JP2001172520A - Pigment dispersant, pigment composition, and pigment dispersion - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a pigment dispersant which is effective for dispersing a pigment, especially a benzimidazolone pigment, in a nonaqueous vehicle. SOLUTION: This dispersant comprises a benzimidazolone pigment derivative represented by formula (1) [R1 is -CH(COCH3)- or napthtylene; X1 to X5 are each SO3H or its salt group, COOH or its salt group, H, Cl, Br, F, CF3, CH3, NO2, OH, OCH3, OC2H5, COOR2, CONHC6H4CONH2, CONHC6H5, SO2NHR2, or the like or a grop represented by formula (2) (at least one of X1 to X9 is SO3H or its salt group or COOH or its salt group)].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a pigment dispersant and a pigment composition which provide a pigment dispersion excellent in usability, especially non-aggregation, non-crystallinity and fluidity.

[0002]

2. Description of the Related Art When fine particles of pigment are dispersed in non-aqueous vehicles such as offset inks, gravure inks, and paints, it is difficult to obtain a stable dispersion, and this is a problem in terms of manufacturing operations and the value of the resulting product. It is known to cause various problems that have significant effects. For example, a dispersion containing a pigment composed of fine particles often has a high viscosity, which not only makes it difficult to remove and transport the product from the disperser, but also worse, causes gelation during storage and causes use. It can be difficult. When different kinds of pigments are mixed and used, color unevenness or marked reduction in coloring power may be caused in a colored product due to phenomena such as color separation due to aggregation and precipitation. Pigment dispersants in which various substituents are introduced into pigments to solve the above problems are known, but effective pigment dispersants are known for yellow pigments, particularly benzimidazolone pigments. Had not been.

[0003]

SUMMARY OF THE INVENTION The present invention provides a pigment dispersant effective for dispersing a pigment, particularly a benzimidazolone pigment, in a non-aqueous vehicle.

[0004]

The present invention relates to a pigment dispersant comprising a benzimidazolone pigment derivative represented by the following general formula (1). General formula (1)

Embedded image In the formula, R ¹ represents —CH (COCH ₃ ) — or a naphthylene group; X ^{1 to} X ⁵ each independently represent —SO ₃ H or an alkali metal salt or ammonium salt thereof;
COOH or alkali metal or ammonium salts thereof, -H, -Cl, -Br, -F , -CF 3, -C
_{H 3, -NO 2, -OH,} -OCH 3, -OC 2 H 5,
_{^{-COOR 2, -OCNHC 6 H 4 CONH}} 2, -CON
HC ₆ H ₅ , —SO ₂ NHR ² , a group represented by the general formula (2) (R ² represents an alkyl group having 1 to 4 carbon atoms), and a general formula (2)

Embedded imageIn the formula (2), X⁶~ X⁹Are each independently -SO_Three H
Or its alkali metal salt or ammonium salt,
COOH or its alkali metal salt or ammonia
Salt, -H, -Cl, -Br, -F, -CF_Three , -C
H_Three , -NO_Two , -OH, -OCH_Three , -OC_Two H_Five ,
-COOR^Two , -CONHC₆H_FourCONH _Two, -CON
HC₆ H_Five , -SO_TwoNHR^TwoRepresents (R^Two Has 1 to 1 carbon atoms
4 represents an alkyl group. ), X¹ ~ X⁹At least one of
Is -SO_Three H or its alkali metal salt or
Ammonium salt, or -COOH or its alkali
Represents a metal salt or an ammonium salt (however, X¹But-
COOH, X^Two~ X^FiveIs -H and R¹Is -CH (COC
H_Three)-Is excluded. ). Further, the present invention provides
The present invention relates to a pigment composition comprising the above pigment dispersant. More books
The invention provides a pigment dispersion comprising the pigment composition and a vehicle.
About the body. X¹Is -COOH, X^Two~ X^FiveIs a hydrogen atom,
R¹Is -CH (COCH3)-, PY1
51, already known as pigment
Extremely low solubility in solvents and solvents, making it suitable as a pigment dispersant.
Does not show sex.

[0005]

DESCRIPTION OF THE PREFERRED EMBODIMENTS As a method for producing a benzimidazolone pigment derivative, there is a method by azo coupling or sulfonation of a benzimidazolone pigment. As a sulfonating agent, fuming sulfuric acid, concentrated sulfuric acid, chlorosulfuric acid or the like is used. It is common to use this. Some typical examples of the benzimidazolone pigment derivatives used in the present invention are shown below.

Benzimidazolone pigment derivatives (a)

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Benzimidazolone pigment derivative (b)

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Benzimidazolone pigment derivative (c)

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Benzimidazolone pigment derivative (d)

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Benzimidazolone pigment derivative (e)

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The benzimidazolone pigment derivative (f)

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Benzimidazolone pigment derivative (g)

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Benzimidazolone pigment derivative (h)

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Benzimidazolone pigment derivative (i)

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Benzimidazolone pigment derivative (j)

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[0016]

[0017]

Benzimidazolone pigment derivative (k)

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The pigment composition of the present invention is effective for almost all commercially available pigments, but is particularly effective for dispersing benzimidazolone pigments. Examples of the pigment that can be used in the present invention include, for example, benzimidazolone pigments, azo pigments such as soluble and insoluble azo pigments, condensed azo pigments, phthalocyanine pigments, quinacridone pigments, isoindolinone pigments, and isoindoline pigments. , Quinophthalone pigments, perylene / perinone pigments,
Dioxazine pigments, Anthraquinone pigments, Dianthraquinonyl pigments, Anthrapyrimidine pigments, Ansanthrone pigments, Indanthrone pigments, Flavanthrone pigments, Pyranthrone pigments, Diketopyrrolopyrrole pigments, Vat dyes And organic pigments such as basic pigments and basic dye pigments.

The benzimidazolone pigments include C.I.
I. Pigment Yellow 120, 151, 154, 15
6, 175, 180, 181, 194, Pigment Orange 36, 60, 62, 72, Pigment Red 17
1, 175, 176, 185, 208, Pigment Violet 32, Pigment Brown 25, and the like.

The amine component used for forming the organic ammonium salt type pigment dispersant of the present invention includes a primary amine, a secondary amine, a tertiary amine and a quaternary amine.
There are secondary amines. Specifically, primary amines include secondary amines such as ethylamine, propylamine, isopropylamine, butylamine, isobutylamine, sec-butylamine, ethanolamine, isopropanolamine, octylamine, dodecylamine, laurylamine, stearylamine, and oleylamine. The amines are dimethylamine, diethylamine, dipropylamine, diethanolamine, distearylamine, etc., and the tertiary amines are trimethylamine, triethylamine, triethanolamine, triisopropanolamine, dimethylethanolamine, diethylethanolamine, n-butyldiethanolamine, N, N-dimethyl-1,3-diaminopropane, N, N-diethyl-1,3-diaminopropane, dimethyloctylamine, dimethyl Shiruamin,
Dimethyl lauryl amine, dimethyl myristyl amine,
The quaternary amines include dimethyl palmidoylamine, dimethylstearylamine, dimethylbehenylamine, dilaurylmonomethylamine, and trioctylamine. Examples of the quaternary amine include dimethyldidodecylammonium chloride, dimethyldioleylammonium chloride, and trimethylstearylammonium chloride.

The method for producing the pigment composition of the present invention is as follows. 1. A pigment composition obtained by previously mixing a pigment and a pigment dispersant is added to a non-aqueous vehicle or the like and dispersed. 2. A pigment and a pigment dispersant are separately added and dispersed in a non-aqueous vehicle or the like. 3. A pigment and a pigment dispersant are separately dispersed in a non-aqueous vehicle or the like, and the resulting dispersion is mixed. In this case, the pigment dispersant may be dispersed only with the solvent. 4. After dispersing the pigment in a non-aqueous vehicle or the like, a pigment dispersant is added to the resulting dispersion.

The preferred compounding amount of the pigment dispersant in the pigment composition shown in the above 1 is 100 parts by weight of the pigment.
0.1 to 40 parts by weight, more preferably 5 to 20 parts by weight. If the amount of the pigment dispersant is less than the above values,
A sufficient pigment dispersing effect cannot be obtained, and the effect of the used amount cannot be obtained even if the amount is more than the above value.

Even if the pigment composition is prepared by simply mixing the pigment powder and the pigment dispersant powder, the desired effect can be sufficiently obtained. However, mechanical mixing with various pulverizers such as kneaders, rolls, attritors, and super mills,
A solution containing a pigment dispersant is added to the suspension of the pigment in water or an organic solvent, and the pigment dispersant is adsorbed on the pigment surface, or the organic pigment and the pigment dispersant are co-dissolved in a solvent having strong dissolving power such as sulfuric acid. If a close mixing method such as coprecipitation with a poor solvent such as water is used, better results can be obtained.

In the use of the pigment dispersant of the present invention as described in the above items 2 to 4, dispersion of the pigment or the pigment dispersant in an aqueous vehicle or water, a non-aqueous vehicle or a solvent, or a mixture thereof, etc. By using a dissolver, a high-speed mixer, a homomixer, a kneader, a roll mill, a sand mill, an attritor, or the like as a machine, good dispersion of the pigment can be achieved.

The vehicle in which the pigment composition of the present invention is preferably used is a gravure ink such as lime rosin varnish, polyamide resin varnish or vinyl chloride resin varnish, nitrocellulose lacquer, amino-alkyd resin dry or baked paint, urethane Base resin paint, acrylic resin paint and the like. Note that the use of the pigment composition of the present invention is not limited to non-aqueous vehicles, and other printing inks and paints, coloring of plastics, and also aqueous inks, aqueous paints, emulsion-type inks, and emulsion-type paints can be dispersed. An excellent effect and a colored product having coloring power can be obtained.

[0027]

The present invention will be described in more detail with reference to the following examples. In the examples, “parts” means “parts by weight”. Production Example 1 (Production of benzimidazolone-based pigment derivative by coupling reaction) 8.0 parts of sodium hydroxide was dissolved in 200 parts of water, and 3
-18.1 parts of aminophthalic acid were added. Add concentrated hydrochloric acid 5
0 parts were added and cooled to below 0 ° C. Next, 7.2 parts of sodium nitrite were dissolved in 20 parts of water, added dropwise to the reaction system, and stirred at 5 ° C. or lower for 1 hour. Next, 10.4 parts of sodium hydroxide were dissolved in 1000 parts of water, and 23.3 parts of acetoacetylbenzimidazole was added. 8
25.5 parts of 5% acetic acid was added, and the diazonium salt solution prepared above was added dropwise, followed by stirring at room temperature for 1 hour. The precipitate was filtered, washed with water, and dried to produce 43 parts of a benzimidazolone pigment derivative (a). Production Example 2 (Production of Dodecyl Ammonium Salt of Production Example 1) 2.0 parts of sodium hydroxide was dissolved in 200 parts of water, and 10 parts of the pigment derivative described in Production Example 1 was added to adjust the pH to 9.0. Next, 15 parts of dodecylamine was added, and the precipitate was filtered, washed with water, and dried to produce 19 parts of a zimidazolone pigment derivative (b). Production Example 3 (Production of benzimidazolone pigment derivative by sulfonation reaction) 50 parts of pigment (PY180) was added to 750 parts of 95% by weight sulfuric acid at 10 ° C or lower. Next, the mixture was heated and stirred at 15 ° C. for 2 hours, and then poured into ice water to precipitate. The precipitate was filtered, washed with brine, and dried to produce 53 parts of a benzimidazolone pigment derivative (f). Production Example 4 (Production of dimethyldidodecylammonium salt of Production Example 3) 0.5 part of sodium hydroxide was dissolved in 200 parts of water, and 5 parts of the pigment derivative described in Production Example 1 was added to adjust the pH to 9.0. Next, 3.5 parts of dimethyldidodecylammonium chloride was added, and the precipitate was filtered, washed with water, and dried.
7.0 parts of a benzimidazolone pigment derivative (g) was produced. Example 1 A coating material was prepared using the benzimidazolone pigment (PY156) and the benzimidazolone pigment derivative (a) according to the following formulation. The paint was prepared by placing components other than the mixed varnish to be added after dispersing in the following composition into a container, adding a steel ball, dispersing with a paint shaker, and then adding the mixed varnish. Pigment (PY156) 9.5 parts Benzimidazolone pigment derivative (a) 0.5 part Alkyd resin varnish (nonvolatile content 60%) 26.4 parts Melamine resin varnish (nonvolatile content 50%) 13.6 parts Thinner (Xylene / n-butanol = 8/2) 20.0 parts Mixed varnish added after dispersion (alkyd resin varnish / melamine resin varnish = 7/3 (solid content)) 48.3 parts As a result, good fluidity and gloss of the film were shown.

Method for Evaluating Paint Viscosity The viscosity of the obtained paint was evaluated using a B-type viscometer (measuring temperature 25 ° C., rotation speed 6 (rpm) and 60 (rpm)).

Evaluation Method for Film Gloss The obtained paint was applied to a Ford Cup 4 having a final paint viscosity of 23.
Seconds were prepared with a thinner, sprayed on a tin plate with an air spray gun and baked, and the glossiness of the coated surface was evaluated by measuring 20 ° gloss with a gloss meter.

Comparative Example 1 A coating material was prepared in the same manner as in Example 1 except that the benzimidazolone-based pigment derivative (a) was not added and the pigment content was 10 parts. The obtained paint was inferior to Example 1 in fluidity and gloss. In Example 1, the benzimidazolone-based pigment derivatives (b), (c), (d), and (e) were used in place of the benzimidazolone-based pigment derivative (a). Equivalent good results were obtained.

Example 2 A coating material was prepared using the benzimidazolone pigment (PR171) and the benzimidazolone pigment derivative (i) according to the following formulation. The paint was prepared by placing components other than the mixed varnish to be added after dispersing in the following formulation into a container, adding a steel ball, dispersing with a paint shaker, and then adding the mixed varnish. When the obtained paint was evaluated in the same manner as in Example 1, it showed good fluidity and gloss of the coating film. Pigment (PR171) 9.5 parts Benzimidazolone pigment derivative (i) 0.5 part Oil-free polyester resin varnish (nonvolatile content 60%) 26.4 parts Melamine resin varnish (nonvolatile content 50%) 13.6 Part Swazol 20.0 parts Mixed varnish added after dispersion (oil-free polyester resin varnish / melamine resin varnish = 7/3 (solid content)) 48.3 parts

Comparative Example 2 A coating material was prepared in the same manner as in Example 2 except that the benzimidazolone-based pigment derivative (i) was not added and the pigment content was 10 parts. The obtained paint was inferior to Example 1 in fluidity and gloss. When the benzimidazolone pigment derivative (j) and (h) were used in Example 2 in place of the benzimidazolone pigment derivative (i), good results equivalent to those of the benzimidazolone pigment derivative (i) were obtained. Was done.

Example 3 A coating material was prepared using the benzimidazolone pigment (PY180) and the benzimidazolone pigment derivative (f) according to the following formulation. For the paint, components other than the resin to be added after dispersion of the following formulation are put into a container, 3 mmφ alumina beads are added, and the mixture is dispersed with a paint conditioner. Then, 37.5 parts of the following acrylic resin and methylated melamine resin (trade name) 3. Cymel 303 manufactured by Mitsui Cytec)
Prepared by adding 3 parts. Pigment (PY180) 9.9 parts Benzimidazolone pigment derivative (f) 0.1 part Acrylic resin solution (weight average molecular weight 25,000, acid value 60, monomer composition (weight ratio) acrylic acid / dimethylaminoethyl methacrylate / acrylic acid Ethyl / methyl methacrylate / vinyl acetate = 7.7 / 15 / 37.3 / 30/10 (solid content 20%)) 12.5 parts Ion-exchanged water 20.0 parts As a result of the evaluation, good fluidity and gloss of the film were shown.

Evaluation method of coating film gloss The obtained water-based coating material was spread on a PET film using a 4 mil film applicator, baked at 140 ° C for 30 minutes, and measured with a digital variable gloss meter at 20 ° gloss. The sharpness of the surface was evaluated.

Comparative Example 3 A coating material was prepared in the same manner as in Example 3 except that the benzimidazolone-based pigment derivative (f) was not added and the pigment content was 10 parts. The obtained paint was inferior to Example 3 in fluidity and gloss.

In Example 3, instead of the benzimidazolone pigment derivative (f), the benzimidazolone pigment derivative (a), (b), (c), (d), (e), (g)
When a benzimidazolone pigment derivative (f) is used
As good results as were obtained.

Example 4 A coating material was prepared using the benzimidazolone pigment (PY175) and the benzimidazolone pigment derivative (k) according to the following formulation. The paint was prepared by placing components other than the mixed varnish to be added after dispersing in the following formulation into a container, adding a steel ball, dispersing with a paint shaker, and then adding the mixed varnish. The obtained paint was used in Example 1
When evaluated in the same manner as above, good fluidity and gloss of the coating film were shown. Pigment (PY175) 9.5 parts Benzimidazolone pigment derivative (k) 0.5 part Oil-free polyester resin varnish (nonvolatile content 60%) 26.4 parts Melamine resin varnish (nonvolatile content 50%) 13.6 Part Swazol 20.0 parts Mixed varnish added after dispersion (oil-free polyester resin varnish / melamine resin varnish = 7/3 (solid content)) 48.3 parts

Comparative Example 4 A pigment was prepared in the same manner as in Example 4 except that the pigment (PY151) was added instead of the benzimidazolone-based pigment derivative (k), and the pigment (PY175) was 10 parts. The obtained paint was inferior to Example 4 in fluidity and gloss. Comparative Example 5 A coating material was prepared in the same manner as in Example 4 except that the benzimidazolone-based pigment derivative was not added and the pigment (PY151) was 10 parts. The obtained paint had poor fluidity and gloss as compared with Comparative Example 4.

[0039]

The pigment composition of the present invention shows good dispersibility in various vehicles, shows good fluidity such as a decrease in the viscosity of the dispersion and a decrease in the structural viscosity, and at the same time, shows color separation and crystallinity. Inks and paints free from problems such as changes in color. As a result, it is possible to obtain a printed product or a coated film with good gloss and thus a beautiful product.

Claims (5)

[Claims] 1. A benzimid represented by the following general formula (1):
A pigment dispersant comprising a dazolone pigment derivative. General formula (1)Where R¹ Is -CH (COCH_Three )-Or naphthylene
X represents a group¹ ~ X^Five Are each independently -SO_Three H
Or its alkali metal salt or ammonium salt,
COOH or its alkali metal salt or ammonia
Salt, -H, -Cl, -Br, -F, -CF_Three , -C
H_Three , -NO_Two , -OH, -OCH_Three , -OC_Two H_Five ,
-COOR^Two , -CONHC₆H_FourCONH_Two, -CON
HC₆ H_Five, -SO_TwoNHR^Two Represented by the general formula (2)
Represents a group (R^Two Represents an alkyl group having 1 to 4 carbon atoms.
You. ), General formula (2)In the formula (2), X⁶~ X⁹Are each independently -SO_Three H
Or its alkali metal salt or ammonium salt,
COOH or its alkali metal salt or ammonia
Salt, -H, -Cl, -Br, -F, -CF_Three , -C
H_Three , -NO_Two , -OH, -OCH_Three , -OC_Two H_Five ,
-COOR^Two , -CONHC₆H_FourCONH _Two, -CON
HC₆ H_Five , -SO_TwoNHR^TwoRepresents (R^Two Has 1 to 1 carbon atoms
4 represents an alkyl group. ), X¹ ~ X⁹ At least one of
Is -SO_Three H or its alkali metal salt or
Ammonium salt, or -COOH or its alkali
Represents a metal salt or an ammonium salt (however, X¹But-
COOH, X^Two~ X^FiveIs -H and R¹Is -CH (COC
H_Three)-Is excluded. ). 2. At least one of X ^{1 to} X ⁹ is —SO ₃ H
The pigment dispersant according to claim 1, which is an organic ammonium salt of -COOH or an organic ammonium salt of -COOH. 3. A pigment composition comprising a pigment and the pigment dispersant according to claim 1 or 2. 4. The pigment composition according to claim 3, wherein the pigment is a benzimidazolone pigment. 5. A pigment dispersion comprising the pigment composition according to claim 3 and a vehicle.