JP2503468B2 - Disazo pigment composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a disazo pigment composition having improved fluidity, tinting strength and transparency when used in printing inks, paints and the like.

(Prior art) Conventionally, when disazo pigments are used in printing inks, paints, etc., as a method for improving the fluidity and transparency of the product,
A mixture of these sulfonates with a disazo pigment (Japanese Patent Publication No. 4511026/1985) or a mixture of a polar coupling component and a non-polar coupling component having a carboxylic acid group and / or a sulfonic acid group as a coupling component. Is disclosed (Japanese Patent Publication No. 55-49087).

(Problems to be Solved by the Invention) However, in these methods, fluidity, coloring power,
The effect of improving the transparency is not always sufficient, and for example, even if the initial viscosity of the ink can be lowered, it may cause a problem in practical use due to thickening over time, which is not always a satisfactory effect. It was

(Means for Solving the Problems) As a result of earnest research, the present inventors have found that these aptitudes can be satisfied by mixing a disazo compound having a specific structure with a disazo pigment, and It came to completion.

That is, the present invention provides a disazo pigment composition comprising a disazo pigment and a disazo compound comprising the disazo compound represented by the general formula (I).

[In the formula, X and Y represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a lower alkoxycarbonyl group, but they do not all take a hydrogen atom at the same time.

A ₂ is (1) general formula (A) Wherein W is a sulfonic acid group and / or a carboxylic acid group.
A naphthyl group containing 1 to 4 phenyl groups or 1 to 4 sulfonic acid groups, and further containing 1 to 4 of a lower alkyl group, a halogen atom, a lower alkoxy group, a hydroxyl group and an acetamino group as a substituent. Well, these may be the same or different. ) Or a group of the general formula (B) (In the formula, R represents an aliphatic chain having 1 to 4 carbon atoms, and V represents a sulfonic acid group or a carboxylic acid group.).

A ₁ is the general formula (In the formula, Z is (1) an unsubstituted naphthyl group, or (2)
A phenyl group substituted with 1 to 4 substituents selected from the group consisting of a lower alkyl group, a halogen atom, a lower alkoxy group, a carbonamido group, a sulfonamide group or an acetamino group is shown.

Provided that X and Y represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, but do not simultaneously take a hydrogen atom, and A ₂ is a group represented by the general formula (A). Wherein W is (a) a phenyl group having only one sulfonic acid group or carboxyl group which may have 1 or 2 substituents selected from the group consisting of chlorine atom, methyl group and methoxy group. Or (b) 1 selected from the group consisting of chlorine atom, methyl group and methoxy group
In the case of a naphthyl group having only one sulfonic acid group which may have 2 to 2 substituents, Z is a substituent selected from the group consisting of an unsubstituted phenyl group, a methyl group, a methoxy group and a chlorine atom. No phenyl group having 1 to 3 is taken. ) Represents a group represented by.

Further, the sulfonic acid group and / or the carboxylic acid group may be in the form of an alkaline earth metal salt or an aluminum salt, respectively. There are several possible methods for producing the disazo compound represented by the general formula (1) (hereinafter referred to as the present disazo compound). In general formula (I), a diamine having a skeleton structure represented by B is used. After tetrazotization, an acetoacetamide compound having a skeleton structure represented by A ₂ (hereinafter referred to as a coupling component A ₂ ) is added and reacted, and then this reaction product is represented by A ₁ . A method of reacting with an acetoacetamide compound having a skeletal structure (hereinafter referred to as coupling component A ₁ ) is a practically advantageous means.

When the present disazo compound is produced by the above method, the ratio of the coupling component A ₁ and the coupling component A ₂ used is preferably 1: 1 (molar ratio) in principle, but the coupling component A 1 is used. It is okay to keep the usage rate of _{1 high} . In this case, when preparing the pigment composition, the disazo compound may be mixed so that the content of the present disazo compound becomes an amount necessary for improving the suitability.

On the other hand, when the proportion of the coupling component A ₂ used is increased, a disazo compound having the coupling component A ₂ on both sides and represented by the following general formula (II) is produced. As shown in the example, this compound rather deteriorates the suitability of the pigment composition.
It is necessary to avoid increasing the proportion of A ₂ used.

(In the formula, A ₂ , X and Y have the same meaning as described above.) In the above-mentioned conventionally known method, the coupling component A ₂
Since the coupling component having a sulfonic acid group and / or a carboxylic acid group corresponding to is present in the reaction system (in water) in a dissolved state, the coupling component preferentially reacts with the tetrazo component, and in the general formula (II), It is presumed that a disazo compound of the type shown is formed and a sufficient improvement effect cannot be obtained.

General formula (In the formula, X and Y represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a lower alkoxycarbonyl group, but they do not all take a hydrogen atom at the same time.), For example, 3,3 ′ -Dichlorobenzidine, 3,3′-dibromobenzidine, 2,2′-dichlorobenzidine, 3,3′-dimethoxybenzidine, 3,3′-
Examples thereof include dimethylbenzidine, 3,3 ', 6,6'-tetrachlorobenzidine and 3,3'-dimethoxycarbonylbenzidine.

Examples of the coupling component A ₂ include 2-acetoacetylaminobenzenesulfonic acid, 3-acetoacetylaminobenzenesulfonic acid, 4-acetoacetylaminobenzenesulfonic acid, 2-acetoacetylamino-5-methylbenzenesulfonic acid, 2 -Acetoacetylamino-
4-chloro-5-methylbenzenesulfonic acid, 2-acetoacetylamino-5-chloro-4-methylbenzenesulfonic acid, 2-acetoacetylamino-5-acetylaminobenzenesulfonic acid, 4-acetoacetylamino-
2,5-Dichlorobenzenesulfonic acid, 3-acetoacetylamino-4-carboxybenzenesulfonic acid, 2-acetoacetylaminonaphthalenesulfonic acid, acetoacetylaminomethanesulfonic acid, acetoacetylaminoethanesulfonic acid, 2-acetoacetylamino benzoic acid,
3-acetoacetylaminobenzoic acid, 4-acetoacetylaminobenzoic acid, 3-acetoacetylamino-4-chlorobenzoic acid, 2-acetoacetylamino-5-bromobenzoic acid, 3-acetoacetylamino-4-methoxybenzoic acid Acid, 2-acetoacetylamino-5-chlorobenzoic acid, 2-acetoacetylamino-5-acetylaminobenzoic acid, 2-acetoacetylaminoterephthalic acid, 3-
Acetoacetylaminoisophthalic acid, 4-acetoacetylamino-2-hydroxybenzoic acid, 5-acetoacetylamino-2-hydroxybenzoic acid, acetoacetylaminoglycine, acetoacetylamino-β-alanine and the like and alkali metal salts thereof are used. can give.

Examples of the coupling component A ₁ include acetoacetanilide, acetoaceto-o-toluidide, acetoaceto-p-toluidide, acetoaceto-m-xylidide, acetoaceto-o-chloroanilide, and acetoaceto-p-.
Promoanilide, acetoaceto-o-anisidide, acetoaceto-p-anisidide, acetoaceto-4-chloro-2,5-dimethoxyanilide, acetoaceto-4-ethylanilide, 3-acetoacetylamino-4-chlorobenzamide, 4-acetoacetyl Aminobenzenesulfonamide, 4-acetoacetylaminoacetanilide,
Examples include 1-acetoacetylaminonaphthalene.

Even if the water-soluble group in the present disazo compound is an acid group as it is, the suitability improving effect is sufficient, but it can also be used as an alkaline earth metal salt or an aluminum salt. The use of these salts has little effect on the suitability improving effect.

The disazo pigment that can be used as a pigment composition by mixing with the present disazo compound is not particularly limited, but a disazo pigment represented by the following general formula (III) is preferable.

[In the formula, A ₃ and A ₄ may be the same or different from each other. (Q represents a substituted or unsubstituted phenyl group or naphthyl group, and the substituent is 1 to 4 of a lower alkyl group, a halogen atom, a lower alkoxy group, and an acetamino group, which may be the same or different. .) Represents a group represented by. ] Specific examples of the disazo pigment include CI pigment yellow 12, CI pigment yellow 13, CI pigment yellow 14, CI pigment yellow 17, CI pigment yellow 83, CI pigment orange 16 and the like.

As a method of mixing the present disazo compound and the disazo pigment, (A) a method of simply mixing the present disazo compound and the disazo pigment by a dry method, and (B) a slurry of the present disazo compound and a slurry of the disazo pigment are optionally heated. And (C) a method of synthesizing the disazo pigment in the presence of the present disazo compound, and (D) a method of synthesizing the present disazo compound in the presence of the disazo pigment.
The mixing ratio of the present disazo compound and the disazo pigment can be any ratio necessary for improving suitability, but usually, the present disazo compound is 0.5 to 50 parts by weight with respect to 100 parts by weight of the disazo pigment. Is.

(Effects of the Invention) The disazo pigment composition obtained by mixing the disazo compound according to the present invention has improved fluidity, tinting strength and transparency when used in printing inks, paints and the like.

(Example) Hereinafter, the present invention will be described with reference to production examples, examples, comparative examples and test examples. All parts and% in the examples are based on weight unless otherwise specified.

Production Example 1 [Synthesis of disazo compound] 3,8.2 parts of 3,3'-dichlorobenzidine, 85 parts of 35% hydrochloric acid and 800 parts of water were mixed and stirred, and then an aqueous solution containing 21.9 parts of sodium nitrite was added in an ice bath. Thus, a tetrazo solution of 3,3'-dichlorobenzidine was obtained. While stirring, an aqueous solution in which 32.8 parts of acetoacetylaminomethanesulfonic acid sodium salt was dissolved in 250 parts of water was added dropwise over 2 hours, and the mixture was stirred for 1 hour to obtain an orange slurry.

After dissolving 28.8 parts of acetoaceto-o-toluidide in an aqueous solution consisting of 30.6 parts of sodium hydroxide and 600 parts of water,
A solution obtained by diluting 52.1 parts of acetic acid with 200 parts of water was added dropwise over 1 hour to precipitate crystals. Then, this was cooled to 5 to 10 ° C., and the above orange slurry was added dropwise over 2 hours while stirring to obtain an orange yellow slurry of the disazo compound according to the present invention. This is designated as slurry (1).

A part of the slurry (1) was filtered, washed with water, and dried. The FAB mass spectrum of this product has a peak derived from a molecular ion at M / Z = 661, and the desired structural formula (I
It was confirmed that the compound V) was produced.

Production Examples 2 to 9 [Same as above] The coupling components A ₂ shown in Table 1 are shown in Table 1
A slurry of the disazo compound was obtained in the same manner as in Production Example 1 except that the reaction solution was reacted with the tetrazotized solution of the diamine shown in ( ₁₎ and then the reaction solution was reacted with the coupling component A ₁ . These are made into slurries (2) to (9) in order.

Example 1 The pH of a yellow slurry of CI Pigment Yellow 14 (including 100 parts of pigment solid content) was adjusted to 8.5 to 9.0, and then the slurry (1) synthesized in Production Example 1 was added to the solid content while stirring. Was heated for 30 minutes at 90 ° C., 1.39 parts of aluminum sulfate (0.13 parts as Al) was added, and the mixture was stirred for 30 minutes, filtered, and washed with water. Dry at 90 ° C and
A pigment composition according to the present invention containing I. Pigment Yellow 14 as a main component was obtained.

Examples 2 to 10 The conventionally known pigment slurry and the disazo compound slurries (2) to (9) according to the present invention were mixed at a ratio shown in Table 2 in the same manner as in Example 1 to prepare the present invention. The pigment composition thus obtained was obtained.

Comparative Example 1 (Method according to Example 4 of JP-B-45-11026) [Synthesis of Disazo Dye] 38.2 parts of 3,3′-dichlorobenzidine, 85 parts of 35% hydrochloric acid and 800 parts of water were mixed and stirred. Then, an aqueous solution containing 21.9 parts of sodium nitrite was added in an ice bath to obtain a tetrazo solution of 3,3′-dichlorobenzidine.

On the other hand, 89.2 parts of 4-acetoacetylaminobenzenesulfonic acid potassium salt was added to 30.6 parts of sodium hydroxide and 52.1 parts of acetic acid.
And dissolved in an aqueous solution of 800 parts of water. Then, this is cooled to 5 to 10 ° C., and then the above tetrazo solution is added dropwise with stirring over 2 hours to consist of only a coupling component containing a sulfonic acid group as a coupling component. A disazo dye slurry corresponding to (II) was obtained. This is referred to as slurry (1 ').

[Preparation of Disazo Pigment Composition] The pH of a yellow slurry of CI Pigment Yellow 14 (including 100 parts of pigment solid content) was adjusted to 8.5 to 9.0, and the slurry (1 ′) was added to the solid content while stirring. As 1.7
And added at 90 ° C. for 30 minutes. After heating, add 1.28 parts of aluminum sulfate (0.12 parts as Al), stir for 30 minutes,
Excessively, washed with water. It was dried at 90 ° C. to obtain a pigment composition containing CI Pigment Yellow 14 as a main component.

Comparative Example 2 (Method according to Example 3 of JP-B-45-11026) [Synthesis of disazo pigment composition by coprecipitation method with coupling component] 3,8.2 parts of 3,3'-dichlorobenzidine, 60 parts of 35% hydrochloric acid and water After mixing with 800 parts and stirring, an aqueous solution containing 21.9 parts of sodium nitrite was added in an ice bath to obtain a tetrazo solution of 3,3′-dichlorobenzidine.

On the other hand, acetoaceto-o-toluidide 56.8 parts and 4-
Acetoacetylaminobenzenesulfonic acid potassium salt 1.
After dissolving 34 parts in an aqueous solution consisting of 30.6 parts of sodium hydroxide and 600 parts of water, a solution obtained by diluting 52.1 parts of acetic acid with 200 parts of water was added dropwise over 1 hour to precipitate crystals. Then, this was cooled to 5 to 10 ° C., and the above-mentioned tetrazo solution was added dropwise over 2 hours while stirring and coupling was performed. After the coupling was completed, the pH was adjusted to 8.5 to 9.0, and the mixture was heated at 90 ° C for 30 minutes while stirring. After heating, add 1.28 parts of aluminum sulfate (0.12 parts as Al), stir for 30 minutes,
Excessively, washed with water. It was dried at 90 ° C. to obtain a pigment composition containing CI Pigment Yellow 14 as a main component.

Comparative Example 3 (Method according to Example 12 of JP-B-55-49087) [Synthesis of Disazo Pigment Composition by Sequential Addition of Water-Soluble Coupling Component] 38.2 parts of 3,3′-dichlorobenzidine and 60 parts of 35% hydrochloric acid After mixing and stirring 800 parts of water with water, an aqueous solution of 21.9 parts of sodium nitrite was added in an ice bath to obtain a tetrazo solution of 3,3′-dichlorobenzidine.

On the other hand, 56.8 parts of acetoaceto-o-toluidide was dissolved in an aqueous solution consisting of 30.6 parts of sodium hydroxide and 600 parts of water, and then 52.1 parts of acetic acid diluted with 200 parts of water was added dropwise over 1 hour to precipitate crystals. It was Then this is 5-10 ° C
While cooling and stirring, the above tetrazo solution was added dropwise over 2 hours for coupling, and separately from this, 1.34 parts of 4-acetoacetylaminobenzenesulfonic acid potassium salt was added from a second dropping funnel to water. An aqueous solution dissolved in 250 parts was added dropwise for 100 minutes for coupling. After the coupling was completed, the pH was adjusted to 8.5 to 9.0, and the mixture was heated at 90 ° C for 30 minutes while stirring. After heating, add 1.28 parts of aluminum sulfate (0.12 parts as Al), stir for 30 minutes,
Excessively, washed with water. It was dried at 90 ° C. to obtain a pigment composition containing CI Pigment Yellow 14 as a main component.

Comparative Example 4 (Method according to Example 5 of JP-B-55-49087) [Synthesis of disazo pigment composition by coprecipitation method with coupling component] 3,8.2 parts of 3,3'-dichlorobenzidine, 60 parts of 35% hydrochloric acid and water After mixing with 800 parts and stirring, an aqueous solution containing 21.9 parts of sodium nitrite was added in an ice bath to obtain a tetrazo solution of 3,3′-dichlorobenzidine.

On the other hand, 50.8 parts of acetoacetanilide and 3.34 parts of 2-acetoacetylaminobenzoic acid were dissolved in an aqueous solution consisting of 30.6 parts of sodium hydroxide and 600 parts of water, and then 52.1 parts of acetic acid was diluted with 200 parts of water, which took 1 hour. It was dripped to precipitate crystals. Then, this was cooled to 5 to 10 ° C., and the above-mentioned tetrazo solution was added dropwise over 2 hours while stirring and coupling was performed. After coupling, adjust pH to 8.
It was adjusted to 5 to 9.0 and heated at 90 ° C. for 30 minutes with stirring.
After heating, 4.74 parts of aluminum sulfate (0.45 parts as Al) was added, and the mixture was stirred for 30 minutes, then washed with water and excess. Dried at 90 ℃,
A pigment composition containing CI Pigment Yellow 12 as a main component was obtained.

Test Example 1 Pigment composition containing CI Pigment Yellow 14 as a main component obtained in Examples 1 to 4 and Comparative Examples 1 to 3 (all of which have a sulfonic acid group-containing coupling component of 1.5 mol based on all coupling components). %)), And CI Pigment Yellow 14 pigment, urethane gravure ink was prepared, and fluidity, tinting strength, and transparency were examined.

Gravi ink contains 15 parts of pigment composition and 135 urethane varnish.
Part, 3φ steel beads 300 parts in a polyethylene bottle, paint conditioner (Toyo Seiki Seisakusho)
For 30 minutes.

The fluidity of the ink is the viscosity immediately after the ink is made and after being left at 50 ° C for 1 week (viscosity at 60 rpm with a B type viscometer), and thixotropic index (TI value: viscosity at 6 rpm / viscosity at 60 rpm). It was evaluated by. The tinting strength was evaluated by measuring the Gretag density with a Gretag densitometer (reflection densitometer) for the color developed on the acetate film with a 0.15 mm bar coater, and the transparency was CI Pigment Yellow.
Using a color-developing film of the ink using 14 as a standard sample, ∘ is marked when the transparency is remarkably superior to this, ∘ is excellent, Δ is equivalent, and x is poor.

The results are shown in Table 3, and the pigment composition according to the present invention was excellent in fluidity, ink storability, tinting strength and transparency. What is particularly noteworthy is that the pigment composition of Comparative Example 1 in which the disazo dye corresponding to the general formula (II) is mixed is inferior in fluidity to the conventionally known CI Pigment Yellow 14 pigment. This indicates that the structure of the disazo compound having a coupling component containing a water-soluble group to be mixed is extremely important for improving suitability.

Test Example 2 CI Pigment Yellow 83-based pigment composition obtained in Example 5, CI Pigment Yellow 83, C. obtained in Examples 6 to 8.
With respect to I. Pigment Orange 16-based pigment composition and CI Pigment Orange 16 as well, urethane gravure ink was prepared in the same manner as in Test Example 1, and the fluidity, tinting strength and transparency were examined. The results are shown in Table 5, and the pigment composition according to the present invention was excellent in fluidity, stability over time, tinting strength, and transparency. For the evaluation of transparency, a color spread film of ink using CI Pigment Yellow 83 and CI Pigment Orange 16 was used as a standard sample.

Test Example 3 Pigment composition containing CI Pigment Yellow 12 produced in Examples 9 to 10 and Comparative Example 4 as a main component (in each case, the coupling component containing a carboxylic acid group was about 5 mol% based on all coupling components). ), And CI Pigment Yellow 12 pigment, lithographic inks were prepared and their fluidity, tinting strength and transparency were examined.

The lithographic ink was 1 part pigment composition and 4 parts rosin-modified phenolic resin with a Hoover Mahler under a load of 150 pounds.
It was prepared by kneading meat for 00 rotations x 3 times.

The fluidity of the ink was evaluated by flowing it through a glass plate at 70 ° for 30 minutes. The coloring power is about 1 part of the yellow ink prepared above and 5 parts of the blue standard ink with a Hoover Mahler, and the green ink prepared by kneading 100 revolutions x 3 times under a load of 150 pounds was spread on the art paper. The Gretag concentration was measured with a Gretag densitometer and evaluated. The transparency was visually evaluated in the same manner as in Test Example 1 using a yellow ink spread on black paper, using a yellow ink spread paper using CI Pigment Yellow 12 as a standard sample.

The results are shown in Table-6, and the pigment composition according to the present invention was excellent in fluidity, tinting strength and transparency.

Claims (1)

(57) [Claims] 1. A disazo pigment composition comprising a disazo pigment and a disazo compound represented by the general formula (I). [In the formula, X and Y represent a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group or a lower alkoxycarbonyl group, but they do not all take a hydrogen atom at the same time. A ₂ is (1) general formula (A) Wherein W is a sulfonic acid group and / or a carboxylic acid group.
A naphthyl group containing 1 to 4 phenyl groups or 1 to 4 sulfonic acid groups, and further containing 1 to 4 of a lower alkyl group, a halogen atom, a lower alkoxy group, a hydroxyl group and an acetamino group as a substituent. Well, these may be the same or different. ) Or a group of the general formula (B) (In the formula, R represents an aliphatic chain having 1 to 4 carbon atoms, and V represents a sulfonic acid group or a carboxylic acid group.). A ₁ is the general formula (In the formula, Z is (1) an unsubstituted naphthyl group, or (2)
A phenyl group substituted with 1 to 4 substituents selected from the group consisting of a lower alkyl group, a halogen atom, a lower alkoxy group, a carbonamido group, a sulfonamide group or an acetamino group is shown. Provided that X and Y represent a hydrogen atom, a halogen atom, a lower alkyl group or a lower alkoxy group, but do not simultaneously take a hydrogen atom, and A ₂ is a group represented by the general formula (A). Wherein W is (a) a phenyl group having only one sulfonic acid group or carboxyl group which may have 1 or 2 substituents selected from the group consisting of chlorine atom, methyl group and methoxy group. Or (b) 1 selected from the group consisting of chlorine atom, methyl group and methoxy group
In the case of a naphthyl group having only one sulfonic acid group which may have 2 to 2 substituents, Z is a substituent selected from the group consisting of an unsubstituted phenyl group, a methyl group, a methoxy group and a chlorine atom. No phenyl group having 1 to 3 is taken. ) Represents a group represented by. Further, the sulfonic acid group and / or the carboxylic acid group may be in the form of an alkaline earth metal salt or an aluminum salt, respectively.