effect from the interaction with the dispersant and the resin. In addition, an effect contributing to pigment crystal stabilization and dispersion stabilization can be expected. Specifically, as examples of commercially available products, EFKA-6745, 6750 (manufactured by EFKA Additive), BYK-Synerg
ist2100 (manufactured by Big Chemie Japan Co., Ltd.), Solsperse 5000, 12000, 22000 (manufactured by Nihon Lubrizol Co., Ltd.).

<Paint>
The second embodiment of the present invention relates to a paint (hereinafter also referred to as an aqueous paint or an aqueous paint composition) containing at least the pigment composition of the first embodiment and a binder resin described later. The ratio of the pigment composition to the binder resin varies depending on the required use and is not particularly limited. It can also be used in applications where the pigment concentration is very low. In one embodiment, the content of the binder resin (active ingredient) in the coating composition (total amount of solid components) is preferably 10 to 95% by mass, and more preferably 40 to 90% by mass.

[Binder resin]
The binder resin is not particularly limited as long as it is usually used as a binder resin for paints. For example, an acrylic resin, a polyester resin, an alkyd resin, a fluororesin, a urethane resin, a silicon-containing resin containing a crosslinkable functional group. And a melamine resin, urea resin, polyisocyanate compound, block polyisocyanate compound, epoxy compound or epoxy resin, carboxyl group-containing compound or resin having a role as a crosslinking agent capable of reacting with the functional group of the base resin An acid anhydride, an alkoxysilane group-containing compound, a resin, or the like can be used.
It is desirable to use a resin containing a crosslinkable functional group in combination with a resin having a role as a crosslinking agent. Among them, it is preferable to use one kind selected from an acrylic resin, a polyester resin, an alkyd resin, a melamine resin, an epoxy resin, and a urea resin as the binder resin, and one kind selected from an acrylic resin, a polyester resin, an alkyd resin, and a melamine resin. Is more preferable, and it is more preferable to use an acrylic resin and a melamine resin in combination.

The melamine resin is particularly preferably used because it has thermosetting properties and acts as a curing agent. The acrylic resin is preferably obtained by polymerizing a monomer having a polymerizable unsaturated double bond well known by those skilled in the art by a conventional method. Examples of the monomer having a polymerizable unsaturated double bond include acrylic acid, methacrylic acid, crotonic acid, isocrotonic acid, ethacrylic acid, propylacrylic acid, isopropylacrylic acid, itaconic acid, maleic anhydride, and fumaric acid. Carboxylic acid group-containing monomers, hydroxyl group-containing monomers such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and ε-caprolactone-modified acrylic monomer, (meth) acrylic acid Methyl, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, (meth ) 2-ethylhexyl acrylate, ( (Ta) Octyl acrylate, (meth) acrylate nonyl, (meth) acrylate decyl, (meth) acrylate dodecyl, (meth) acrylate ester monomers such as stearyl (meth) acrylate, styrene, α-methylstyrene, Examples thereof include styrene monomers such as α-methylstyrene dimer, vinyltoluene and divinylbenzene. For the polymerization, it is preferable to use a radical polymerization initiator or the like well known by those skilled in the art.

The water-based coating composition further includes various additives such as water or an organic solvent, a rheology control agent, an anti-settling agent, a curing catalyst, an antifoaming agent, an antioxidant, an ultraviolet absorber, and a surface conditioner, if necessary. An extender pigment etc. can be suitably mix | blended as an additional component.

In one embodiment, the aqueous coating composition can be prepared by mixing and dispersing the components of the pigment composition, the binder resin, and, if necessary, the aforementioned additional components. Moreover, after mixing the said binder resin and water previously, the said pigment composition and the above-mentioned additional component as needed are further mixed and disperse | distributed, and an aqueous coating composition can also be obtained.

The said coating material is not specifically limited, It can apply to various base materials. In one embodiment, a coated product obtained by applying the coating material on a substrate can be provided.
As a base material, for example, a metal base material such as iron, stainless steel, aluminum, etc. and a surface treated product thereof; a cement base material such as cement, lime, gypsum; polyvinyl chloride, polyester, polycarbonate, acrylic Examples thereof include plastic base materials. In addition, various articles to be coated in the building / building materials field such as building materials, buildings, and structures made of metal or plastic materials constituting these various substrates can be used as the substrate.

The coating method of the paint is not particularly limited, and examples thereof include brush coating, roller coating, and spray coating. After coating, the coating film can be usually obtained by drying at room temperature or drying by heating. The coating amount; the order of coating such as undercoating, intermediate coating, and topcoating; the coating film thickness; the drying time, and the like can be arbitrarily set according to the type of coating composition and the substrate to be applied.

Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In Examples and Comparative Examples, “part” means “part by mass” and “%” means “% by mass” unless otherwise specified.

(Measurement method of weight average molecular weight)
The weight average molecular weight is determined by using two separation columns “TSK-GEL SUPER HZM-N” connected in series in Gel Permeation Chromatography (GPC) “HLC-8220GPC” (manufactured by Tosoh Corporation). It is the polystyrene conversion value measured using tetrahydrofuran (THF) for the phase.

(Measurement method of acid value)
The acid value was measured according to a JIS standard measurement method (JIS K 5601-2-1: 1999).

<Production of acidic group-containing dispersant (S)>
[Production Example 1]
(Production of acidic group-containing dispersant (S1))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 40.0 parts of methyl methacrylate, 10.0 parts of methacrylic acid, 20.0 parts of ethyl acrylate, 30.0 parts of acrylic acid-t-butyl Was replaced with nitrogen gas. The reaction vessel was heated to 80 ° C., and 0.1 part of 2,2′-azobisisobutyronitrile was added to propylene glycol monomethyl ether acetate with respect to 6.0 parts of 3-mercapto-1,2-propanediol. The solution dissolved in 45.3 parts was added and the reaction was carried out for 10 hours. Solid content measurement confirmed that 95% of the raw material had reacted. At this time, the weight average molecular weight was 4,000.
Next, 8.8 parts of pyromellitic dianhydride, 69.2 parts of propylene glycol monomethyl ether acetate and 1,8-diazabicyclo- [5.4.0] -7 as a catalyst are added to the above reaction solution. -0.2 part of undecene was added and the reaction was carried out at 120 ° C for 7 hours. The acid value was measured to confirm that 98% or more of the acid anhydride was half-esterified, and the reaction was completed.
After completion of the reaction, propylene glycol monomethyl ether acetate was distilled off under reduced pressure so that the nonvolatile content was 0% by mass to obtain an acidic group-containing dispersant S1 having a weight average molecular weight of 10,000 and an acid value of 65 mgKOH / g.

[Production Examples 2 to 7]
(Production of acidic group-containing dispersant (S2 to S7))
Synthesis was performed in the same manner as in Production Example 1 except that the raw materials and the amounts charged were listed in Table 1-1, and acidic group-containing dispersants S2 to S7 were obtained.

[Production Examples 8 to 10]
(Production of acidic group-containing dispersant (S8 to S10))
The synthesis was carried out in the same manner as in Production Example 1 except that the raw materials and preparation amounts described in Table 1-1 were changed, and then the solvent was removed at 80 ° C. under reduced pressure to obtain acidic group-containing dispersants S8 to S10. It was.

[Production Example 11]
(Production of acidic group-containing dispersant (S11))
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser and a stirrer, 6.0 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic dianhydride, 23. propylene glycol monomethyl ether acetate. 6 parts and 0.1 part by weight of mono-n-butyltin (IV) oxide were charged and replaced with nitrogen gas. The reaction vessel was heated to 100 ° C. and reacted for 7 hours.
After confirming that 98% or more of the acid anhydride was half-esterified, the temperature in the system was cooled to 70 ° C., and 80.0 parts of methyl methacrylate, 5.0 parts of methacrylic acid, 10.0 parts of hydroxyethyl methacrylate And 5.0 parts of acrylic acid were added, and a solution prepared by dissolving 0.1 part of 2,2′-azobisisobutyronitrile in 26.2 parts of propylene glycol monomethyl ether acetate was added over 10 hours. Reaction was performed. The solid content measurement confirmed that the polymerization had progressed 95%, and the reaction was completed.
After completion of the reaction, the nonvolatile content was adjusted to 50% by weight, and an acidic group-containing dispersant S11 having an acid value of 108 mgKOH / g and a weight average molecular weight of 9,500 was obtained.

[Production Example 12]
(Production of acidic group-containing dispersant (S12))
Synthesis was carried out in the same manner as in Production Example 11 except that the raw materials and preparation amounts shown in Table 1-2 were changed, and an acidic group-containing dispersant S12 was obtained.

The abbreviations in Table 1-1 and Table 1-2 are shown below.
Acid component: tricarboxylic anhydride and / or tetracarboxylic dianhydride MAA: methacrylic acid AA: acrylic acid 2-MTA: methoxyethyl acrylate MMA: methyl methacrylate EA: ethyl acrylate BzMA: benzyl methacrylate t-BA: tarsal Butyl acrylate HEMA: hydroxyethyl methacrylate thioglycerol: 3-mercapto-1,2-propanediol AIBN: 2,2′-azobisisobutyronitrile PGMAc: propylene glycol monomethyl ether acetate PMA: pyromellitic dianhydride BPDA: 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride Ricacid BT-100: 1,2,3,4-butanetetracarboxylic dianhydride (manufactured by Shin Nippon Rika Co., Ltd.)
TMA: trimellitic anhydride DBU: 1,8-diazabicyclo- [5.4.0] -7-undecene BTO: mono-n-butyltin (IV) oxide

<Production of pigment composition>
[Example 1]
(Preparation of pigment composition P-1)
As a pigment, 15 parts of PR179 (“Paliogen Red L3885” manufactured by BASF), 0.8 part of an acidic group-containing dispersant (S1), 1.1 parts of dimethylaminoethanol, and 83.2 parts of ion-exchanged water are preliminarily dispersed with a spatula. After that, 112.5 parts of zirconia beads having a diameter of 0.8 mm were charged as a dispersion medium, and dispersion treatment was performed with a paint shaker, whereby a neutralized product of the acidic group-containing dispersant (S1) and dimethylaminoethanol was obtained. A pigment composition P-1 containing was obtained. The formation of the neutralized product was confirmed by measuring the pH of the pigment composition.

[Examples 2 to 75, Comparative Examples 1 to 6]
(Preparation of pigment compositions P-2 to P-81)
The acidic group-containing dispersant (S) was changed in the same manner as in Example 1 except that the acidic group-containing dispersant (S), pigment, dye derivative, and basic compound shown in Tables 2-1 to 2-4 were changed. And pigment compositions P-2 to P-81 containing a neutralized product of the basic compound.

[Comparative Examples 7 to 15]
(Preparation of pigment compositions P-82 to P-90)
A pigment composition P-82-containing an acidic group-containing dispersant (S) was prepared in the same manner as in Example 1 except that the acidic group-containing dispersant (S), pigment, and dye derivative were changed to those shown in Table 2-4. P-90 was obtained.

<Evaluation of pigment composition>
The following evaluation was performed about the obtained pigment composition. The results are shown in Tables 2-1 to 2-4.
(Measurement of pH)
The pH of the produced pigment composition was measured with a pH meter (F-50 series manufactured by HARIBO) and evaluated according to the following criteria. When the pH is 6 or more, it is determined that a neutralized product of the acidic group-containing dispersant (S) and the basic compound has been formed.
S: pH is 8 or more and 11 or less A: pH is 6 or more and less than 8 B: pH is less than 6 or more than 11

(Measurement of particle size)
The prepared pigment composition was diluted by adding water so that the loading index value of the laser dynamic light scattering method (manufactured by Nikkiso Co., Ltd., UPA150EX) was within the range of 0.8 to 1.2. The median diameter (D50) of the cumulative volume at ° C was measured. Subsequently, evaluation was performed according to the following criteria.
A: D50 is 50 nm or less B: D50 is greater than 50 nm and 100 nm or less Δ: D50 is greater than 100 nm and 200 nm or less X: D50 is greater than 200 nm

(Visual evaluation of color)
The prepared pigment composition was put in a glass bottle, and the color was visually determined. Subsequently, evaluation was performed according to the following criteria.
◎: Deep and clear color ○: Deep color but poor sharpness ×: Low density and not clear

The abbreviations in Table 2-1 to Table 2-4 are shown below.
Comparative resin 1: Florene G700AMP (manufactured by Kyoeisha Chemical Co., Ltd .: α-olefin maleic anhydride copolymer partial ester, 2-amino-2-methyl-1-propanol salt)
Comparative resin 2: DisperBYK-190 (manufactured by Big Chemie: acrylic block copolymer)
Comparative resin 3: ARUFON UC-3000 (manufactured by Toa Gosei Co., Ltd .: all acrylic polymer)

PR122: “FASTOGEN Super Magenta RGT” manufactured by DIC
PR177: “Cinilex Red SR4C” manufactured by Cinic
PR179: “Paliogen Red L3885” manufactured by BASF
PR254: “Cinilex DPP Red SR2P” manufactured by Cinic
PR264: “Cinilex DPP Rubine SR5H” manufactured by Cinic
PB15: 1: “Cyanine Blue G-314” manufactured by Sanyo Dye
PB15: 3: “LIONOL BLUE 7919” manufactured by Toyocolor Co., Ltd.
PB15: 6: “LIONOL BLUE ESP-S 74160” manufactured by Toyocolor Co., Ltd.
PG7: “LIONOL GREEN YS-07” manufactured by Toyocolor Co., Ltd.
PG36: “LIONOL GREEN 6Y-501” manufactured by Toyocolor Co., Ltd.
PY14: "SYMULER FAST YELLOW 4400" manufactured by DIC
PY74: “FAST YELLOW 7413” manufactured by Sanyo Dye
PY138: “Paliotol Yellow L0960HD” manufactured by BASF
PY139: “Cinilex Yellow SY3CN” manufactured by Cinic
PY150: “Hostaperm Yellow HN4G” manufactured by Clariant
PY185: “Paliotol Yellow D1155” manufactured by BASF
PY213: “Hostaperm Yellow H5G” manufactured by Clariant
PV23: “Hosta Palm Violet RL COF” manufactured by Clariant
PV29: manufactured by BASF "Paligen Red Violet K 5011"

Below, the pigment derivative used for the Example or the comparative example is shown.

<Manufacture of paints>
[Example 76]
(Preparation of coating composition C-1)
The pigment composition P-1 obtained in Example 1 and the binder resin were blended in a solid content so as to have the following composition to obtain a coating composition C-1.
Pigment composition P-1: 3.2 parts Watersol S-751: 60.0 parts (acrylic resin for baking paints manufactured by DIC)
Cymel 303: 45.0 parts (Melamine resin manufactured by Mitsui Cytec)

[Examples 77 to 150, Comparative Examples 16 to 30]
(Preparation of coating compositions C-2 to C-90)
Coating compositions C-2 to C-90 were obtained in the same manner as in Example 76 except that the pigment compositions and additive resins (binder resins) shown in Table 4-1 to Table 4-3 and Table 5 were changed. It was.

<Evaluation of paint>
The obtained coating composition was coated on an corona discharge-treated PET film or a BT-144 treated steel plate with an applicator so that the film thickness was 37 ± 2 μm, and set for 30 minutes. Subsequently, after drying the obtained coating film at 60 degreeC for 20 minutes, baking was performed at 140 degreeC for 20 minutes, and the test piece of each coating composition was produced. The test piece was evaluated as follows. The results are shown in Tables 4-1 to 4-3 and Table 5.

(Deep feeling)
Each coating composition was applied to a PET film to obtain a test piece. The determination was made by visually observing the coating film of each test piece at a low angle under white light. Subsequently, the feeling of depth was evaluated according to the following criteria.
○: Excellent color depth ×: No color depth

(Glossy)
Each paint composition was coated on an aluminum plate (0.8 mm x 70 mm x 150 mm, manufactured by Miki Coating Co., Ltd.) that had been mirror-finished using sandpaper (ie, water-polished), and test pieces were obtained. According to the method of JI Z 8741, 60 ° specular gloss was measured on the coating film of the test piece. Next, the gloss was evaluated according to the following criteria.
○: [Gloss value]> 50 (good)
×: [Gloss value] ≦ 50 (defect)

(Color development)
The test piece coated on the PET film was visually judged. Evaluation was performed according to the following criteria.
○: Color density and high concealment △: Color density and concealment are slightly inferior ×: Color density and concealment are considerably inferior and sharpness is low

(water resistant)
What was coated on the “BT-144 treated steel plate” was immersed in water at a temperature of 50 ° C., and the occurrence of blisters was visually judged after 48 hours. Evaluation was performed according to the following criteria.
◎: No abnormality was observed. ○: Slight blister was observed. △: A considerable amount of blister was observed. ×: Blister was generated on the front surface of the test piece.

(Haze value)
The haze of the coated surface of the test piece coated on the PET film was measured with a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd.). Evaluation was performed according to the following criteria.
○: [Haze value] <60 (good)
Δ: 60 ≦ [haze value] <80 (can be implemented)
×: [Haze value] ≧ 80 (defect)

(Flip-flop property)
The test piece coated on the PET film was visually judged. Evaluation was performed according to the following criteria.
○: Changes in color tone and glitter depending on the viewing angle of the paint surface ×: Small changes in color tone and glitter even when the angle of viewing the paint surface is changed

The abbreviations in Table 4-1 to Table 4-3 and Table 5 are shown below.
Binder resin A: acrylic resin for water-coating paint “Watersol S-751” manufactured by DIC, non-volatile content = 50%
Binder resin B: Alkyd resin “Watersol S-212” manufactured by DIC, nonvolatile content = 65%
Binder resin C: Melamine resin “Cymel 303” manufactured by Mitsui Cytec Co., Ltd., active ingredient content = 98%)
Binder resin D: Melamine resin “Cymel 204” manufactured by Mitsui Cytec, nonvolatile content = 80%

From the results shown in Tables 4-1 to 4-3 and Table 5, the coating composition using the pigment composition of the present invention has a sense of color depth, gloss, color development, water resistance, haze value and flip-flop. It was shown to be excellent in performance.

Claims (13)

1. A pigment composition comprising a neutralized product of an acidic group-containing dispersant (S) and a basic compound, a pigment, and water, wherein the acidic group-containing dispersant (S) is the following (S1) or (S2 The pigment composition containing the resin of).
   (S1) A resin which is a reaction product of the hydroxyl group of the polymer (A) having a hydroxyl group and an acidic group and the acid anhydride group of a tricarboxylic acid anhydride and / or tetracarboxylic dianhydride.
   (S2) In the presence of the reaction product of the hydroxyl group of the compound (B) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride, an acidic group-containing ethylenically unsaturated monomer A resin which is a polymer obtained by polymerizing an ethylenically unsaturated monomer (C) containing a monomer (c1).
2. The polymer (A) having a hydroxyl group and an acidic group in the resin (S1) is in the presence of a compound (b1) having two hydroxyl groups and one thiol group in the molecule. The pigment composition according to claim 1, which is a polymer (a1) obtained by polymerizing an ethylenically unsaturated monomer (C) containing a monomer (c1).
3. The content of the acidic group-containing ethylenically unsaturated monomer (c1) is 3% by mass to 30% by mass with respect to the total amount of the ethylenically unsaturated monomer (C). The pigment composition described in 1.
4. The pigment according to any one of claims 1 to 3, wherein the acidic group-containing dispersant (S) has a weight average molecular weight of 7,000 to 25,000 and an acid value of 20 to 130. Composition.
5. The pigment composition according to any one of claims 1 to 4, wherein the content of the acidic group-containing dispersant (S) is 10% by mass to 30% by mass with respect to the total amount of the pigment.
6. The pigment composition according to any one of claims 1 to 5, wherein the basic compound contains an organic amine.
7. The pigment composition according to claim 6, wherein the organic amine contains an alkanolamine.
8. The pigment composition according to any one of claims 1 to 7, wherein the pH of the pigment composition is 8 to 11.
9. The pigment composition according to any one of claims 1 to 8, wherein the pigment is at least one selected from the group consisting of diketopyrrolopyrrole, quinacridone, and perylene.
10. A paint containing the pigment composition according to any one of claims 1 to 9 and a binder resin.
11. The paint according to claim 10, wherein the binder resin includes an acrylic resin and a melamine resin.
12. A coated product obtained by applying the paint according to claim 10 or 11 on a substrate.
13. A dispersant that is a neutralized product of an acidic group-containing dispersant (S) and a basic compound, wherein the acidic group-containing dispersant (S) contains a resin of the following (S1) or (S2). Dispersant.
    (S1) A resin which is a reaction product of the hydroxyl group of the polymer (A) having a hydroxyl group and an acidic group and the acid anhydride group of a tricarboxylic acid anhydride and / or tetracarboxylic dianhydride.
    (S2) In the presence of the reaction product of the hydroxyl group of the compound (B) having a hydroxyl group and the acid anhydride group of tricarboxylic anhydride and / or tetracarboxylic dianhydride, an acidic group-containing ethylenically unsaturated monomer A resin which is a polymer obtained by polymerizing an ethylenically unsaturated monomer (C) containing a monomer (c1).