JPH0741689A - Aqueous pigment dispersing agent and pigment composition containing the agent - Google Patents

Abstract

PURPOSE:To obtain an aqueous pigment dispersing agent having self-dispersing or dissolving property in water, containing organic pigment group, exhibiting excellent color-developing property, coating film luster, sharpness and storage stability and useful for water-based paint, etc. CONSTITUTION:This dispersing agent is self-dispersible or soluble in water and has organic pigment group containing a structure bonded through amide bond, ester bond, ether bond or urethane bond. A pigment composition is produced by compounding the dispersing agent and an organic pigment.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel and useful aqueous pigment dispersant and a pigment composition. More specifically, the present invention relates to a water-based pigment dispersant which is a compound that self-disperses or dissolves in water, and further has an organic dye atomic group. In addition, a pigment containing the water-based pigment dispersant. It relates to a composition.

[0002]

2. Description of the Related Art Organic pigments have often been a problem with the dispersibility of paints and printing inks.

Particularly in recent years, due to environmental problems or various problems related thereto, paints and printing inks are gradually becoming water-based, and such so-called water-based systems such as water-based paints and water-based inks. The issue of dispersibility in articles is often being highlighted.

That is, for example, in the manufacturing process of organic pigments, crystal particles of such pigments often cause strong aggregation themselves. In order to disperse such a shape, strong shearing force is necessary, but in water-based paints and water-based inks, the surface tension of water, which is their solvent, is significantly higher than that of pigments. If the agglomerates cannot be dispersed from the process, or even if the dispersion can be done once, it is troublesome that the flocculation occurs again and the dispersion is not stabilized in the final process. It's over.

Further, as in the case of the non-aqueous type, the pigment crystal particles are
Since it is extremely small in itself, it becomes difficult to disperse due to high viscosity, and it is difficult to obtain a coating film having high gloss and high image clarity.

In particular, since the affinity between the organic pigment and the dispersion medium is weak, flocculation causes high viscosity, poor leveling, lack of gloss, color separation, deterioration of coloring power, and storage. Unfavorable problems such as thickening may occur.

In addition, it is often the case that the same hue and coloring power cannot be obtained without the same color development as in the non-aqueous system.

By the way, various surfactants and pigment dispersants have been developed so far for the purpose of improving problems such as various suitability and dispersibility of pigments in an aqueous system. Enter

That is, for example, it can be obtained by copolymerizing a cationic or anionic surfactant, a nonionic surfactant, or a vinyl monomer having a nitrogen-containing heterocycle, a macromonomer, or another vinyl monomer. , A dispersant which is a neutralized product of various polymers or a quaternary ammonium salt compound (JP-A-59-22794).
No. 0, No. 60-81252, No. 60-81253,
60-86171, 60-92360, 60-
No. 123563, No. 61-166866, No. 61-2
No. 35466 or No. 63-154776),

Amphoteric aqueous polymer (JP-A-63-356)
No. 13), or a resin having both an acidic functional group and a basic functional group, which are neutralized with a basic compound. A pigment-dispersed resin (JP-A-4-13784) whose base strength is less than or equal to the base strength of the basic compound has already been proposed.

However, in the cases 1 and 2, the surfactant migrates to the coating film interface due to the fact that the surfactant itself has a small molecular weight, which adversely affects the water resistance and adhesion of the coating film. Influences.

In particular, in the case of the anionic surfactant and in the case of the nonionic surfactant in the case of, the hydrophobic (functional) group in these surfactants and the pigment are
On the other hand, in the case of the above, in the dispersant,
Although the affinity between the nitrogen-containing heterocycle in the dispersion and the pigment is increased by the hydrophobic interaction, the hydrophobic interaction is originally insufficient. The pigment composition in the form of using such a surfactant or a dispersant has various required performances.
It can be said that it is hard to say that it is completely satisfied, but rather that it is rarely satisfied.

The aqueous polymer in the above case is
Often used by neutralizing so-called acidic groups such as carboxylic acid in the polymer with so-called basic compounds such as ammonia and triethylamine, and therefore such an aqueous resin solution exhibits weak alkalinity. ing.

On the other hand, the usual organic pigments often show a negative zeta potential in a weakly alkaline aqueous solution.
By utilizing these electrostatic properties, the polymers and resins in the above cases and and, respectively, are introduced with an acidic group or a basic group, and such a basic group and a negatively charged pigment are mixed with each other. The base interaction enhances the affinity, and these acidic groups enhance the affinity with the solvent.

Since these polymers and resins are themselves of high molecular weight, they are entangled with the water-based resin and thus enhance the resin adsorption. However, in the case of the polymer in the case described above, depending on the type of the basic group of the polymer, it is possible to form a salt with an acidic group in the aqueous resin to cause the aqueous resin to aggregate. is there.

In the case of 1, all pigments do not necessarily show a negative charge, and it is possible to use those in which the basic strength of the basic group present in the resin is sufficiently strong. There is no such thing.

For this reason, the above and / or
When a dispersant having such a form is used, it becomes a process lacking in affinity with the pigment due to acid-base interaction, and it is difficult to say that the properties required are completely satisfied. Rather, it can be said that there are few cases to satisfy.

Further, depending on the kind of the neutralizing base compound in the aqueous polymer, the aqueous resin may be aggregated or the dispersion may not be achieved.
It remains.

[0019]

As described above, in the various techniques up to now, a more or less fatal defect of the pigment dispersant of this type is mainly inferior in dispersibility or dispersion stability. Or, since there are drawbacks, the conventional pigment dispersants are required to have various required performances.
It can be said that it is hard to say that it is completely satisfied, but rather that it is rarely satisfied.

In view of the above-mentioned circumstances, however, the present inventors have earnestly started research in order to solve the above-mentioned various drawbacks of the conventional technique. Therefore, the problem to be solved by the present invention takes one
To provide a pigment composition containing the pigment dispersant, in addition to a pigment dispersant having extremely high practical performance, which can satisfy various performances required for this kind of pigment composition. In particular, this is, of course, also the object of the invention.

[0021]

Therefore, the present inventors have
Focusing on the problems to be solved by the invention as described above, as a result of intensive studies, as a result, first, it has self-dispersibility or solubility in water, and an organic dye atom A novel aqueous water-based pigment dispersant having a group is one that meets the purpose of the present invention.

In addition, such a novel compound itself may be a polymer compound containing an oligomer, of course, but a pigment composition containing the novel aqueous pigment dispersant as an essential component. However, above all, when the pigment composition in the form containing the aqueous pigment dispersant and the organic pigment uses an aqueous resin,

The organic dye atomic group of the water-based pigment dispersant and the organic pigment have sufficient pigment affinity due to the hydrophobic interaction, and further, depending on the kind of the base compound used for neutralizing the water-based resin. In particular, the present invention has been completed here by discovering that, among other things, it exhibits extremely excellent pigment dispersibility and pigment dispersion stability.

That is, the present invention is basically a novel water-based pigment, which is a compound self-dispersing or dissolving in water, and is a polymer compound having an organic dye atomic group. In addition to providing a dispersant, a pigment composition containing this aqueous pigment dispersant as an essential component is also composed of the aqueous pigment dispersant and an organic pigment. It is also intended to provide a specific pigment composition.

Here, the above-mentioned aqueous pigment dispersant according to the present invention may be any compound as long as it is a compound which is self-dispersed or dissolved in water and further has an organic dye atomic group, and the kind thereof may be used. , The manufacturing method is not particularly limited,

Of these, only typical ones are exemplified. Carboxyl group, sulfonic acid group, primary amino group, secondary amino group, epoxy group, hydroxyl group, isocyanate group or halogen group. Organic dyes having a reactive group of (halogen atom) and self-dispersing or dissolving in water (hereinafter abbreviated as reactive group-containing organic dyes);

An amide bond, an ester bond, an ether through another reactive group such as a carboxyl group, a sulfonic acid group, a primary amino group, a secondary amino group, an epoxy group, a hydroxyl group, an isocyanate group or a halogen group. Examples of the compound include a compound which is self-dispersible or soluble in water, which is obtained by reacting in a non-reactive solvent in the presence or absence of a catalyst so as to form a bond or a urethane bond.

The above-mentioned self-dispersing / dissolving compound has an organic dye atomic group and also has a self-dispersing ability or a dissolving ability, and is a so-called hydrophilic compound such as an emulsifier or a protective colloid. It is a compound that disperses or dissolves uniformly in water without using a substance, and is usually 1,000 to 200,000.
Within the range of 0, preferably 3,000 to 100,0
Any polymer compound having a number average molecular weight in the range of 00 may be used.

The self-dispersing ability or dissolving ability of the self-dispersing / dissolving compound means that various acidic groups such as a carboxyl group and a sulfonic acid group; Introducing various basic groups such as primary amino groups and quaternary ammonium; and / or various hydrophilic groups such as hydroxyl group and polyethylene glycol,

If desired, for example, by using the carboxyl group in the compound as a neutralizing agent for various basic compounds such as triethylamine, or by changing the tertiary amino group in the compound, Like acetic acid,
It refers to the ability to self-disperse or dissolve by neutralizing with various acidic compounds.

The self-dispersing / dissolving compound possesses such ability or property.

As the self-dispersing / dissolving compound, only typical ones are exemplified, and various polymer compounds such as vinyl-based, urethane-based, ether-based or ester-based compounds are further included. Examples thereof include composite polymer compounds.

The above-mentioned reactive group-containing organic dyes are selected from the group consisting of carboxyl group, sulfonic acid group, primary amino group, secondary amino group, epoxy group, hydroxyl group and isocyanate group. What has at least one reactive group may be used.

For example, it is originally a dye or pigment having at least one reactive group, or a form in which at least one reactive group is introduced into the dye or pigment. Alternatively, various types of organic dyes such as dyes and pigments in a form synthesized by using a raw material having at least one reactive group can be mentioned.

As the organic dyes used here, quinacridone type, quinacridone quinone type, dioxazine type, phthalocyanine type, anthrapyrimidine type, ansanthuron type, and
Indanthrone, flavanthrone, perylene, perinone, diketopyrrolopyrrole, quinophthalone,
Examples include various dyes and pigments such as anthraquinone type, thioindigo type, benzimidazolone type and azo type.

The method for obtaining such a reactive group-containing organic dye is not particularly limited, but of these, only typical ones will be exemplified. A method of introducing a phthalimido group into a compound and then hydrolyzing it to obtain an organic dye having an aminomethyl group,

Alternatively, the organic dyes may be dissolved in sulfuric acid and the amino group may be directly introduced into the organic dyes by the Redox reaction in the presence of hydroxylamine, or the organic dye may be added to sulfuric acid. It is a method of obtaining organic dyes having a sulfonic acid group by dissolving the compounds and heating them for sulfonation.

Various hydroxyalkylanilines, which may have a --O-- group, a --COO-- group, a --CONH-- group or a --SO ₂ NH-- group, are diazotized by a conventional method, and then various It is a method of obtaining an organic dye having a hydroxyl group by performing a coupling reaction with a coupler of the organic dye of

Furthermore, as described above, various hydroxyalkylanilines are converted into acetoacetic acid arylide derivatives by a conventional method, and then a coupling reaction is carried out with a coupler of various organic dyes to remove hydroxyl groups. For example, a method of obtaining the organic dyes possessed by the method.

As a method for producing the aqueous pigment dispersant of the present invention, only representative ones will be exemplified. Self-dispersion or typified by a carboxyl group or a hydroxyl group in a non-reactive solvent. A vinyl-based monomer having a group that imparts the property of dissolving is copolymerized with another monomer having a copolymerizability with the vinyl-based monomer, and then a self-dispersible / soluble compound (co) thus obtained The polymer and the organic dye having a reactive group capable of forming an amide bond, an ester bond, an ether bond or a urethane bond are allowed to stand at room temperature to reflux for 10 minutes in the presence or absence of a catalyst. It is a method of reacting with esterification, amidation, etherification or urethanization for about 50 hours,

First, an amide bond, an ester bond, an ether bond or a urethane bond is formed with the vinyl monomer having a reactive group as described above and another monomer having a copolymerizability with the reactive group-containing vinyl monomer. Organic dyes having a reactive group that can be formed, in a non-reactive solvent,
In the presence of a polymerization inhibitor, for 10 minutes to 50 hours,
React at room temperature to under reflux,

Then, a reaction product obtained by removing the polymerization inhibitor and a vinyl-based monomer having a group which gives a self-dispersing or dissolving property, represented by a carboxyl group or a hydroxyl group, are further added. If necessary, a method of removing the solvent after copolymerizing another monomer having copolymerizability with the vinyl monomer,

Alternatively, first, an alkyd having many hydroxyl groups
After synthesizing a prepolymer, a polybasic acid is added to prepare a self-dispersing / dissolving polyester compound, and then this self-dispersing / dissolving polyester compound is combined with an amide bond, an ester bond, an ether bond or a urethane bond. A method of reacting with an organic dye having a reactive group capable of forming a bond in the presence or absence of a catalyst for 10 minutes to 50 hours at room temperature to reflux, etc., Of course, the method is not limited to these methods.

In this case, the equivalent ratio of the reactive group in the organic dye to the reactive group in the self-dispersing / dissolving compound or the reactive group in the monomer is usually 1: 1 or more. Used for.

The non-reactive solvent is usually used in an amount of 1 to 100 times by weight, preferably 1 to 10 times by weight of the self-dispersing / dissolving compound.

Further, if only representative examples of the above-mentioned catalysts are exemplified, various organometallic compounds such as tin, lead or manganese, and further,
Examples thereof include metal chelate compounds, or fatty acid metal acyl compounds.

Further, as only the non-reactive solvents mentioned above are specifically exemplified, various aliphatic hydrocarbon solvents such as hexane or mineral spirit; or benzene, toluene or xylene. Various aromatic hydrocarbon solvents such as;

Alternatively, various ester solvents such as ethyl acetate; various alcohol solvents such as methanol or butanol; or dimethylformamide,
Various aprotic polar solvents such as dimethylsulfoxide, N-methylpyrrolidone or pyridine.

These non-reactive solvents may be used alone,
Of course, two or more kinds may be used in combination.

On the other hand, to exemplify only a typical method for preparing the pigment composition of the present invention, the organic pigment is mixed with the organic pigment by a Henschel mixer, an air mixer or a V-type blender as described above. It is a method of mixing with a different aqueous pigment dispersant,

A method of kneading and grinding the organic pigment and the above-mentioned aqueous pigment dispersant by a ball mill, attritor, two rolls, three rolls or a pressure kneader,

An aqueous dispersion of a wet pigment or a powdered pigment is mixed with an organic solvent solution of an aqueous pigment dispersant as described above to form an emulsion, and then the pigment dispersant is deposited on the surface of the pigment. After soaking, it is a method of filtering, washing with water, and drying,

Alternatively, a water / alcohol dispersion of a wet pigment or a powder pigment is mixed with an aqueous pigment dispersant as described above to dissolve or disperse the pigment, and then the pigment dispersant is applied to the surface of the pigment. After depositing, it is dealcoholized, then filtered, washed with water, and dried.

Further, the above-mentioned aqueous pigment dispersant is neutralized with respect to an aqueous dispersion of a wet pigment or a powder pigment to dissolve or disperse it. A method in which the pigment dispersant is acid-deposited or salted-out to deposit and then filtered, washed with water, and dried, but the present invention is by no means limited to these methods.

The amount of the aqueous pigment dispersant used in this case is usually 0.1 to 100 parts by weight of the organic pigment.
A range of 40 parts by weight, preferably 5 to 25 parts by weight is suitable.

The organic pigment used here is not particularly limited, but if only typical ones are exemplified, a quinacridone pigment, a quinacridone quinone pigment, and a dioxazine pigment are given. ,
Phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments,

Flavanthuron type pigments, perylene type pigments,
Examples thereof include diketopyrrolopyrrole pigments, perinone pigments, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments.

The thus obtained aqueous pigment dispersant and pigment composition of the present invention are prepared mainly as an aqueous paint or aqueous printing ink by dispersing them together with an aqueous resin varnish.

The thus-prepared water-based paints and printing inks are all excellent in color developability, coating gloss, image clarity and storage stability, and are extremely good paints and coatings. give.

Therefore, it can be said that the aqueous pigment dispersant and the pigment composition of the present invention have extremely high practicality.

[0061]

EXAMPLES Next, the present invention will be explained more specifically with reference to Reference Examples, Examples and Comparative Examples, but the present invention is not limited to the following examples. In the following, all parts and% are based on weight unless otherwise specified.

Reference Example 1 (Preparation Example of Reactive Group-Containing Organic Dyes) After injecting 300 parts of 98% concentrated sulfuric acid into a reaction vessel,
After adding 25 parts of quinacridone at a temperature of 20 to 30 ° C. and stirring at 40 ° C. for 2 hours, 13 parts of phthalimide and 2. of 80% paraformaldehyde.
6 parts were added and the reaction was allowed to continue for 3 hours at 50-60 ° C.

Then, the reaction solution was poured into 5,000 parts of ice water, filtered, washed with water and dried to obtain 37 parts of phthalimidomethylquinacridone.

Thereafter, 400 parts of water and 37 parts of phthalimidomethylquinacridone were put into a reaction vessel, and further, 7 parts of a 20% sodium hydroxide aqueous solution was added.
After injecting 3 parts and stirring at 85 ° C. for 4 hours, 105 parts of 20% hydrochloric acid was added and stirring at 85 ° C. for 4 hours.

After cooling to room temperature, 45 parts of a 20% aqueous sodium hydroxide solution was added, filtered, washed with water and dried to obtain 27.9 parts of aminomethylquinacridone.

Reference Example 2 (Same as above) In a reaction vessel, the perylene tetracarboxylic anhydride of 18.
6 parts, 400 parts of water and 2 of hexamethylenediamine
Inject 3.2 parts at a temperature of 140 ° C. and 4.5
The pressure reaction was carried out for 5 hours with stirring at a pressure of kg / cm ² .

Then, the reaction solution thus obtained was filtered, washed with water, and dried to obtain 29.5 parts of aminohexamethyleneperylene.

Reference Example 3 (Example of Preparation of Self-Dispersing / Soluble Compound) First,

A mixed solution of 25.6 parts of n-butyl acrylate, 17.4 parts of methacrylic acid, 20.0 parts of methyl methacrylate, 41.7 parts of styrene, and 2.0 parts of tert-butyl peroxyoctate was prepared.

Then, 105.0 parts of butyl cellosolve was charged into a reaction vessel equipped with a thermometer, a cooling tube and a stirrer, and the temperature was raised to 80 ° C. with stirring under a nitrogen blanket, and the above-mentioned was conducted. The mixture was added dropwise over 2 hours.

After the dropping was completed, the reaction was continued at 80 ° C. for 12 hours to give a nonvolatile content of 48.8%, and
A resin solution having an acid value of 106 was obtained. This resin solution is
When 100% neutralized with dimethylaminoethanol and dissolved in water, it was dissolved and exhibited self-dispersion and solubility.

Reference Example 4 (same as above) First,

A mixed solution of n-butyl acrylate 19.2 parts methacrylic acid 34.8 parts methyl methacrylate 15.0 parts styrene 31.3 parts tert-butyl peroxyoctate 2.0 parts was prepared.

Then, 100.3 parts of butyl cellosolve was charged into a reaction vessel equipped with a thermometer, a cooling tube and a stirrer, and the temperature was raised to 80 ° C. with stirring under a nitrogen blanket, and the above-mentioned procedure was performed. The mixed solution was added dropwise over 2 hours, and the reaction was continued for 12 hours at 80 ° C. even after the completion of the addition to obtain a resin solution having a nonvolatile content of 49.8% and an acid value of 223. Obtained.

This resin solution was 100% neutralized with dimethylaminoethanol and dissolved in water.
It was dissolved and exhibited self-dispersion and solubility.

Example 1 Using a reaction vessel equipped with a thermometer, a condenser and a stirrer, 37.7 parts of the self-dispersing / dissolving compound solution obtained in Reference Example 3 was added with 3.3 parts of aminomethylquinacridone. Parts and 25.3 parts of N-methyl-2-pyrrolidone were added with stirring, the temperature was gradually raised, and the reaction was continued under reflux for 5 hours. Was removed by vacuum filtration to obtain a target pigment dispersant solution having a nonvolatile content of 30.5%. Hereinafter, this is abbreviated as pigment dispersant (1).

Then, 6.6 parts of the pigment dispersant (1) and an unsubstituted quinacridone pigment (CI Pigmen) were used.
t Violet 19;
It was dispersed in 400 parts of a mixed solvent of water / isopropyl alcohol = 2/1 (weight part ratio).

After that, the temperature was raised to 80 ° C. and kept at the same temperature for 2 hours, and then 98 ° C. under reflux.
The temperature was raised to and the solvent was removed. After removing the solvent, the product was filtered, washed with water, and dried to obtain 21.5 parts of a pigment composition.

Then, 1 of the pigment composition thus obtained
0 parts and solids weight ratio of "Waterzol S-751" [water-soluble acrylic resin manufactured by Dainippon Ink and Chemicals, Inc.] / "Cymel 303" [water-soluble melamine resin manufactured by Mitsui Cyanamid] Is a 7/3 acrylic / melamine resin mixture for paint, and the pigment content is 3.75% (20 p
hr. ) And adjusted with 30% aqueous ammonia to a pH of 9.4, and dispersed with a paint conditioner manufactured by Toyo Seiki Co., Ltd. for 2 hours. A water-based acrylic / melamine-based paint was prepared.

Thereafter, this coating material was applied onto a polyester film with a 6 mil doctor blade, and baked and dried at 150 ° C. for 30 minutes to obtain a coating film.

Next, for each of the coating films,
The gloss (60 degree specular reflectance) and the dispersed particle size of the pigment in the paint (that is, the particle size of the pigment particle) were measured.
The results of these measurements are summarized in Table 1, and the paint obtained in this example has a small dispersed particle size and is particularly excellent in color development, film clarity, gloss and tinting strength. It was that.

The dispersed particle size was measured by a centrifugal sedimentation type particle size distribution analyzer "CAPA-5" manufactured by Horiba, Ltd.
00 ", and the rotation speed is 5,000 rpm. age,
In addition, ion dispersion water was used as the dispersion medium.

COMPARATIVE EXAMPLE 1 The use of pigment dispersant (1) was dispensed with entirely,
A control paint was prepared in the same manner as in Example 1 except that the amount of the unsubstituted quinacridone pigment used was changed to 10 parts.
Then, a control coating film was obtained.

With respect to this coating film, a coating test from both sides, that is, the measurement of gloss and the dispersed particle diameter of the pigment in the coating material, was carried out in the same manner as in Example 1. The measurement results are shown together in Table 1. The coating material obtained in this example has a large dispersed particle size, and the surface of the coating film is
It was very rough and low gloss.

Example 2 While using the pigment dispersant (1) in an amount of 1.6 parts, an unsubstituted quinacridone pigment (CI Pigment Vi) was used.
olet 19) instead of 10.0 parts of dimethylquinacridone pigment (CI Pigment Red 1
22; the same applies hereinafter) except that the coating composition was prepared in the same manner as in Example 1 except that the coating film was obtained.

Also for this coating film, in the same manner as in Example 1, a paint test was conducted from both sides, that is, the measurement of gloss and the dispersed particle size of the pigment in the paint. The results of these measurements are summarized in Table 1. The paint obtained in this example has a small dispersed particle size, and among other things, color developability, coating clarity, gloss and tinting strength Was excellent.

COMPARATIVE EXAMPLE 2 The use of the pigment dispersant (1) was completely absent,
Furthermore, 10 parts of dimethylquinacridone pigment and N-
A control coating material was prepared in the same manner as in Example 1 except that 1.1 parts of methyl-2-pyrrolidone was used, and then a control coating film was obtained.

With respect to this coating film, a coating test from both sides, that is, the measurement of gloss and the dispersed particle diameter of the pigment in the coating material, was carried out in the same manner as in Example 1. The results are shown together in Table 1. The coating material obtained in this example has a large dispersed particle size, and the surface of the coating film is very rough and has a low gloss. It was only.

Example 3 Using a reaction vessel equipped with a thermometer, a cooling tube and a stirrer, 42.4 parts of the self-dispersing / dissolving compound solution obtained in Reference Example 4 was added to diaminodianthraquinonyl. 1.
5 parts and 82.6 parts of N-methyl-2-pyrrolidone were added with stirring, the temperature was gradually raised, the reaction was carried out under reflux for 5 hours, and then the solid matter was filtered under reduced pressure. Removed by squeezing to remove non-volatile components 17.3%
A target pigment dispersant solution was obtained. Hereinafter, this is abbreviated as pigment dispersant (2).

Then, in 8. of the pigment dispersant solution (2).
7 parts and diaminodianthraquinonyl pigment (C.I.P.
igment Red 177; the same applies hereinafter) 10.0
A coating material was prepared in the same manner as in Example 1 except that parts were used, and then a coating film was obtained.

With respect to this coating film, a coating test from both sides, that is, the measurement of gloss and the dispersed particle diameter of the pigment in the coating material, was carried out in the same manner as in Example 1. The results are collectively shown in Table 1. The paint obtained in this example has a small dispersed particle size and is particularly excellent in the clearness, gloss and tinting strength of the coating film. Met.

COMPARATIVE EXAMPLE 3 The use of the pigment dispersant (2) was completely eliminated.
And 10 parts of diaminodianthraquinonyl pigment and N
A control coating material was prepared in the same manner as in Example 1 except that 7.2 parts of -methyl-2-pyrrolidone was used, and then a control coating film was obtained.

With respect to this coating film as well, in the same manner as in Example 1, a coating test was conducted from both sides, that is, the measurement of gloss and the dispersed particle diameter of the pigment in the coating material. The results are collectively shown in Table 1. The coating material obtained in this example has a large dispersed particle size, and the surface of the coating film is rough and has a low gloss. It was only.

Example 4 Using a reaction vessel equipped with a thermometer, a cooling tube and a stirrer, 39.1 parts of the self-dispersing / dissolving compound solution obtained in Reference Example 4 was added to 3.3.1 parts of aminohexamethyleneperylene. Three
Part, 22.2 parts of butyl cellosolve and N-methyl-
Add 40.0 parts of 2-pyrrolidone with stirring,
After gradually raising the temperature and carrying out the reaction under reflux for 5 hours, the solid matter is removed by filtration under reduced pressure to remove the non-volatile content of 19.8%. A solution was obtained. Hereinafter, this is abbreviated as pigment dispersant (3).

Then, 20.2 parts of the thus-obtained pigment dispersant (3) and a perylene pigment (CI Pig.
ment Red 179; the same hereinafter) and 20.0 parts of water / isopropyl alcohol = 2/1 (parts by weight)
Disperse it in 400 parts of the mixed solvent, raise the temperature to 80 ° C., hold at the same temperature for 2 hours, and then
Under reflux, the temperature was raised to 98 ° C. to remove the solvent.

After removing the solvent, 23.6 parts of a pigment composition was obtained by successively filtering, washing with water and drying.

Thereafter, a coating material was prepared in the same manner as in Example 1 except that 10 parts of the thus obtained pigment composition was used, and then a coating film was obtained. This coating film was also subjected to the paint test from both sides, that is, the gloss measurement and the dispersed particle diameter of the pigment in the paint were performed in the same manner as in Example 1.

The results are shown together in Table 1. The paint obtained in this example has a small dispersed particle size, and in particular, the coloring property, the sharpness of the coating film, the luster and the coloring. It was said to be excellent in strength.

COMPARATIVE EXAMPLE 4 The use of the pigment dispersant (3) was totally absent,
A control coating material was prepared in the same manner as in Example 1 except that 10 parts of the perylene pigment was used, and then a control coating film was obtained.

With respect to this coating film as well, in the same manner as in Example 1, a coating test from both sides of the measurement of gloss and the dispersed particle diameter of the pigment in the coating material was carried out. The results are collectively shown in Table 1. The coating material obtained in this example has a large dispersed particle size, and the surface of the coating film is rough and has a low gloss. It was only.

Example 5 Using a reaction vessel equipped with a thermometer, a cooling tube and a stirrer, 42.4 parts of the self-dispersing / dissolving compound solution obtained in Reference Example 4 was charged with aminomethyl copper phthalocyanine. 82.6 parts of 2.4 parts and N-methyl-2-pyrrolidone
Parts were added with stirring, the temperature was gradually raised, the reaction was carried out under reflux for 5 hours, and then the solid matter was removed by filtration under reduced pressure to obtain a nonvolatile content of 17.3%. A desired pigment dispersant solution was obtained. Hereinafter, this is abbreviated as pigment dispersant (4).

Then, 17.3 of this pigment dispersant (4) was used.
And a copper phthalocyanine pigment (CI Pigment
20.0 parts of Blue 15; the same applies hereinafter) are dispersed in 400 parts of water so that the pH becomes 10.0,
It was adjusted with dimethylaminoethanol.

Thereafter, the temperature was raised to 80 ° C., the temperature was kept at the same temperature for 2 hours, and then the temperature was cooled to room temperature.
The pH was adjusted to 4.0 with 35% hydrochloric acid. After that, it is filtered, washed with water, dried, and then 22.
5 parts of pigment composition are obtained.

Subsequently, a coating material was prepared in the same manner as in Example 1 except that 10 parts of the pigment composition thus obtained was used, and then a coating film was obtained. This coating film was also subjected to the paint test from both sides, that is, the gloss measurement and the dispersed particle diameter of the pigment in the paint were performed in the same manner as in Example 1.

The results are summarized in Table 1. The paint obtained in this example has a small dispersed particle size, and in particular, the coloring property, the sharpness of the coating film, the luster and the coloring. It was said to be excellent in strength.

COMPARATIVE EXAMPLE 5 The use of the pigment dispersant (4) was completely absent,
A control paint was prepared in the same manner as in Example 1 except that 10 parts of the copper phthalocyanine pigment was used, and then a control coating film was obtained.

With respect to this coating film as well, in the same manner as in Example 1, a paint test was conducted from both sides, that is, the measurement of gloss and the dispersed particle diameter of the pigment in the paint. The results are collectively shown in Table 1. The coating material obtained in this example has a large dispersed particle size, and the surface of the coating film is rough and has a low gloss. It was only.

Example 6 Using a reaction vessel equipped with a thermometer, a cooling tube and a stirrer, 42.4 parts of the self-dispersing / dissolving compound obtained in Reference Example 4 was mixed with aminohexamethylenesulfonic acid amide. 2.1 parts of carbazoledioxazine and 82.6 parts of N-methyl-2-pyrrolidone were added with stirring, the temperature was gradually raised, and the reaction was carried out under reflux for 5 hours. Then, the solid matter was removed by filtration under reduced pressure to obtain a target pigment dispersant solution having a nonvolatile content of 16.6%. Hereinafter, this is abbreviated as pigment dispersant (5).

Next, 9.0 parts of this pigment dispersant (5) and dioxazine violet pigment (CI Pigm) were used.
ent Violet 23; the same applies hereinafter) was changed to 10.0 parts to prepare a coating material and then obtain a coating film in the same manner as in Example 1.

With respect to this coating film as well, in the same manner as in Example 1, a coating test was conducted from both sides, that is, the measurement of gloss and the dispersed particle diameter of the pigment in the coating material. The results are collectively shown in Table 1. The paint obtained in this example has a small dispersed particle size, and especially, the coloring property, the sharpness of the coating film, the luster and the tinting strength. It was excellent.

COMPARATIVE EXAMPLE 6 The use of pigment dispersant (5) was completely absent,
And 10 parts of dioxazine violet pigment and N
A control paint was prepared in the same manner as in Example 1 except that 7.5 parts of -methyl-2-pyrrolidone was used, and then a control coating film was obtained.

With respect to this coating film as well, in the same manner as in Example 1, a coating test from both sides, that is, the measurement of gloss and the dispersed particle diameter of the pigment in the coating material was carried out. The results are collectively shown in Table 1. The coating material obtained in this example has a large dispersed particle size, and the surface of the coating film is rough and has a low gloss. It was only.

[0113]

[Table 1]

<< Footnote in Table 1 >>"Gloss" in the table is 60
It represents the degree of specular reflectance (%).

[0115]

INDUSTRIAL APPLICABILITY The pigment dispersant and the pigment composition of the present invention are dispersed in a wide range by being dispersed in an aqueous resin varnish, mainly in the form of an aqueous paint or an aqueous printing ink. Is used.

In addition, the aqueous paints and printing inks obtained by using the pigment dispersant and the pigment composition of the present invention are, in particular, color development, coating gloss, sharpness and storage stability. It provides excellent paints and coatings.

[Procedure amendment]

[Submission date] August 12, 1994

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0027

[Correction method] Change

[Correction content]

An amide bond, an ester bond, an ether through another reactive group such as a carboxyl group, a sulfonic acid group, a primary amino group, a secondary amino group, an epoxy group, a hydroxyl group, an isocyanate group or a halogen group. Examples of the compound include a compound which is self-dispersible or soluble in water, which is obtained by reacting in a non-reactive solvent in the presence or absence of a catalyst so as to form a bond or a urethane bond.

Claims (9)

[Claims] 1. A water-based pigment dispersant which is self-dispersible or soluble in water and further has an organic dye atomic group. 2. An aqueous pigment dispersant self-dispersing or dissolving in water, having a structure in which the above-mentioned organic dye atomic group is bound by an amide bond, an ester bond, an ether bond or a urethane bond. 3. The above-mentioned organic dye atomic group is a carboxyl group, a sulfonic acid group, a primary amino group, a secondary amino group, an epoxy group, an isocyanate group, a reactive group which is a hydroxyl group or a halogen group, and a carboxyl group. , Sulfonic acid group, primary amino group, secondary amino group, epoxy group, isocyanate group, hydroxyl group or other reactive group such as a halogen group through the above amide bond, ester bond,
The aqueous pigment dispersant according to claim 1 or 2, which has a structure in which it is bound by an ether bond or a urethane bond. 4. The aqueous pigment dispersant according to claim 1, which has a number average molecular weight of 1,000 to 200,000. 5. A pigment composition which is self-dispersing or dissolving in water and further contains an aqueous pigment dispersant having an organic dye atomic group. 6. A pigment composition comprising an organic pigment and an aqueous pigment dispersant which is self-dispersible or soluble in water and has an organic dye atomic group. 7. The water-based pigment dispersant as described above, wherein the organic dye atomic group has a structure in which the organic dye atomic group is bound by an amide bond, an ester bond, an ether bond or a urethane bond. The pigment composition according to item 6. 8. The above-mentioned organic dye atomic group is a carboxyl group, a sulfonic acid group, a primary amino group, a secondary amino group, an epoxy group, an isocyanate group, a reactive group which is a hydroxyl group or a halogen group, and a carboxyl group. , Sulfonic acid group, primary amino group, secondary amino group, epoxy group, isocyanate group, hydroxyl group or other reactive group such as a halogen group through the above amide bond, ester bond,
The pigment composition according to claim 5 or 6, which is the above-mentioned aqueous pigment dispersant having a structure in which it is bound by an ether bond or a urethane bond. 9. The above-mentioned aqueous pigment dispersant is 1,000.
The pigment composition according to claim 5 or 6, which has a number average molecular weight in the range of ˜200,000.